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We present observational, meteoritic, and physical-chemical arguments for an oxidized Fe-metal free mantle and an oxidized sulfate-carbonate rich ocean on Europa. The ocean should be out of equilibrium even with oxidized igneous rocks at the oceanic floor. Additional information is contained in the original extended abstract.
An animated sequence of maps of simulated carbon monoxide concentrations graphically portrays the extent of residual continental influence upon the tropical Pacific Ocean as studied by NASA aircraft during the PEM-Tropics B intensive sampling campaign. We used the MM5 at a 90 km resolution in a globally wrapped grid to simulate the meteorology of transport, and our GRACES model to follow the basic chemistry. The CO we simulate derives from different sources, and so we distinguish anthropogenic, natural terpenoid oxidation, biomass burning, and pervasive CH4-oxidation influences. "Influence" is always judged with an implicit timescale, and these maps describe influence on the 15-45 day timescale appropriate for CO oxidation. In consequence, the maps are useful in assessing the origins of slowly reacting compounds like acetone, methanol, and the lightest hydrocarbons. At 8 km altitude, The Eastern South Pacific to ca. 130 W (eastern Polynesia) was frequently affected by continental influences but NASA's DC-8's flight path did not happen to take it into these regions very often. Near the surface, continentally influenced air crossed into t he Western South Pacific, in the region northwest of the Southern Pacific Convergence Zone but south of the Intertropical Convergence Zone. This air originated from the NE Pacific, and partly from North America. Comparisons are made to CO and other compounds measured aboard the DC-8 and the P-3 aircraft. We will also use tracers to describe the influence of marine convection in the upper troposphere. As time allows, we will discuss the "age" of ozone within the very cleanest region sampled in portions of the near-equatorial Western South Pacific, using a simple chemical mechanism for ozone levels. These simulations describe the chemistry of an atmosphere with very low ozone.
The first transition row oxides and sulfides are studied using several different levels of theory. The calculations show the bonding mechanism in the sulfides and oxides to be very similar. For the oxides, accurate experimental data allow the theoretical methods to be calibrated. The same level of theory is used to study the sulfides where there is far less experimental information. For ScO through MnO and CuO the coupled cluster singles and doubles technique including a perturbational estimate of the unliked triple excitations [CCSD(T)] yields spectroscopic constants ((tau)e, (omega)e, and D0) in good agreement with experiment. The triple excitations are found to be very important in achieving this accuracy. For FeO to NiO, the single determinant self-consistent-field (SCF) approach yields pi orbitals that are localized on the metal or oxygen. This appears to cause problems for the single reference techniques; this is discussed in detail for NiO. The complete-active-space SCF/internally contracted averaged coupled pair functional approach (CASSCF/ICACPF) works well for FeO to NiO. The calculation of accurate dipole moments is found to be very difficult.
Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.
We describe a chemometric array sensor, the Mars Atmospheric Oxidant Sensor (MAOS) that is designed to measure the oxidation rate of thin films on the martian surface. MAOS will discriminate among leading hypotheses for oxidant production. Additional information is contained in the original extended abstract.
This paper discusses a study of two alternate oxidizers, liquid oxygen and hydrogen peroxide, for use in a rocket based combined cycle (RBCC) demonstrator vehicle. The flight vehicle is baselined as an airlaunched self-powered Mach 0.7 to 7 demonstration of an RBCC engine through all or its air breathing propulsion modes. Selection of an alternate oxidizer has the potential to lower overall vehicle size, system complexity/ cost and ultimately the total program risk. This trade study examined the oxidizer selection effects upon the overall vehicle performance, safety and operations. After consideration of all the technical and programmatic details available at this time, 90% hydrogen peroxide was selected over liquid oxygen for use in this program.
We use a biological nano-scale pore to distinguish among individual DNA hairpins that differ by a single site of oxidation or a nick in the sugar-phosphate backbone. In earlier work we showed that the protein ion channel alpha-hemolysin can be used as a detector to distinguish single-stranded from double-stranded DNA, single base pair and single nucleotide differences. This resolution is in part a result of sensitivity to structural changes that influence the molecular dynamics of nucleotides within DNA. The strand cleavage products we examined here included a 5-base-pair (5-bp) hairpin with a 5-prime five-nucleotide overhang, and a complementary five-nucleotide oligomer. These produced predictable shoulder-spike and rapid near-full blockade signatures, respectively. When combined, strand annealing was monitored in real time. The residual current level dropped to a lower discrete level in the shoulder-spike blockade signatures, and the duration lengthened. However, these blockade signatures had a shorter duration than the unmodified l0bp hairpin. To test the pore sensitivity to nucleotide oxidation, we examined a 9-bp hairpin with a terminal 8-oxo-deoxyguanosine (8-oxo-dG), or a penultimate 8-oxo-dG. Each produced blockade signatures that differed from the otherwise identical control 9bp hairpins. This study showed that DNA structure is modified sufficiently by strand cleavage or oxidation damage at a single site to alter in a predictable manner the ionic current blockade signatures produced. This technique improves the ability to assess damage to DNA, and can provide a simple means to help characterize the risks of radiation exposure. It may also provide a method to test radiation protection.
An investigation was conducted to examine the friction and wear behavior of the two types of oxide ceramic films furnished by the U.S. Army Research Laboratory, Development and Engineering Center (ARDEC) under Space Act Agreement SAA3 567. These two types of oxide ceramics were grown on 55Ni-45Ti (60 wt% Ni and 40 wt% Ti) substrates: one was a TiO2 with no other species (designated the B film) and the other was a TiO2 with additional species (designated the G film). Unidirectional ball-on-disk sliding friction experiments were conducted with the oxide films in contact with sapphire at 296 K (23 C) in approx. 50-percent relative humidity laboratory air in this investigation. All material characterization and sliding friction experiments were conducted at the NASA Glenn Research Center. The results indicate that both films greatly improve the surface characteristics of 55Ni-45Ti, enhancing its tribological characteristics. Both films decreased the coefficient of friction by a factor of 4 and increased wear resistance by a two-figure factor, though the B film was superior to the G film in wear resistance and endurance life. The levels of coefficient of friction and wear resistance of both films in sliding contact with sapphire were acceptable for NASA and Department of Defense tribological applications. The decrease in friction and increase in wear resistance will contribute to longer wear life for parts, lower energy consumption, reduced related breakdowns, decreased maintenance costs, and increased reliability.
Ceramic thermal barrier coatings will play an increasingly important role in advanced gas turbine engines because of their ability to further increase engine operating temperatures and reduce cooling, thus helping achieve future engine low emission, high efficiency and improved reliability goals. Advanced multi-component zirconia-based thermal barrier coatings are being developed using an oxide defect clustering design approach to achieve the required coating low thermal conductivity and high temperature stability. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of the candidate coating materials was conducted using conventional furnace cyclic oxidation tests. In this paper, furnace cyclic oxidation behavior of plasma-sprayed zirconia-based defect cluster thermal barrier coatings was investigated at 1163 C using 45 min hot cycles. The ceramic coating failure mechanisms were studied using scanning electron microscopy (SEM) combined with X-ray diffraction (XRD) phase analysis after the furnace tests. The coating cyclic lifetime is also discussed in relation to coating processing, phase structures, dopant concentration, and other thermo-physical properties.
Bioregenerative life support systems may be necessary for long-term space missions due to the high cost of lifting supplies and equipment into orbit. In this study, we investigated two biological wastewater treatment reactors designed to recover potable water for a spacefaring crew being tested at Johnson Space Center. The experiment (Lunar-Mars Life Support Test Project-Phase III) consisted of four crew members confined in a test chamber for 91 days. In order to recycle all water during the experiment, an immobilized cell bioreactor (ICB) was employed for organic carbon removal and a trickling filter bioreactor (TFB) was utilized for ammonia removal, followed by physical-chemical treatment. In this study, the spatial distribution of various microorganisms within each bioreactor was analyzed by using biofilm samples taken from four locations in the ICB and three locations in the TFB. Three target genes were used for characterization of bacteria: the 16S rRNA gene for the total bacterial community, the ammonia monooxygenase (amoA) gene for ammonia-oxidizing bacteria, and the nitrous oxide reductase (nosZ) gene for denitrifying bacteria. A combination of terminal restriction fragment length polymorphism (T-RFLP), sequence, and phylogenetic analyses indicated that the microbial community composition in the ICB and the TFB consisted mainly of Proteobacteria, low-G+C gram-positive bacteria, and a Cytophaga-Flexibacter-Bacteroides group. Fifty-seven novel 16S rRNA genes, 8 novel amoA genes, and 12 new nosZ genes were identified in this study. Temporal shifts in the species composition of total bacteria in both the ICB and the TFB and ammonia-oxidizing and denitrifying bacteria in the TFB were also detected when the biofilms were compared with the inocula after 91 days. This result suggests that specific microbial populations were either brought in by the crew or enriched in the reactors during the course of operation.
Oxidative processes are probable determinants of longevity of seeds in storage. Measurements of actual oxygen uptake rates were made for soybean and pea seeds as a comparison of short and long lived seeds when light, temperature, and moisture contents were varied. In both peas and soybeans, the oxygen uptake was depressed at low temperatures (<16 degrees C) and low water contents (< 0.25 gram H2O per gram dry weight). Apparent activation energies under these conditions are very high, while apparent activation energies of seeds at higher water contents and at temperatures greater than 22 degrees C are much less. Light enhances the level of oxygen uptake in pea, but reduces the level of oxygen uptake in soybean. The complexities of the interactions of oxygen uptake with environmental conditions in soybean compared to pea suggest that oxidative processes occur in soybean at low water contents, but are essentially absent in pea. It is suggested that the additional oxidative processes in soybean with moisture contents between 0.10 and 0.24 gram per gram may contribute to the poorer longevity of soybean seed compared to pea seed.
Vasodilation is one of the most prominent effects of adenosine and one of the first to be recognized, but its mechanism of action is not completely understood. In particular, there is conflicting information about the potential contribution of endothelial factors. The purpose of this study was to explore the role of nitric oxide in the vasodilatory effect of adenosine. Forearm blood flow responses to intrabrachial adenosine infusion (125 microg/min) were assessed with venous occlusion plethysmography during intrabrachial infusion of saline or the nitric oxide synthase inhibitor NG-monomethyl-L-arginine (L-NMMA) (12.5 mg/min). Intrabrachial infusions of acetylcholine (50 microg/min) and nitroprusside (3 microg/min) were used as a positive and negative control, respectively. These doses were chosen to produce comparable levels of vasodilation. In a separate study, a second saline infusion was administered instead of L-NMMA to rule out time-related effects. As expected, pretreatment with L-NMMA reduced acetylcholine-induced vasodilation; 50 microg/min acetylcholine increased forearm blood flow by 150+/-43% and 51+/-12% during saline and L-NMMA infusion, respectively (P<.01, n=6). In contrast, L-NMMA did not affect the increase in forearm blood flow produced by 3 microg/min nitroprusside (165+/-30% and 248+/-41% during saline and L-NMMA, respectively) or adenosine (173+/-48% and 270+/-75% during saline and L-NMMA, respectively). On the basis of our observations, we conclude that adenosine-induced vasodilation is not mediated by nitric oxide in the human forearm.
The influence of spaceflight on the oxidative burst of neutrophils is not known. The present study was designed to evaluate the influence of antiorthostatic suspension, a ground-based modeling system designed to simulate certain aspects of weightlessness that occur after spaceflight, on the capacity of rat neutrophils to express the oxidative burst, an important host defense mechanism against microbial pathogens. Rats were suspended in whole body harnesses in the antiorthostatic orientation for a 3- or 7-day period. Control rats were suspended orthostatically or allowed to remain in vivarium cages without the attachment of any suspension materials. After suspension, peripheral blood was harvested and neutrophils were isolated by density gradient centrifugation. The enriched neutrophil preparations were stimulated with N-formyl-methionyl-leucine-phenylalanine and phorbol myristic acid to induce the oxidative burst. It was found that neutrophils isolated from suspended animals released the same levels of superoxide anion as did vivarium control animals that were not suspended, indicating that whole body suspension did not alter this aspect of rat neutrophil function.
Spinel can be a significant host phase for V which has multiple oxidation states V(sup 2+), V(sup 3+), V(sup 4+) or V(sup 5+) at oxygen fugacities relevant to natural systems. The magnitude of D(V) spinel/melt is known to be a function of composition, temperature and fO2, but the uncertainty of the oxidation state under the range of natural conditions has made elusive a thorough understanding of D(V) spinel/melt. For example, V(sup 3+) is likely to be stable in spinels, based on exchange with Al in experiments in the CaO-MgO-Al2O3-SiO2 system. On the other hand, it has been argued that V(sup 4+) will be stable across the range of natural oxygen fugacities in nature. In order to build on our previous work in more oxidized systems, we have carried out experiments at relatively reducing conditions from the FMQ buffer to 2 log fO2 units below the IW buffer. These spinel-melt pairs, where V is present in the spinel at natural levels (approx. 300 ppm V), were analyzed using an electron microprobe at NASA-JSC and micro- XANES at the Advanced Photon Source at Argonne National Laboratory. The new results will be used together with previous results to understand the valence of V in spinel-melt systems across 12 orders of magnitude of oxygen fugacity, and with application to natural systems.
Boron nitride (BN) is a prime candidate for fiber coatings in silicon carbide (SiC) fiber-reinforced SiC matrix composites. The properties of BN allow the fiber to impart beneficial composite properties to the matrix, even at elevated temperatures. The problem with BN is that it is readily attacked by oxygen. Although BN is an internal component of the composite, a matrix crack or pore can create a path for hot oxygen to attack the BN. This type of attack is not well understood. A variety of phenomena have been observed. These include borosilicate glass formation, volatilization of the BN, and under some conditions, preservation of the BN. In this study at the NASA Lewis Research Center, a series of BN materials and BN-containing model composites were methodically examined to understand the various issues dealing with the oxidation of BN in composites. Initial studies were done with a series of monolithic BN materials prepared by hot pressing and chemical vapor deposition (CVD). From these studies, we found that BN showed a strong orientation effect in oxidation and was extremely sensitive to the presence of water vapor in the environment. In addition, CVD material deposited at a high temperature showed much better oxidation behavior than CVD material deposited at a lower temperature.
Solid-oxide fuel cells (SOFCs) show great potential as a power source for future space exploration missions. Because SOFCs operate at temperatures significantly higher than other types of fuel cells, they can reach overall efficiencies of up to 60% and are able to utilize fossil fuels. The SOFC team at GRC is leading NASA's effort to develop a solid oxide fuel cell with a power density high enough to be used for aeronautics and space applications, which is approximately ten times higher than ground transport targets. layers must be able to operate as a single unit at temperatures upwards of 900'C for at least 40,000 hours with less than ten percent degradation. One key challenge to meeting this goal arises from the thermal expansion mismatch between different layers. The amount a material expands upon heating is expressed by its coefficient of thermal expansion (CTE). If the CTEs of adjacent layers are substantially different, thermal stresses will arise during the cell's fabrication and operation. These stresses, accompanied by thermal cycling, can fracture and destroy the cell. While this is not an issue at the electrolyte-cathode interface, it is a major concern at the electrolyte-anode interface, especially in high power anode-supported systems. electrolyte are nearly identical. Conventionally, this has been accomplished by varying the composition of the anode to match the CTE of the yittria-stabilized zirconia (YSZ) electrolyte (approx.10.8x10(exp -6/degC). A Ni/YSZ composite is typically used as a base material for the anode due to its excellent electrochemical properties, but its CTE is about 13.4x10(exp -6/degC). One potential way to lower the CTE of this anode is to add a small percentage of polycrystalline Al2TiO5, with a CTE of 0.68x10(exp -6/degC, to the Ni/YSZ base. However, Al2TiO5 is thermally unstable and loses its effectiveness as it decomposes to Al2O3 and TiO2 between 750 C and 1280 C. be used as additives to increase the thermal stability of Al2TiO5 in SOFC operating conditions without adversely affecting the electrochemical properties of the SOFC anode. Three candidate materials were chosen through an extensive literature review: MgO, Fe2O3, and ZrTiO4. Although all three have been shown to prevent Al2TiO5 decomposition under various conditions, their effectiveness in the temperature range and atmosphere of the SOFC has not yet been evaluated. Several batches of Al2TiO5 with varying amounts of additives were prepared, exposed to reducing and oxidizing atmospheres at elevated temperatures, and the resulting decomposition of Al2TiO5 was measured. The most promising additives were further evaluated with the goal of ultimately preparing low CTE anodes that are chemically compatible to current systems. Adding minor constituents to stabilize Al2TiO5 could ultimately preserve its low CTE for the life of the fuel cell and improve the cell's long-term performance without a drop in anode conductivity. Further, these low CTE filler additions could allow the use of new sulfur tolerant anode materials, improving the viability of SOFCs for future aeronautics and space applications. Every SOFC consists of a cathode and an anode separated by an electrolyte, These three One way to avoid this problem is to design the cell such that the CTEs of the anode and The objective of this summer research project was to evaluate several materials that could
The troposphere above the West Antarctic Ice Sheet (WAIS) was sampled for hydroperoxides at 21 locations during 2-month-long summer traverses from 2000 to 2002, as part of US ITASE (International Transantarctic Scientific Expedition). First time quantitative measurements using an HPLC method showed that methylhydroperoxide (MHP) is the only important organic hydroperoxide occurring in the Antarctic troposphere, and that it is found at levels ten times those previously predicted by photochemical models. During three field seasons, means and standard deviations for hydrogen peroxide (H2O2) were 321+/-158 pptv, 650+/-176 pptv and 330+/-147 pptv. While MHP was detected, but not quantified in December 2000, levels in summer 2001 and 2002 were 317+128 pptv and 304+/-172.2 pptv. Results from firn air experiments and diurnal variability of the two species showed that atmospheric H2O2 is significantly impacted by a physical snow pack source between 76 and 90degS, whereas MHP is not. We show strong evidence of a positive feedback between stratospheric ozone and H2O2 at the surface. Between November-27 and December-12 in 2001, when ozone column densities dropped below 220 DU (means in 2000 and 2001 were 318 DU and 334 DU, respectively), H2O2 was 1.7 times that observed in the same period in 2000 and 2002, while MHP was only 80% of the levels encountered in 2002. Photochemical box model runs suggest that NO and OH levels on WAIS are closer to coastal values, while Antarctic Plateau levels are higher, confirming that region to be a highly oxidizing environment. The modeled sensitivity of H2O2 and particularly MHP to NO offers the potential to use atmospheric hydroperoxides to constrain the NO background and thus estimate the past oxidation capacity of the remote atmosphere. Index Terms: 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 1610 Global Change: Atmosphere (03 15,0325); 0736 Cryosphere: Snow (1827, 1863); 0724 Cryosphere: Ice Cores (4932) Keywords: hydrogen peroxide, methylhydroperoxide, Antarctica, air-snow exchange, stratospheric ozone, atmospheric oxidation capacity
The gateway to affordable and reliable space transportation in the near future remains long-lived rocket-based propulsion systems; and because of their high conductivities, copper alloys remain the best materials for lining rocket engines and dissipating their enormous thermal loads. However, Cu and its alloys are prone to oxidative degradation -- especially via the ratcheting phenomenon of blanching, which occurs in situations where the local ambient can oscillate between oxidation and reduction, as it does in a H2/02- fuelled rocket engine. Accordingly, resistance to blanching degradation is one of the key requirements for the next generation of reusable launch vehicle (RLV) liner materials. Candidate copper alloys have been studied with a view to comparing their oxidation behavior, and hence resistance to blanching, in ambients corresponding to conditions expected in rocket engine service. These candidate materials include GRCop-84 and GRCop-42 (Cu - Cr-8 - Nb-4 and Cu - Cr-4 - Nb-2 respectively); NARloy-Z (Cu-3%Ag-0.5%Y), and GlidCop (Cu-O.l5%Al2O3 ODS alloy); they represent different approaches to improving the mechanical properties of Cu without incurring a large drop in thermal conductivity. Pure Cu (OFHC-Cu) was included in the study to provide a baseline for comparison. The samples were exposed for 10 hours in the TGA to oxygen partial pressures ranging from 322 ppm to 1.0 atmosphere and at temperatures of up to 700 C, and examined by SEM-EDS and other techniques of metallography. This paper will summarize the results obtained.