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NASA NTRS2012

Changes in Liver Metabolic Gene Expression from Radiation Exposure

Increased exposure to radiation is one physiological stressor associated with spaceflight. While known to alter normal physiological function, how radiation affects metabolism of administered medications is unclear. Crew health could be affected if the actions of medications used in spaceflight deviated from expectations formed during terrestrial medication use. Three different doses of gamma radiation (50 mGy - 6.05 Gy) and a sham were administered to groups of 6 mice each, and after various intervals of recovery time, liver gene expression was measured with RT-qPCR arrays for drug metabolism and DNA repair enzymes. Results indicated approx.65 genes of the 190 tested were significantly affected by at least one of the radiation doses. Many of the affected genes are involved in the metabolism of drugs with hydrophobic or steroid-like structures, maintenance of redox homeostasis and repair of DNA damage. Most affected genes returned to near control expression levels by 7 days post-treatment. With 6 Gy exposure, metallothionein expression was 132-fold more than control at the 4 hr time point, and fell at each later time point (11-fold at 24 hrs, and 8-fold at 7 days). In contrast, Cyp17a1 showed a 4-fold elevation at 4 hrs after exposure and remained constant for 7 days.

Peters, C. P.↗

NASA NTRSDate not supplied

Constraining the Hydration of X-Ray Amorphous and Clay Mineral Phases in Gale Crater, Mars

Clay minerals and salts in the Gale crater stratigraphy investigated by the Mars Science Laboratory (MSL) Curiosity rover preserve information about sediment sources, depositional environment, and post-depositional alteration history. The compositions of amorphous components in samples have bearing on the redox potential, pH, and chemistry of alteration fluids, and on the heterogeneity of these conditions. Interlayer clay hydration in present-day Gale crater could be an indication of high water/rock ratios of late-stage fluid alteration events, which increases the potential habitability of these post-depositional environments. The MSL Dynamic Albedo of Neutrons instrument (DAN) measures bulk hydration and here we attempt to determine the hydration states of both clay minerals and amorphous components throughout the Curiosity traverse to constrain the abundance of individual amorphous phases and determine if clay interlayer water is present today. These implications are also more broadly applicable to similar sedimentary successions outside Gale crater. In this study, we compare hydration results from DAN to mineralogical results from the MSL Chemistry and Mineralogy instrument (CheMin) for 16 different fluvio-lacustrine sample locations. These samples typically contain one or more hydrated crystalline phases, a hydrated X-ray amorphous fraction composed of multiple amorphous phases, and one or more clay mineral phases which CheMin has consistently measured as collapsed (i.e., no interlayer water). However, Gale samples are known to dehydrate during sample acquisition and handling, and because DAN measures hydration to a depth of tens of cm, we can test for the presence of clay interlayer water in situ by comparing DAN bulk hydration to CheMin mineralogy. We can also constrain the hydration of the samples’ amorphous fractions, and with geochemical data from the ChemCam and APXS instruments, this will allow us to better define the phases which compose this fraction.

S Czarnecki↗

NASA NTRS1980

Energy status and oxidation reduction status in rat liver at high altitude /3.8 km/

Adult male rats were exposed to 3.8-km altitude for intervals ranging from 1 h-60 d. Liver samples were taken under light ether anesthesia and were examined by enzymatic analyses. Within 1-6 h of hypoxic exposure, ATP levels decreased while ADP and AMP levels increased, producing a fall in calculated ATP/ADP and adenylate charge ratios. Concurrently, lactate/pyruvate and alpha-glycerophosphate/dihydroxyacetone phosphate ratios increased markedly. Direct measurements of cellular pyridine nucleotides indicated increased NADH/NAD and NADPH/NADP ratios. Levels of total adenosine phosphates and pyridine nucleotides decreased in a significant accompanying response. Many metabolite levels and calculated ratios returned to near-normal values within 1 week of exposure, indicating secondary intracellular adjustments to hypoxic stress; however, persistence of that stress is reflected in lactate concentrations and both substrate redox ratios. Results support and explore concepts that increased oxidation-reduction status and decreased energy status are primary events during hypoxia.

Reed, R. D.↗

NASA NTRS1982

Anion permselective membrane

The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

Hodgdon, R. B.↗

NASA NTRS1992

Redox effects in ordinary chondrites and implications for asteroid spectrophotometry

The sensitivity of reflectance spectra to mean ferrous iron content and olivine and pyroxene proportion enhancements in the course of metamorphic oxidation is presently used to examine whether metamorphically-induced ranges in mineralogy, and corresponding spectral parameters, may explain the observed variations in S-asteroid rotational spectra. The predicted spectral variations within any one chondrite class are, however, insufficient to account for S-asteroid rotational spectra, and predicted spectral-range slopes have a sign opposite to the rotational measurements. Metamorphic oxidation is found unable to account for S-asteroid rotational spectra.

Mcsween, Harry Y., Jr.↗

NASA NTRS1993

Metal-silicate thermochemistry at high temperature - Magma oceans and the 'excess siderophile element' problem of the earth's upper mantle

Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.

Capobianco, Christopher J.↗

NASA NTRS2011

Changes in Liver Metabolic Gene Expression from Radiation Exposure

Radiation exposure is one of the unique physiological challenges of human spaceflight that is not encountered on earth. While radiation exposure is known to impart physiological stresses and alter normal function, it is unclear how it specifically affects drug metabolism. A major concern is that the actions of medications used in spaceflight may deviate from the expectations formed from terrestrial use. This concern was investigated at the molecular level by analyzing how gamma radiation exposure affected gene expression in the livers of mice. Three different doses of radiation were administered and after various intervals of recovery time, gene expression was measured with RT-qPCR screening arrays for drug metabolism and DNA repair. After examining the results of 192 genes total from each of 72 mice, 65 genes were found to be significantly affected by at least one of the doses of radiation. In general, the genes affected are involved in the metabolism of drugs with lipid or steroid hormone-like structures, as well as the maintenance of redox homeostasis and repair of DNA damage.

Peters, C. P.↗

NASA NTRS1993

The Mn-Fe negative correlation in olivines in ALHA 77257 ureilite

An electron probe microanalyzer is used to measure the Mn, Fe, and oxygen zoning profiles of olivines in the ALHA 77257 ureilite. This is done to study the effects of reduction on the Mn-Fe value, as ureilite olivines exhibit thin reduced rims. Since the Mn content gradually increases toward the rim of ureilite olivines, while the Fa (= 100 x Fe/(Mg + Fe), mol percent) component decreases, the Mn-Fe content of olivine is likely related to redox conditions. The results of melting experiments suggest that the Mn-Fe positive correlation is related to temperature and that the negative correlation of Mn-Fe in olivine and low-Ca pyroxene is related to reduction.

Miyamoto, M.↗

NASA NTRS2018

Enabling Experimental Evolution: Multi-Parameter Sensor System Integration into a Culture/Stressor Biofluidics System

Experimental evolution (EE) exposes microbial communities to ecological stressors, simulating dynamics up to near-extinction events. Combined with comparative sequencing and other molecular tools, such data can inform the genetic and other biological mechanisms underlying extremophile adaptation, and other observed effects. Automating this type of experiment using biofluidics can mitigate many traditional obstacles, including delays in assay results and environment adjustment and the need for many replicates. A first-generation device for automating EE procedures, the Automated Adaptive Directed Evolution Chamber (AADEC), was developed at NASA Ames. UV-C radiation was the stressor, an LED-photodiode array measured optical density, magnetic agitation and peristaltic pump systems ensured nutrient availability, and Arduino microcontrollers provided control. Escherichia coli in LB kanamycin media was used for testing and performance verification. A manual laboratory procedure with timed exposure to UV-C was performed to typify tolerance acquisition. Approximately a 106 factor increase in survival ratio was recorded over multiple iterations. Currently, a second-generation device is being developed integrating more real-time sensors: redox potential (ORP), indicating available/consumed metabolic energy; dissolved oxygen (DO), indicating aerobic/anaerobic growth; pH, indicating metabolic products; and electrical conductivity (EC), another indicator of metabolic products. The EC sensor system was constructed and calibrated in-house and matched commercial sensors in the required range. A Raspberry Pi computer automated the electrical system, allowing real-time data acquisition. The fluidics card was made of CNC-milled polycarbonate for biocompatibility. Each sensor parameter can also be used as a selection pressure alone or in combination with others to create extreme microbial environments. As a proof of concept, this work demonstrated sensor operation in one pair of growth-sensor chambers. It can be expanded to a multi-chamber system to enable inter-culture comparisons and multi-population studies. The prior Arduino system will be ported to the RPi system. Future stressors to be added include thermal, reactive oxygen species, and varying nutrient availability.

Govinda Raj, Chinmayee↗

NASA NTRS1992

Estimation of high temperature metal-silicate partition coefficients

It has been known for some time that abundances of siderophile elements in the upper mantle of the Earth are far in excess of those expected from equilibrium between metal and silicate at low pressures and temperatures. Murthy (1991) has re-examined this excess of siderophile element problem by estimating liquid metal/liquid silicate partition coefficients reduces from their measured values at a lower temperature, implying that siderophile elements become much less siderophilic at high temperatures. Murthy then draws the important conclusion that metal/silicate equilibrium at high temperatures can account for the abundances of siderophile elements in the Earth's mantle. Of course, his conclusion is critically dependent on the small values of the partition coefficients he calculates. Because the numerical values of most experimentally-determined partition coefficients increase with increasing temperature at both constant oxygen fugacity and at constant redox buffer, we think it is important to try an alternative extrapolation for comparison. We have computed high temperature metal/silicate partition coefficients under a different set of assumptions and show that such long temperature extrapolations yield values which are critically dependent upon the presumed chemical behavior of the siderophile elements in the system.

Jones, John H.↗

NASA NTRS1985

Cycling Performance of the Iron-Chromium Redox Energy Storage System

Extended charge-discharge cycling of this electrochemical storage system at 65 C was performed on 14.5 sq cm single cells and a four cell, 867 sq cm bipolar stack. Both the anolyte and catholyte reactant fluids contained 1 molar concentrations of iron and chromium chlorides in hydrochloric acid and were separated by a low-selectivity, cation-exchange membrane. The effect of cycling on the chromium electrode and the cation-exchange membrane was determined. Bismuth and bismuth-lead catalyzed chromium electrodes and a radiation-grafted polyethylene membrane were evaluated by cycling between 5 and 85 percent state-of-charge at 80 mA/sq cm and by periodic charge-discharge polarization measurements to 140 mA/sq cm. Gradual performance losses were observed during cycling but were recoverable by completely discharging the system. Good scale-up to the 867 sq cm stack was achieved. The only difference appeared to be an unexplained resistive-type loss which resulted in a 75 percent W-hr efficiency (at 80 mA/sq cm versus 81 percent for the 14.5 sq cm cell). A new rebalance cell was developed to maintain reactant ionic balance. The cell successfully reduced ferric ions in the iron reactant stream to ferrous ions while chloride ions were oxidized to chlorine gas.

Gahn, R. F.↗

NASA NTRS1985

Cycling performance of the iron-chromium redox energy storage system

Gahn, R. F.↗

NASA NTRS1983

Electrochemical Studies of Redox Systems for Energy Storage

Particular attention was paid to the Cr(II)/Cr(III) redox couple in aqueous solutions in the presence of Cl(-) ions. The aim of this research has been to unravel the electrode kinetics of this redox couple and the effect of Cl(1) and electrode substrate. Gold and silver were studied as electrodes and the results show distinctive differences; this is probably due to the role Cl(-) ion may play as a mediator in the reaction and the difference in state of electrical charge on these two metals (difference in the potential of zero charge, pzc). The competition of hydrogen evolution with CrCl3 reduction on these surfaces was studied by means of the rotating ring disk electrode (RRDE). The ring downstream measures the flux of chromous ions from the disk and therefore separation of both Cr(III) and H2 generation can be achieved by analyzing ring and disk currents. The conditions for the quantitative detection of Cr(2+) at the ring electrode were established. Underpotential deposition of Pb on Ag and its effect on the electrokinetics of Cr(II)/Cr(III) reaction was studied.

Wu, C. D.↗

NASA NTRS1979

Investigation of effects of temperature, salinity, and electrode design on the performance of an electrochemical coliform detector

The results of two research programs to determine the optimum detector design for measuring fecal coliforms in saline waters for operational systems are presented. One program was concerned with the effects of temperature and salinity on endpoint response time, and the other, the interaction between electrode configurations and the test organisms. Test results show that the endpoint response time is related to salinity and seawater temperature; however, these results can be minimized by the correct choice of growth media. Electrode configurations were developed from stainless steel, Parlodion-coated stainless steel, and platinum that circumvented problems associated with the commercial redox electrodes.

Grana, D. C.↗

NASA NTRSDate not supplied

Supercool(ed) Olivine Morphology in Shergottites Revealed Using X-ray Computed Tomography

Shergottites comprise most of the Martian meteorites and have a mafic to ultramafic bulk composition and a diversity of igneous textures [1].Olivine-phyric and poikilitic shergottites are sub-classes of shergottites and characterized by having a crystal cargo of large mafic minerals. Olivine-phyric shergottites have porphyritic textures of large olivinemegacrysts set in a fine-grained groundmass of pyroxene and maskelynite [2]. The poikilitic shergottites have assemblages of olivine chadocrysts poikilitically-enclosed by cm-sized pyroxene oikocrysts set in a coarse-grained groundmass of olivine and maskelynite [3,4]. The large crystal cargos in these samples are some of the first minerals to crystallize from their respective parent melts and have been extensively studied to understand shergottite petrogenesis. For instance, compositions of early-formed olivine and pyroxene in equilibrium with other phases (e.g. spinels) are used to establish depths, temperatures, and redox conditions of crystallization. There is increasing agreement that olivine megacrysts and poikilitic assemblages formed at or near the crust – mantle boundary (~85 km) before entrainment, ascent, and complete crystallization at or near the surface [1,3,4,6,7,8,9]. Additionally, linear olivine megacryst crystal size distribution (CSD)patterns and observations of polyhedral morphologies[8,9,10] are commonly interpreted to reflect steady-state crystallization under equilibrium conditions. However, oscillatory phosphorus zonation patterns in olivine from many samples indicate fluctuations in growth rates[10,12]. Recent studies measuring dendritic phosphorus zonation in terrestrial olivines [13] and experimental studies measuring how undercooling (undercooling is defined as the liquidus temperature minus the temperature being considered) controls changes in olivine morphology [14] have questioned the canonical view that large olivine megacrysts grow slowly and concentrically under equilibrium conditions. Here we present X-ray CT results from olivine-phyric and poikilitic shergottites that challenge the notion that early-formed minerals grew slowly under equilibrium conditions.

S A Eckley↗

NASA NTRS1985

Chemical and electrochemical behavior of the Cr(III)/Cr(II) half-cell in the iron-chromium redox energy storage system

The Cr(III) complexes present in the acidified chromium solutions used in the iron-chromium redox energy storage system have been isolated and identified as Cr(H2O)6(3+) and Cr(H2O)5Cl(2+) by ion-exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles have been followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations of the Cr(III) species calculated using Beer's law. During the charge mode, Cr(H2O)5Cl(2+) is reduced to Cr(H2O)5Cl(+), and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(2+). Electrode potential measurements also support this interpretation. Hysteresis effects in the charge-discharge curves can be explained by the slow attainment of equilibrium between Cr(H2O)6(3+) and Cr(H2O)5Cl(2+).

Johnson, D. A.↗

NASA NTRS2004

Evolution of the Ureilite Parent Body

Ureilites are ultramafic achondrites composed primarily of olivine and pyroxene with intergranular fine-grained metal, sulfides, and silicates. Ureilites contain significant amounts of carbon (up to about 6.5 wt%) as graphite, lonsdaleite, and/or diamond. It has been shown that carbon-silicate redox (i.e. "smelting") reactions are responsible for the negative FeO-MnO (or positive Fe/Mn-Fe/Mg with constant Mn/Mg) trend seen in the mineral and bulk compositions of ureilites and for the positive correlation between modal percent pigeonite and mg#. Carbon redox reactions are strongly exothermic and pressure dependent; so ureilites with the largest mg# are the most reduced, experienced the highest temperatures, and formed at the lowest pressures, i.e. near the surface of the ureilite parent body. Ureilites with the largest mg# have the smallest the delta(sup 18)O and the largest Delta(sup 17)O. To explain this, Singletary and Grove proposed that heterogeneous accretion took place on the ureilite parent body, which lead to a radial distribution of the oxygen isotopes. To further investigate possible relationships, we performed carbon isotope and electron probe measurements on a suite of 27 ureilites in order to see the type of correlation that exists between mg#, oxygen isotopes, and carbon.

Hudson, P.↗

NASA NTRS1984

Intrinsic oxygen fugacities of diogenites and mesosiderite clasts

Oxygen fugacities of diogenite and mesosiderite clast material were measured with the double ZrO2 cell technique between 800 and 1150 C. The samples were taken from large clasts in the diogenites Johnstown (En73) and Tatahouine (En75), and the mesosiderites Estherville (En81), West Point (Fo88) and Emery (En68). Fugacity values for all except Emery plot near the wuestite-iron buffer curve and are interpreted as indicating similar source regions and environments of crystallization for the two suites. Emery orthopyroxene records a lower fugacity, close to the fayalite-quartz-iron buffer curve, probably as a result of equilibration with the mesosiderite matrix assemblage. The similarity of redox conditions experienced by mesosiderite orthopyroxenite and diogenites is not sufficient to require a single parent body and, if the common achondrites were derived from Vesta, mesosiderites probably came from a different body.

Hewins, R. H.↗