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At least 361 records · Page 20

Mars Surveyor Program '01 Mars Environmental Compatibility Assessment wet chemistry lab: a sensor array for chemical analysis of the Martian soil

The Mars Environmental Compatibility Assessment (MECA) instrument was designed, built, and flight qualified for the now canceled MSP (Mars Surveyor Program) '01 Lander. The MECA package consisted of a microscope, electrometer, material patch plates, and a wet chemistry laboratory (WCL). The primary goal of MECA was to analyze the Martian soil (regolith) for possible hazards to future astronauts and to provide a better understanding of Martian regolith geochemistry. The purpose of the WCL was to analyze for a range of soluble ionic chemical species and electrochemical parameters. The heart of the WCL was a sensor array of electrochemically based ion-selective electrodes (ISE). After 20 months storage at -23 degrees C and subsequent extended freeze/thawing cycles, WCL sensors were evaluated to determine both their physical durability and analytical responses. A fractional factorial calibration of the sensors was used to obtain slope, intercept, and all necessary selectivity coefficients simultaneously for selected ISEs. This calibration was used to model five cation and three anion sensors. These data were subsequently used to determine concentrations of several ions in two soil leachate simulants (based on terrestrial seawater and hypothesized Mars brine) and four actual soil samples. The WCL results were compared to simulant and soil samples using ion chromatography and inductively coupled plasma optical emission spectroscopy. The results showed that flight qualification and prolonged low-temperature storage conditions had minimal effects on the sensors. In addition, the analytical optimization method provided quantitative and qualitative data that could be used to accurately identify the chemical composition of the simulants and soils. The WCL has the ability to provide data that can be used to "read" the chemical, geological, and climatic history of Mars, as well as the potential habitability of its regolith.

Non-NASA Center↗

Experimental Effervescence and Freezing Point Depression Measurements of Nitrogen in Liquid Methane-Ethane Mixtures

NASA is designing an unmanned submarine to explore the depths of the hydrocarbon-rich seas on Saturn's moon Titan. Data from Cassini indicates that the Titan north polar environment sustains stable seas of variable concentrations of ethane, methane, and nitrogen, with a surface temperature near 93 K. The submarine must operate autonomously, study atmosphere/sea exchange, interact with the seabed, hover at the surface or any depth within the sea, and be capable of tolerating variable hydrocarbon compositions. Currently, the main thermal design concern is the effect of effervescence on submarine operation, which affects the ballast system, science instruments, and propellers. Twelve effervescence measurements on various liquid methane-ethane compositions with dissolved gaseous nitrogen are thus presented from 1.5 bar to 4.5 bar at temperatures from 92 K to 96 K to simulate the conditions of the seas. After conducting effervescence measurements, two freezing point depression measurements were conducted. The freezing liquid line was depressed more than 15 K below the triple point temperatures of pure ethane (90.4 K) and pure methane (90.7 K). Experimental effervescence measurements will be used to compare directly with effervescence modeling to determine if changes are required in the design of the thermal management system as well as the propellers.

Submarine↗

Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

Righter, K.↗

Using high pressure solutions of polyfluoroacrylate and CO 2 to Seal cement cracks for improved wellbore integrity

Polyfluoroacrylate (PFA) is a hydrophobic and oleophobic polymer that is soluble in high pressure carbon dioxide (CO 2 ). In this study, the ability of PFA-CO 2 solutions to greatly reduce the apparent permeability of split or cracked Portland cement cylindrical samples is assessed. The apparent permeability values of confined samples were determined before and after treatment with PFA-CO 2 solutions. In four tests, PFA-CO 2 solutions were continuously displacing pure CO 2 from the cracked cement and the decrease in apparent permeability due to PFA adsorption and wettability alteration was monitored. The lowest apparent permeability cracked cement sample (81 nD) was completely sealed with a very small amount of solution. Samples with initial apparent permeabilities of 89 μD and 29.4 mD exhibited 92% and 99% reductions in permeability, respectively, before the experiments had to be stopped because of the excessively large increase in pressure drop. A 50% reduction in apparent permeability was observed with a 3.80 mD sample. Four other split cement samples (bound together with tape) with an initial apparent permeability in the 9.0–70 mD range were removed from the core holder and immersed in a PFA-CO 2 solution for 24 h to allow for PFA adsorption. Then the PFA-CO 2 solution was depressurized, allowing for the deposition of additional PFA from the solution within the crack as the pressure fell below the cloud point pressure of the PFA-CO 2 solution. These four samples were then confined again in a core holder and apparent permeability reductions of 29–93% were observed. Finally, results from these eight experiments indicates that the more substantial reductions in the nD – mD apparent permeability of the cracked cement correlated to lower initial crack permeability, higher PFA concentration, and slower injection rate of the PFA-CO 2 solution into the crack.

58 GEOSCIENCES↗

Diffusive Gas Loss from Silica Glass Ampoules at Elevated Temperatures

Changes in the pressure of hydrogen, helium and neon due to diffusion through the wall of silica crystal growth ampoules at elevated temperatures were determined experimentally. We show that, while both He- and Ne-losses closely follow conventional model of diffusive gas permeation through the wall, hydrogen losses, in particular at low fill pressures, can be much larger. This is interpreted in terms of the high solubility of hydrogen in silica glasses.

Palosz, W.↗

Redox Variations in Early Solar System Materials and Implications for Late Stage Planetary Accretion and Planet Formation

Oxygen fugacity plays an important role in determining the detailed physical and chemical aspects of planets and their building blocks. Basic chemical properties such as the amount of oxidized Fe in a mantle (as FeO), the nature of alloying elements in the core (S, C, H, O, Si), and the solubility of various volatile elements in the silicate and metallic portions of embryos and planets can influence physical properties such as the size of the core, the liquidus and solidus of the mantle and core, and the speciation of volatile compounds contributing to atmospheres. This paper will provide an overview of the range of fO2 variation observed in primitive and differentiated materials that may have participated in accretion (cosmic dust, Star-dust and meteorites), a comparison to observations of planetary fO2 (Mercury, Mars and Earth), and a discus-sion of timing of variation of fO2 within both early and later accreted materials. This overview is meant to promote discussion and interaction between students of these two stages of planet formation to identify areas where more work is needed.

Righter, K.↗

Chemical Weathering Records of Martian Soils Preserved in the Martian Meteorite EET79001

Impact-melt glasses, rich in Martian atmospheric gases, contain Martian soil fines (MSF) mixed with other coarse-grained regolith fractions which are produced during impact bombardment on Mars surface. An important characteristic of the MSF fraction is the simultaneous enrichment of felsic component accompanied by the depletion of mafic component relative to the host phase in these glasses. In addition, these glasses yield large sulfur abundances due to the occurrence of secondary mineral phases such as sulfates produced during acid-sulfate weathering of the regolith material near the Martian surface. Sulfurous gases released into atmosphere by volcanoes on Mars are oxidized to H2SO4 which deposit back on the surface of Mars as aerosol particles. Depending on the water availability, sulfuric acids dissolve into solutions which aggressively decompose the Fe-Mg silicates in the Martian regolith. During chemical weathering, structural elements such as Fe, Mg and Ca (among others) are released into the transgressing solutions. These solutions leach away the soluble components of Mg, Ca and Na, leaving behind insoluble iron as Fe3(+) hydroxysulfate mixed with poorly crystalline hydroxide- precipitates under oxidizing conditions. In this study, we focus on the elemental distribution of FeO and SO3 in the glass veins of EET79001, 507 sample, determined by Electron Microprobe and FE SEM measurements at JSC. This glass sample is an aliquot of a bigger glass inclusion ,104 analysed by where large concentrations of Martian atmospheric noble gases are found.

Rao, M. N.↗

The MECA Payload as a Dust Analysis Laboratory on the MSP 2001 Lander

In a companion abstract, the "Mars Environmental Compatibility Assessment" (MECA) payload for Mars Surveyor Program 2001 (MSP 2001) is described in terms of its capabilities for addressing exobiology on Mars. Here we describe how the same payload elements perform in terms of gathering data about surface dust on the planet. An understanding of the origin and properties of dust is important to both human exploration and planetary geology. The MECA instrument is specifically designed for soil/dust investigations: it is a multifunctional laboratory equipped to assess particulate properties with wet chemistry, camera imagery, optical microscopy (potentially with LTV fluorescence capability), atomic force microscopy (AFM; potentially with mineral-discrimination capabilities), electrometry, active & passive external materials-test panels, mineral hardness testing, and electrostatic & magnetic materials testing. Additionally, evaluation of soil chemical and physical properties as a function of depth down to about 50 cm will be facilitated by the Lander/MECA robot arm on which the camera (RAC) and electrometer are mounted. Types of data being sought for the dust include: (1) general textural and grain-size characterization of the soil as a whole --for example, is the soil essentially dust with other components or is it a clast-supported material in which dust resides only in the clast interstices, (2) size frequency distribution for dust particles in the range 0.01 to 10.00 microns, (3) particle-shape distribution of the soil components and of the fine dust fraction in particular, (4) soil fabric such as grain clustering into clods, aggregates, and cemented/indurated grain amalgamations, as well as related porosity, cohesiveness, and other mechanical soil properties, (5) cohesive relationship that dust has to certain types of rocks and minerals as a clue to which soil materials may be prime hosts for dust "piggybacking", (6) particle, aggregate, and bulk soil electrostatic properties, (7) particle hardness, (8) particle magnetic properties, (9) bulk dust geochemistry (solubility, reactivity, ionic and mineral species). All of these quantities are needed in order for the human exploration program to make assessments of hazards on Mars, and to better enable the production on earth, of soil/dust simulants that can act as realistic test materials in terms of those properties that render dust a contaminant.Such properties include the small grain size that enables penetration of space-suit joints, mechanical interfaces and bearings, seals, etc., and presents difficulty for filtration systems. Size also plays a critical role in the potential for lung disease in long-term habitats. The properties of grain shape and hardness are important parameters in determining the abrasiveness of dust as it enters mechanical systems, or bombards helmet visors and habitat windows in dust-laden winds. Adhesive electrostatic and magnetic properties of dust will be prime causes of contamination of space suits and equipment. Contamination causes mechanical malfunction, tracking of dirt into habitats, "piggybacking" of toxins on dust into habitats, changes in albedo and efficiency of solar arrays and heat exchangers, and changes in electrical conductivity of suit surfaces and other materials that may have specific safety requirements regarding electrical conductivity. Other potentially hazardous properties of dust include the possibility of high solubility of some component grains (rendering them reactive), and toxicity of some materials --grains of superoxidants and heavy metals (there is always the slim, but not inconceivable possibility of biogenic components such as spores). Because Mars has no active surface aqueous regime, volcanic emissions, meteoritic debris, weathering products, and photochemical products of Mars have nowhere to go except reside in the surface; there are few mechanical or chemical (buffering) processes to remove the accumulation of eons. From a planetology perspective, there are many enigmatic issues relating to dust and the aeolian regime in general. MECA will be able to address many questions in this area. For example, if MECA determines a particular particle size distribution (size and sorting values), it will be possible to make inferences about the origin of the dust - - is it all aeolian, or a more primitive residue of weathering, volcanic emissions, and meteoritic gardening? Trenching with the Lander/MECA robot arm will enable local stratigraphy to be determined in terms of depositional rates, amounts and cyclicity in dust storms and/or local aeolian transport. Grain shape will betray the origin of the dust fragments as being the product of recent or ancient weathering, or the comminution products of aeolian transport --the dust-silt ratio might be a measure of aeolian comminution energy. Additional information is contained in the original.

Marshall, J.↗

A Maize GT14 Family Glycosyltransferase Affects Cell Wall Composition and Carbohydrate Export from Source Leaves

Sucrose translocation from photosynthetic leaves to distant parts of a plant, such as seeds and roots, is a critical aspect of plant growth and development and a major determinant of crop yield. To identify genes contributing to this process in maize (Zea mays), we isolated four allelic mutants, carbohydrate partitioning defective7, 48, 49 (cpd7, cpd48, cpd49) and a UniformMu insertion (mu1049954), all of which exhibited reduced growth and fertility and hyperaccumulation of starch and soluble sugars in mature leaves. Consistent with carbohydrate accumulation, cpd7 mutants exhibited reduced sucrose export from mature leaves. Cpd7 encodes a Golgi-resident glucuronosyltransferase belonging to the Glycosyltransferase14 (GT14) family, which is involved in decoration of type II arabinogalactan proteins. No previously described GT14 mutants exhibit reduced sucrose transport or carbohydrate partitioning defects. Additionally, we show that mature leaves of cpd7 mutants have reduced cellulose content and an altered cell wall composition. Further, cpd7 mutants exhibit ectopic phloem lignification likely as a compensatory mechanism for reduced cell wall integrity. Collectively, our data suggest that Cpd7 functions to facilitate cell wall development in the phloem, which is required for efficient sucrose export from mature maize leaves.

59 BASIC BIOLOGICAL SCIENCES↗

Screening of Potential Biomass-Derived Streams as Fuel Blendstocks for Mixing Controlled Compression Ignition Combustion

Mixing controlled compression ignition or diesel engines are highly efficient and are likely to continue to be the primary means for movement of goods for many years to come. Low-carbon biofuels have the potential to significantly reduce the carbon footprint of diesel combustion and could potentially have advantageous properties for combustion such as high cetane number and reduced engine out particle emissions. In this study, we developed a list of potential biomass-derived diesel blendstocks. An online database of properties and characteristics of these bioblendstocks was populated with data. Fuel properties were determined by measurement, model prediction, or literature review. Screening criteria were developed to determine if a bioblendstock met the basic requirements for handling in the diesel distribution system and use as a blend with conventional diesel. Criteria included cetane number =40, flashpoint =52 degrees C, and boiling point or final boiling point <338 degrees C. Blendstocks needed to be soluble in diesel fuel, have a toxicity no worse than conventional diesel, and not be corrosive. Additionally, cloud point or freezing point below 0 degrees C was required. This screening produced a list of 27 potential bioblendstocks. Of these candidates, 13 were available commercially or could be synthesized by biofuels production researchers and included 11 nominally pure components and two mixtures. These 13 candidates were then subjected to further study based on how they impact fuel properties upon blending. Blend properties included cetane number, lubricity, conductivity, oxidation stability and viscosity. Results indicate that all thirteen candidates can meet the basic requirements for diesel fuel blending and are likely to reduce particle emissions from diesel combustion.

09 BIOMASS FUELS↗

Effect of Atmospheric Organics on Bioavailable Fe Lifetime in the Oceans

The deposition of atmospheric aerosols is an important supply pathway of soluble iron (sol-Fe) to the global oceans influencing marine ecosystem processes and climate. Previous studies have shown that natural and anthropogenic acidic trace gases, when mixed with mineral dust, can lead to production of sol-Fe, leading to considerable increase in dust-Fe solubility. Recent studies have further highlighted the importance of atmospheric organic compounds/ligands in the production of sol-Fe during atmospheric transport and transformation of mineral aerosols. However, the actual scope of this aerosol sol-Fe for stimulating the primary productivity in the oceans is determined by both: the total atmospheric fluxes of sol-Fe and the lifetime of sol-Fe after its deposition to the ocean. In this study several atmospheric organic ligands were investigated for their effect on the lifetime of sol-Fe after mixing with seawater. Organic ligands were selected based on their abundance in the marine boundary layer and rainwater and their ability to form bidentate complexes with Fe. The results reveal that the tested organics had minor influence on Fe(II) lifetime in seawater. However, results also show that some organic acid considerably extended the lifetime of colloidal and aqueous Fe(III). Using these results we simulate aerosol sol-Fe lifetime in the ocean for different mineral dust deposition events in the presence and the absence of atmospheric organic ligands. The calculations suggest that when a large dust plume is assumed to contain Fe(II) alone, less than 15% of aerosol sol-Fe gets complexed with marine organic ligands. However, this fraction increases to over 90% when atmospheric Fe is allowed to bond with atmospheric organic acids prior to deposition to the oceans. Calculations also show that for the conditions when seawater organic ligands get titrated by Fe released from dust aerosol particles, retention of sol-Fe in the ocean depends on surface ocean mixing, i.e., replenishing rates for Fe-bonding ligands from below. This study suggests that in future ocean biogeochemistry models more attention should be devoted to better quantification of the role of atmospheric organic acids in the lifetime of aerosol sol-Fe after its deposition to the ocean and the improvements of upper ocean turbulence parameterizations.

Oceans↗

Combined Experimental and Computational Efforts to Establish Ion Mobility, Solubility and Stability of Functional Liquids for Electrochemical Energy Storage

This work provides a computation-driven investigation of the stability of organic electrolytes for lithium-air batteries. Electrolyte instability is currently a key challenge that limits practical use of aprotic Li-air batteries, and the chemical processes that cause this instability are often kinetically-driven. Computational screening for kinetic stability involves the determination of reaction barriers for the numerous potential reaction mechanisms, barriers that are challenging to calculate due to the difficulty of locating transition state structures. Here we screen a broad set of substituted electrolytes for susceptibility to nucleophilic attack by superoxide. We find that carbonates are not typically expected to be stable and that sulfones are generally stable, validating literature trends. We study the effects of chemical functionalization with electron-donating and withdrawing groups and their interplay with steric factors, identifying functional groups and other chemical modifications that increase stability in these groups. User-input driven transition state identification is used for these initial calculations, and an automated computational pipeline is subsequently presented and validated as a means to perform further high-throughput searches across mechanisms and chemistries. The pipeline integrates cheminformatics-based reaction encoding, relaxed potential energy scans, and nudged elastic band calculations for an end-to-end approach to barrier calculations. We review this automated search approach and its current limitations, and discuss challenges and further work.

25 ENERGY STORAGE↗

The effect of alloy composition on the mechanism of stress corrosion cracking of titanium alloys in aqueous environments

Emphasis has been placed on determining the interrelations among the composition, phase structure, deformation, and fracture properties of the alpha phase in susceptible alpha-beta alloys. The program is divided into two parts: (1) evaluation of the aqueous stress corrosion susceptibility of a series of alloys that contain various alpha-soluble elements; and (2) investigations of the metallurgical aspects of the mechanism of aqueous stress corrosion cracking.

Williams, D. N.↗

Three distinct cell phenotypes of induced-TNF cytotoxicity and their relationship to apoptosis

We have identified three distinct cell phenotypes with respect to the conditions under which cells became susceptible to TNF-mediated lysis. These conditions include: 1) treatment with the protein synthesis inhibitor, cycloheximide; 2) contact with activated macrophages, and 3) infection with vaccinia virus. Whereas vaccinia virus-infected 3T3 cells became sensitive to soluble TNF, F5b cells required contact with activated macrophages. We showed that the "macrophage-resistant" F5m cells did not become sensitive to TNF or to killing by activated macrophages after infection with vaccinia virus. Therefore, vaccinia infection does not sensitize all cells to TNF. We also determined the pathways of lysis for cells after sensitization. Whereas 3T3, LM929, and F5b cells were killed by the process of necrosis, F5m cells lysis was characterized by the release of low mol wt DNA fragments (apoptosis).

Non-NASA Center↗

Trypsin digestion for determining orientation of ATPase in Halobacterium saccharovorum membrane vesicles

Membranes prepared by low pressure disruption of cells exhibited no ATPase activity in the absence of Triton X-100, although 43% of the total menadione reductase activity was detected. Trypsin digestion reduced menadione reductase activity by 45% whereas ATPase activity was not affected. Disruption of the membrane fraction at higher pressure solubilized about 45% of the ATPase activity. The soluble activity was still enhanced by Triton X-100, suggesting that the detergent, besides disrupting membrane vesicles, also activated the ATPase. The discrepancy in localization of menadione reductase and ATPase activities raised questions regarding the reliability of using a single marker enzyme as an indicator of vesicle orientation.

NASA Center ARC↗

DISSOLUTION OF SURROGATE U-Zr FUEL USING ALNIFLEX CONDITIONS

Non-aluminum clad spent nuclear fuel (NASNF) stored in L Basin at the Savannah River Site (SRS) is widely varied in fuel composition, design, packaging, and physical condition. The complexity of the NASNF inventory presents significant challenges, and technology development is necessary for successful disposition. One such fuel in the inventory is metallic uranium-zirconium (U-Zr) alloy fuel, the focus of this study. Electrolytic or nitric acid only dissolution of metallic U-Zr alloy can form insoluble zirconium oxide, which results in up to 52% loss of U to insoluble solids, and can be subject to potentially uncontrolled oxidation reactions [1, 2]. The AlNiflex process was determined to be a viable dissolution flowsheet for the U-Zr alloy fuel. Under a narrow set of solution concentrations, a combination of hydrofluoric acid (HF), nitric acid (HNO3), aluminum nitrate (Al(NO3)3), and hexavalent chromium can safely dissolve U-Zr intermetallic alloys, keep Zr soluble, and not significantly corrode stainless steel (SS) vessels [3, 4.

Gogolski, Jarrod M. [Savannah River National Labor↗

Biofilm Study Under Simulated Microgravity

The goal of this study was to understand biofilm formation under microgravity (µg), in support of biofilm mitigation efforts in exploration water recovery systems. The technical approach was to conduct a mass transfer and bacterial culture study under both simulated µg and ambient gravity. The aim was to correlate nutrient consumption to gene expression to better understand biofilm formation. A representative species of bacteria that is commonly cultured from the International Space Station (ISS) Water Processor Assembly (WPA) was cultured in a WPA influent water ersatz formulation that is tailored for microbiology studies. A mass transfer rate study was carried out using the ersatz WPA influent water by introducing a water-soluble dye to represent dissolved nutrients and nutrient particles. Imaging of dye diffusion over time allowed for the comparison of mass transport rates under a series of rotation per minute (RPM) speeds for the High Aspect Ratio Vessels (HARVs) on a Rotating Wall Vessel (RWV). This was done to determine the speed that will most accurately simulate the low convective rates experienced under actual µg conditions. Three biological replicates of the Burkholderia contaminans (B. contaminans) microbe were cultured under simulated µg with a rotating (R) control in the horizontal plane at the determined optimal RPM of 15, along with a stationary (S) reference culture. At T=0, and then at T=1,2,3 (in exponential phase) and T=4 (in S phase), the bacterial culture and ersatz were harvested for transcriptomic and nutrient content analysis, respectively. The experimental results illustrated that phosphate is a limiting nutrient in the WPA ersatz formula. Nutrient analysis illustrated that the µg treatment culture took up essential nutrients more rapidly than the R and S control cultures, yet non-essential nutrients remained higher in the µg treatment than in the controls at later timepoints. The rapid uptake and subsequent starvation of phosphate in the culture under µg conditions is further illustrated in the transcriptomic response when compared to that of the R control condition. The subsequent starvation response may serve as one element to explain a moderate enhancement of biofilm formation in the µg treatment. One implication of this work is that biofilm mitigation in the ISS environment could be supported by ensuring a steady flow of water as a vehicle for phosphate within the WPA to avoid complete phosphate consumption, which occurs in times of no flow and leads to undesired biofilm formation.

Aubrie O’Rourke↗