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Nanophase Carbonates on Mars: Does Evolved Gas Analysis of Nanophase Carbonates Reveal a Large Organic Carbon Budget in Near-Surface Martian Materials?

Evolved Gas Analysis (EGA), which involves heating a sample and monitoring the gases released, has been performed on Mars by the Viking gas chromatography/mass spectrometry instruments, the Thermal and Evolved Gas Analyzer (TEGA) on the Phoenix lander, and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory. All of these instruments detected CO2 released during sample analysis at abundances of approx. 0.1 to 5 wt% assuming a carbonate source. The source of the CO2 can be constrained by evaluating the temperature of the gas release, a capability of both the TEGA and SAM instruments. The samples analyzed by SAM show that the majority of the CO2 is released below 400C, much lower than traditional carbonate decomposition temperatures which can be as low as 400C for some siderites, with magnesites and calcites decomposing at even higher temperatures. In addition to mineralogy, decomposition temperature can depend on particle size (among other factors). If carbonates formed on Mars under low temperature and relative humidity conditions, the resulting small particle size (nanophase) carbonates could have low decomposition temperatures. We have found that calcite can be synthesized by exposing CaO to water vapor and CO2 and that the resulting mineral has an EGA peak of approx. 550C for CO2, which is about 200C lower than for other calcites. Work is ongoing to produce Fe and Mg-bearing carbonates using the same process. Current results suggest that nanophase calcium carbonates cannot explain the CO2 released from martian samples. If the decomposition temperatures of Mg and Fe-bearing nanophase carbonates are not significantly lower than 400C, other candidate sources include oxalates and carboxylated organic molecules. If present, the abundance of organic carbon in these samples could be greater than 0.1 wt % (1000s of ppm), a signficant departure from the paradigm of the organic-poor Mars based on Viking results.

Archer, P. Douglas, Jr.↗

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.↗

Synthesis, Structure, Characterization, and Decomposition of Nickel Dithiocarbamates: Effect of Precursor Structure and Processing Conditions on Solid-State Products

Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.

microscopy↗

Techniques for Measurement of Nitrate Movement in Soils

Contamination of surface and ground waters with nitrate usually involves leaching through soil of nitrate produced by mineralization of soil organic matter, decomposition of animal wastes or plant residues, or derived from fertilizers. Nitrate concentrations in the soil solution may be measured by several chemical procedures or by the nitrate electrode. since nitrate is produced throughout the soil mass it is difficult to identify a source of nitrate contamination by conventional means. This problem can be solved by use of N-15-enriched or N-15-depleted materials as tracers. The latter is particularly attractive because of the negligible possibility of the tracer hazardous to health.

Broadbent, F. E.↗

Lubricous Deposit Formed In Situ Between Wearing Surfaces at High Temperatures

Many components of future aircraft will be constructed from novel high-temperature materials, such as superalloys and ceramic composites, to meet expected operating temperatures in excess of 300 C. There are no known liquid lubricants that can lubricate above 300 C without significant decomposition. Solid lubricants could be considered, but problems caused by the higher friction coefficients and wear rates of the solid lubricant film make this an undesirable approach. An alternative method of lubrication is currently being investigated: vapor phase lubrication. In vapor phase lubrication, an organic liquid (in our studies a thioether was used) is vaporized into a flowing air stream that is directed to sliding surfaces where lubrication is needed. The organic vapor reacts at the concentrated contact sliding area generating a lubricous deposit. This deposit has been characterized as a thin polymeric film that can provide effective lubrication at temperatures greater than 400 C. Initial tribological studies were conducted at the NASA Lewis Research Center and Cleveland State University with a high-temperature friction and wear tribometer. A cast iron rod was loaded (a 4-kg mass was used to generate a contact pressure of 1.2 MPa) against a reciprocating, cast iron plate at 500 C. This system was then lubricated with the vapor phase of thioether.

Source record↗

Investigating Commercial Off-The-Shelf (COTS) Glovebox and Support Components Compared to Custom Curatorial Laboratories

There is a need envisioned to investigate the application of commercial off-the-shelf (COTS) systems as tools that could be used within commercial preliminary curation as the expected space economy is supported and begins to take flight. NASA is involved with supporting and developing the space economy [1] and therefore it’s feasible that at some point, a commercial space company would bring back materials and either store initially, or permanently, within COTS equipment as a stand-in for custom curation laboratories. While utilizing opportunities to explore this capability at NASA-Johnson Space Center (JSC) during the establishment of other laboratories [2] it was realized that cleanliness and/or other properties could be evaluated for these COTS systems during their installation in advanced research facilities that are not ISO-class rated clean rooms. Several aspects of a COTS-Curation system were explored including various gloves for curation manipulation within a negative pressure glovebox (Fig.1), Balazs organic and inorganic contaminant levels testing prior to glovebox ever being used, mode swapping comparison of recirculation vs. single pass, constant monitoring of oxygen (O2) and moisture (H2O) levels in various conditions, etc. To acquire inorganic and organic compound loads inside the glovebox, Balazs wafer testing and gas sampling were implemented. These are standardized analytical tests provided by Balazs™ NanoAnalysis, a division of Air Liquide USA. Deployment of 8-inch silicon wafer witness plates for 24-hours in an undisturbed environment capture the organic compound load and inorganic trace metal contents which can be obtained by Vapor Phase Decomposition Inductively Coupled Plasma Mass Spectrometry (VPD ICP-MS). Balazs gas sample analysis was also performed for better measurements of volatile organic compounds (VOC) in glovebox air analyzed by Thermal Desorption Gas Chromatography Mass Spectrometry (TD GC-MS). These analytical testings were carried out in a controlled ultra high pure (UHP) gaseous nitrogen (N2)-purged environment where oxygen and moisture contents were continuously monitored at certain temperature and pressure. The preliminary outcomes of these testings are promising. The COTS systems appear to maintain the steady-state controlled environment for days, if not weeks, with uninterrupted gaseous N2-supply which was operated from a standard medium pressure LN2 250L 230L dewar, exchanged as needed. The outgassing load can be maintained by selecting the glove materials that have the least outgassing and particle shedding performances. Further experiments will be considered to validate the preliminary findings. While this project is exploratory, it is not intended as an endorsement by NASA Curation for approved materials or usage for advanced curatorial activities. NASA does not endorse nor promote any one particular product or company. References: [1] McCubbin F. M. et al. (2019) Space Science Reviews 215:A48. [2] Lewis, E.K. et. al (2024) LPSC LV, Abstract #2457.

Curation↗

Development and Testing of a Green-Propellant Micro-Hybrid Thruster with Electrostatic Ignition

As early as 1937 German scientists at Peenemunde experimented with highly unstable fuel blends of nitrous oxide (N2O) and ethanol. These early tests mostly resulted in explosions and destroyed rocket engines. More recently several companies have developed experimental nitrous oxide fuel blends (NOFB) with Isp exceeding 300 sec. Although NOFBx has recently been cleared for tests on the International Space Station, this propellant remains highly experimental and has not been cleared for commercial transport by the US DOT. Recent work by Karabeyoglu et al. has raised concerns about the safety risks of mixing hydrocarbons with N2O. Liquid oxidizer/fuel blends are highly explosive and require extreme care in transport and servicing. By adding small amounts of a liquid organic fuel such as alcohol or a hydrocarbon, the odds of an explosive decomposition event are significantly increased.iv The proposed solution mitigates the explosion hazards of NOFB by separating the oxidizer from the hydrocarbon fuel formed as of a small cylindrical section of ABS thermoplastic. As N2O vapor flows across the grain segment, current enters a 1000 VDC high-tension lead in the ABS fuel grain and produces an inductive spark that vaporizes a small amount of the material. The ablated fuel vapor plus residual energy from the spark seed a localized exothermic N2O dissociation that produces sufficient heat to initiate combustion. The process is also effective when gaseous oxygen is used. A low TRL (2-3) prototype demonstrating the feasibility of controlled hydrocarbon-seeding was recently tested at Utah State University.v The unit features a miniature 2.5 cm ABS fuel grain fabricated using a Stratasys Dimension 3-D printer. The 9-N thruster was pulse-fired up to 27 consecutive times on a single ABS grain segment. Ignition was achieved by as little as 12-15 Joules energy input. This value is contrasted with the typical 30-minute pre-heat requirement for the ECAPS LMP-103S ADN-based monopropellant, requiring an energy input of 14,850 Joules for catalytic dissociation. The hydrocarbon-seeded micro-hybrid was also adapted as a non-pyrotechnic ignitor for a 900 N (200-lbf) thrust hybrid motor. The motor was successfully ignited 4 consecutive times with no hardware swaps or propellant additions. The amount of ABS seed material that can be fit into the injector cap is the only limit to the number of available repeat firings. This series of tests marks the first time a hybrid motor was ever ignited by other than a solid-propellant pyrotechnic charge or bi-propellant flame ignitor. Nitrous oxide hybrid motors are typically difficult to ignite and usually require multiple solid-propellant charges to initiate combustion, so this nonpyrotechnic ignition is a significant accomplishment. The controlled hydrocarbon-seeding approach is fundamentally different from all other green propellant solutions offered by the aerospace industry. Although the proposed system is more correctly a hybrid technology; the system retains all the simple features of a monopropellant design. To date no optimization study has been performed to identify the best grain geometry for electrostatic ignition. Fortunately, because the grain segments are fabricated using rapid-prototyping technology, changing the grain geometry is as simple as modifying the 3-D printer CAD-file. Vacuum Isp exceeding 270 seconds has been demonstrated (Ref v), a value significantly higher than those offered by competing green monopropellant options. The propellants of choice, N2O/GOX and ABS are 100% non-toxic, non-explosive, and environmentally benign. Because the inert oxidizer and fuel components are mixed only within the combustion chamber, the system retains the inherent safety of a hybrid rocket and can be piggy-backed as a secondary payload with no overall mission risk increase to the primary payload, an excellent characteristic for secondary launch systems.

Whitmore, Stephen A.↗

Carbon Storage in Wetlands and Lakes of the Eastern US

Carbon stored underground may participate in a positive feedback with climate warming, as higher temperatures accelerate decomposition reactions and hence CO2 release. Assessing how below-ground carbon storage varies with modern climate and paleoclimate will advance understanding of this feedback in two ways. First, it will estimate the sensitivity of carbon storage to temperature and precipitation changes. Second, it will help quantify the size of carbon stocks available for the feedback, by indicating how current regional climate differences affect carbon storage. Whereas many studies of below-ground carbon storage concentrate on soils, this investigation focuses on the saturated and primarily organic material stored in wetlands and lake sediments. This study surveys research done on organic sediment depth and organic content at 50-100 sites in the eastern U.S., integrating our own research with the work of others. Storage depth is evaluated for sediments from the past 10,000 years, a date reflected in pollen profiles. Organic content is measured chiefly by loss-on-ignition (101). These variables are compared to characteristics of the sites such as latitude, altitude, and vegetation as well as local climate. Preliminary results suggest a strong relationship between latitude and depth of organic material stored over the last 10,000 years, with more accumulation in the northeastern US than the southeastern US. Linking the percent organic matter to actual carbon content is in progress with wetlands from Black Rock Forest and Alpine Swamp.

Renik, Byrdie↗

Carbon Isotopic Composition of CO2, Evolved During Perchlorate-Induced Reactions in Mars Analog Materials: Interpreting SAM/MSL Rocknest Data

The Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL) Rover Curiosity made its first solid sample evolved gas analysis of unconsolidated material at aeolian bedform Rocknest in Gale Crater. The magnitude of O2 evolved in each run as well as the chlorinated hydrocarbons detected by SAM gas chromatograph/ mass spectrometer (GCMS) [1] suggest a chlorinated oxidant such as perchlorate in Rocknest materials [2]. Perchlorate induced combustion of organics present in the sample would contribute to the CO2 volatile inventory, possibly overlapping with CO2 from inorganic sources. The resulting carbon and oxygen isotopic composition of CO2 sent to the Tunable Laser Spectrometer (TLS) for analysis would represent mixed sources. This work was undertaken to better understand a) how well the carbon isotopic composition ( 13C) of CO2 from partially combusted products represents their source and b) how the 13C of combusted products can be deconvolved from other carbon sources such as thermal decomposition of carbonate.

Stern, J. C.↗

Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

Francois, P.↗

Solutions Network Formulation Report. NASA's Potential Contributions for Using Solar Ultraviolet Radiation in Conjunction with Photocatalysis for Urban Air Pollution Mitigation and Increasing Air Quality

This Candidate Solution is based on using NASA Earth science research on atmospheric ozone and aerosols data as a means to predict and evaluate the effectiveness of photocatalytically created surfaces (building materials like glass, tile and cement) for air pollution mitigation purposes. When these surfaces are exposed to near UV light, organic molecules, like air pollutants and smog precursors, will degrade into environmentally friendly compounds. U.S. EPA (Environmental Protection Agency) is responsible for forecasting daily air quality by using the Air Quality Index (AQI) that is provided by AIRNow. EPA is partnered with AIRNow and is responsible for calculating the AQI for five major air pollutants that are regulated by the Clean Air Act. In this Solution, UV irradiance data acquired from the satellite mission Aura and the OMI Surface UV algorithm will be used to help understand both the efficacy and efficiency of the photocatalytic decomposition process these surfaces facilitate, and their ability to reduce air pollutants. Prediction models that estimate photocatalytic function do not exist. NASA UV irradiance data will enable this capability, so that air quality agencies that are run by state and local officials can develop and implement programs that utilize photocatalysis for urban air pollution control and, enable them to make effective decisions about air pollution protection programs.

Underwood, Lauren↗

Formation and Survival of Amino Acids in Space

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in piimitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these inteiesting compounds, and on astrophysically relevant kinetic studies UV photo-decomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Bernstein, M. P.↗

Ionic Liquids to Replace Hydrazine

A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

Koelfgen, Syri↗

Halogen-Containing Gases as Boundary Lubricants for Corrosion-Resistant Alloys at 1200 F

The extreme temperatures anticipated for lubricated parts in advanced flight powerplants dictate the consideration of unconventional methods of lubrication such as solid lubricants and the reactive gases described in the present research. These halogen-containing "reactive" gases such as dichlorodifluoromethane, CF2Cl2, are among the most stable of organic molecules. The high "flash" temperatures generated at the contacting asperities as a result of frictional heat are sufficient to cause local decomposition of the halogen-containing gases. The active atoms thus released (e.g., chlorine) then react with the metal to be lubricated to form halides capable of effective lubrication. The presence of small amounts of a sulfur-containing gas (e.g., 1 percent sulfur hexafluoride, SF6) was found to catalyze the formation of metal halides. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (2 1/2-in. diam.). The specimens of corrosion-resistant 2 alloys were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 120 feet per minute, and temperature from 75 to 1200 F. An effective lubricant for ferritic materials (M-1 tool steel) was CF2Cl2, but significant corrosion occurred above 600 F. Corrosion evaluation in CF2Cl2 suggested a number of nickel- and cobalt-base alloys for additional lubrication study. Several combinations of gases and these metals were found to lubricate to 1200 F without excessive corrosion. The gases were CF2Cl2 Plus 1 percent SF6, monobromotrifluoromethane CF3Br plus 1 percent SF6, dibromodifluoromethane CF2Br2, iodotrifluoromethane, CF3I, and I2. Careful selection of metals and gas are necessary for successful lubrication over specific temperature ranges. Optimum combinations give friction coefficients as low as 0.05 without

Buckley, Donald H.↗

The chemical reactivity of the Martian soil and implications for future missions

Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

Zent, Aaron P.↗

Lessons Learned from Medical System Foundation Development for Long-Duration Lunar Orbit and Lunar Surface Missions

The Human Research Program (HRP) Exploration Medical Capability (ExMC) Element has been tasked with the development of Medical System Foundations for Level of Care IV for both short-duration lunar orbital missions and, subsequently, long-duration lunar orbital and surface operations missions. These Medical System Foundations serve as a framework to aid in early medical system design and mission planning. The content of both Foundation models is similar, consisting of a concept of operations, functional decomposition, clinical content (medical conditions, capabilities, and resources), technical requirements (interface, non-functional, and functional), and traces between these components and to the NASA standards documents and parent-level (Program- and Vehicle habitat system-level) requirements. Additionally, the development of both Foundations employed systems engineering principles and a model-based systems engineering (MBSE) approach. Throughout the development of these Foundations, ExMC has strived to improve the efficiency and robustness of its processes and to be more responsive to change (i.e., in design reference mission parameters and assumptions) and to stakeholders’ feedback. The most significant improvements made between the short- and long-duration Foundation models during this transformation process are the following: • Replacement of the traditional document-based ConOps with a model-based ConOps according to MBSE principles, which facilitated more efficient understanding of the material and the consolidation of all relevant information into a centralized location. • Utilization of an agile approach with tasks organized into sprints. This approach enabled solicitation of more frequent usability feedback from stakeholders, incorporation of more human factors reviews into the sprints, and more efficient tasking of team members. This presentation will discuss the journey of developing both Foundation models, as well as the lessons learned and resulting improvements made between the Short- and Long-Duration models.

M Kaetzer↗

Chemical Evolution of Interstellar Dust into Planetary Materials

Comets are believed to retain some interstellar materials, stored in fairly pristine conditions since-their formation. The composition and properties of cometary dust grains should reflect those of grains in the outer part of the protosolar nebula which, at least in part, were inherited from the presolar molecular cloud. However, infrared emission features in comets differ from their interstellar counterparts. These differences imply processing of interstellar material on its way to incorporation in comets, but C and N appear to be retained. Overall dust evolution from the interstellar medium (ISM) to planetary materials is accompanied by an increase in proportion of complex organics and a decrease in pure carbon phases. The composition of cometary dust grains was measured in situ during fly-by missions to comet Halley in 1986. The mass spectra of about 5000 cometary dust grains with masses of 5 x 10(exp -17) - 5 x 10(exp -12) g provide data about the presence and relative abundances of the major elements H, C, N, O,Na, Mg, Al, Si, S, Cl, K, Ca, Ti, Cr, Fe, Ni. The bulk abundances of major rock-forming elements integrated over all spectra were found to be solar within a factor of 2, while the volatile elements H, C, N, O in dust are depleted in respect to their total cosmic abundances. The abundances of C and N in comet dust are much closer to interstellar than to meteoritic and are higher than those of dust in the diffuse ISM. In dense molecular clouds dust grains are covered by icy mantles, the average composition of which is estimated to be H:C:N:O = 96:14:1:34. Up to 40% of elemental C and O may be sequestered in mantles. If we use this upper limit to add H, C, N and O as icy mantle material to the abundances residing in dust in the diffuse ISM, then the resulting values for H. C, and N match cometary abundances. Thus, ice mantles undergoing chemical evolution on grains in the dense ISM appear to have been transformed into less volatile and more complex organic residues wherein the H, C and N are largely retained and ultimately accreted in cometary dust. The abundance of O is about the same for cometary dust, meteorites and interstellar dust. In all these samples, most of O in a solid phase is bonded to silicates. In dense molecular clouds, the abundance of O in dust+mantles is significantly higher then in cometary dust. This difference may reflect the greater lability of oxygenated species toward astrophysical processing. Laboratory studies show that O-bearing functional groups in organic compounds tend to be relatively easily removed by heating and/or UV and particle irradiation . In Halley's coma, O-containing organic grains, being unstable, were located closest to the nucleus. The decomposition of the organic grain component in the coma provided a significant extended source contribution to O-containing gaseous species such as CO and H2CO.

Fomenkova, M. N.↗

Ultra-Lightweight Hybrid Thin-Film Solar Cells: A Survey of Enabling Technologies for Space Power Applications

The development of hybrid inorganic/organic thin-film solar cells on flexible, lightweight, space-qualified, durable substrates provides an attractive solution for fabricating solar arrays with high mass specific power (W/kg). Next generation thin-film technologies may well involve a revolutionary change in materials to organic-based devices. The high-volume, low-cost fabrication potential of organic cells will allow for square miles of solar cell production at one-tenth the cost of conventional inorganic materials. Plastic solar cells take a minimum of storage space and can be inflated or unrolled for deployment. We will explore a cross-section of in-house and sponsored research efforts that aim to provide new hybrid technologies that include both inorganic and polymer materials as active and substrate materials. Research at University of Texas at Arlington focuses on the fabrication and use of poly(isothianaphthene-3,6-diyl) in solar cells. We describe efforts at Norfolk State University to design, synthesize and characterize block copolymers. A collaborative team between EIC Laboratories, Inc. and the University of Florida is investigating multijunction polymer solar cells to more effectively utilize solar radiation. The National Aeronautics and Space Administration (NASA)/Ohio Aerospace Institute (OAI) group has undertaken a thermal analysis of potential metallized substrates as well as production of nanoparticles of CuInS2 and CuInSe2 in good yield at moderate temperatures via decomposition of single-source precursors. Finally, preliminary work at the Rochester Institute of Technology (R.I.T.) to assess the impact on performance of solar cells of temperature and carbon nanotubes is reported. Technologies that must be developed to enable ultra-lightweight solar arrays include: monolithic interconnects, lightweight array structures, and new ultra-light support and deployment mechanisms. For NASA applications, any solar cell or array technology must not only meet weight and AMO efficiency goals, but also must be durable enough to survive launch conditions and space environments.

Hepp, Aloysius F.↗