Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “REDOX”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 325 records · Page 18

The potential for crustal resources on Mars

Martian resources pose not only an interesting scientific challenge but also have immense astronautical significance because of their ability to enhance mission efficiency, lower launch and program costs, and stimulate the development of large Mars surface facilities. Although much terrestrial mineralization is associated with plate tectonics and Mars apparently possesses a thick, stationary lithosphere, the presence of crustal swells, rifting, volcanism, and abundant volatiles indicates that a number of sedimentary, hydrothermal, dry-magma mineral concentration processes may have operated on Mars. For example, in Colorado Plateau-style (roll-front) deposits, uranium precipitation is localized by redox variations in groundwater. Also, evaporites (either in salt pans or even interstitially in pore spaces) might concentrate Cl, Li, and K. Many Martian impact craters have been modified by volcanism and probably have been affected by rising magma bodies interacting with ground ice or water. Such conditions might produce hydrothermal circulations and element concentrations. If the high sulfur content found by the Viking landers typifies Martian abundances, sulfide ore bodies may have been formed locally. Mineral-rich Africa seems to share many volcanic and tectonic characteristics with portions of Mars and may suggest Mars' potential mineral wealth. For example, the rifts of Valles Marineris are similar to the rifts in east Africa, and may both result from a large mantle plume rising from the interior and disrupting the surface. The gigantic Bushveld complex of South Africa, an ancient layered igneous intrusion that contains ores of chromium and Pt-group metals, illustrates the sort of dry-magma processes that also could have formed local element concentrations on Mars, especially early in the planet's history when heat flow was higher.

Cordell, Bruce M.↗

The mineralogy of ordinary chondrites and implications for asteroid spectrophotometry

Published data from bulk chemical analyses of 94 ordinary chondrites are compiled in a table of normative mineralogy and discussed in detail. Significant variations in olivine, pyroxene, and metal abundance ratios are found within each chondrite class and attributed to redox processes superimposed on initial differences in metal/silicate ratios. The use of the diagrams constructed here to predict the mineralogic characteristics of asteroids on the basis of spectrophotometric observations is suggested.

Mcsween, Harry Y., Jr.↗

Partial melting of the Allende (CV3) meteorite - Implications for origins of basaltic meteorites

Eucrites and angrites are distinct types of basaltic meteorites whose origins are poorly known. Experiments in which samples of the Allende (CV3) carbonaceous chondrite were partially melted indicate that partial melts can resemble either eucrites or angrites, depending only on the oxygen fugacity. Melts are eucritic if this variable is below that of the iron-wuestite buffer or angritic if above it. With changing pressure, the graphite-oxygen redox reaction can produce oxygen fugacities that are above or below those of the iron-wuestite buffer. Therefore, a single, homogeneous, carbonaceous planetoid greater than 110 kilometers in radius could produce melts of drastically different composition, depending on the depth of melting.

Jurewicz, A. J. G.↗

Nitrogen isotopic signatures in the Acapulco meteorite

N isotopic abundances are reported for a bulk sample of the unique meteorite Acapulco. Although the mineral chemistry indicates a high degree of recrystallization under redox conditions between those of H and E chondrites (Palme et al., 1981), the presence of two distinct N isotopic signatures shows that the carriers of these N components were not equilibrated. In stepwise pyrolysis, the larger (65 percent) N component is released mostly below 1000 C and reveals a signature of delta(N-15) = 8.9 + or - 1.2 per mil, which is within the range observed in chondrites. A second 'light' component appears above 1000 C and has a signature of delta(N-15) less than or equal to -110.5 + or - 4.0 per mil (uncorrected for spallation N-15).

Sturgeon, G.↗

Spectroscopy and reactivity of mineral analogs of the Martian soil

To answer the question of why life occurred on Earth but not on Mars requires a study of the geochemical and physical aspects of the Martian soil. Some of the best Mars analog mineral models of the soil have been prepared and justified according to known constraints of chemical composition, reflectance spectroscopy, and chemical reactivity. Detailed laboratory reflectance spectra in the ultraviolet, visible, and near infrared (.30 to 2.5 microns) and the infrared (2.5 to 25 microns) regions have been obtained for the pure candidate minerals and some analog mixtures and compared to Mars reflectance spectra. Modeling of the reflectance spectra from optical constraints determined for the analog minerals has begun and will be interpreted in terms of the effects of particle size variation, component mixing, and soil packing upon remotely sensed reflectance spectra. This has implications not only for Mars, but for other planets and planetoids. The ratio of Fe(II)/Fe(III) in the Martian soil analog materials on spectral reflectance in the visible range has begun, and the results will be evaluated according to conformity with the visible Mars reflectance spectrum. Some initial LR and GEX data have been collected for the mineral samples and their mixtures, which can be compared with the Viking data and interpreted in terms of the redox (Fe(II)/Fe(III) environment.

Banin, A.↗

Biologically controlled minerals as potential indicators of life

Minerals can be produced and deposited either by abiotic or biologic means. Regardless of their origin, mineral crystals reflect the environment conditions (e.g., temperature, pressure, chemical composition, and redox potential) present during crystal formation. Biologically-produced mineral crystals are grown or reworked under the control of their host organism and reflect an environment different from the abiotic environment. In addition, minerals of either biologic or abiotic origin have great longevities. For these reasons, biologically produced minerals have been proposed as biomarkers. Biomarkers are key morphological, chemical, and isotopic signatures of living systems that can be used to determine if life processes have occurred. Studies of biologically controlled minerals produced by the protist, Paramecium tetraurelia, were initiated since techniques have already been developed to culture them and isolate their crystalline material, and methods are already in place to analyze this material. Two direct crystalline phases were identified. One phase, whose chemical composition is high in Mg, was identified as struvite. The second phase, whose chemical composition is high in Ca, has not been previously found occurring naturally and may be considered a newly discovered material. Analyses are underway to determine the characteristics of these minerals in order to compare them with characteristics of these minerals in order to compare them with characteristics of minerals formed abiotically, but with the same chemical composition.

Schwartz, D. E.↗

Origin of the moon and lunar core formation

In a recent version of the giant impact hypothesis by O'Neill, the initial abundances of the siderophile elements in the lunar mantle were established not only by combining impactor material and proto-Earth material, but also by adding a late reduced veneer. O'Neal also appealed to the possible volatilities of some elements (Mo and W) under conditions of lunar accretion, and required the segregation of a small Ni-rich metallic core. An attempt to more rigorously model lunar core formation in the O'Neill scenario is made by correlating degree of partial melting to temperature and extrapolating the 1260 C partition coefficients to the appropriate temperatures along a constant redox buffer.

Hillgren, Valerie J.↗

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.↗

Determining the pH of Mars from the Viking labelled release reabsorption effect

The acid-base properties and redox potentials of solids are two of the more fundamental chemical parameters characterizing a material. Knowledge of these parameters for martian regolith fines would be of considerable value in determining what specific compounds are present and making judgements on what reactions are possible.

Plumb, Robert C.↗

Protecting Li/TiS2 Cells Against Overcharge

New electrolyte additive, N,N,N',N'- tetramethyl-1,4-phenylenediamine (TMPD), helps protect lithium/titanium disulfide rechargeable cells against overcharge. TMPD is redox couple: during overcharge, it undergoes electrochemical reactions at both electrodes and takes up excess input charge. Without TMPD, overcharge results in oxidative degradation of nonaqueous electrolyte, leading to loss of rechargeability and safety problems. Li/TiS2 cells currently being considered for spacecraft and military applications.

Narayanan, S. R.↗

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.↗

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.↗

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Clark, W. D. K.↗

Microelectrode-based technology for the detection of low levels of bacteria

A microelectrode-based electrochemical detection method was used for quantitation of bacteria in water samples. The redox mediator, benzoquinone, was used to accept electrons from the bacterial metabolic pathway to create a flow of electrons by reducing the mediator. Electrochemical monitoring electrodes detected the reduced mediator as it diffused out of the cells and produced a small electrical current. By using a combination of microelectrodes and monitoring instrumentation, the cumulative current generated by a particular bacterial population could be monitored. Using commercially available components, an electrochemical detection system was assembled and tested to evaluate its potential as an emerging technology for rapid detection and quantitation of bacteria in water samples.

Rogers, Tom D.↗

Remote sensing of wetland biomass and productivity for global biosystem research

The study of ecosystem function and the contributions of particular ecosystems to global elemental cycling will require data collection from orbital platforms. Presently used ground sampling techniques are not adequate for large area vegetation assessments. The research was directed toward an understanding of the relationship between spectral radiance and plant canopy biomass. Changes in the architecture of the canopy alters the observed spectral radiance patterns. The green components of a plant canopy interacts most strongly with incident radiation and usually reflect edaphic conditions as they relate to plant vigor. Plant biomass serves as an excellent integrator of the environmental factors encountered by the plant and can be used as an indicator for predicting soil redox, nutrient status, microbial activity, etc. The use was examined of TM spectral data to discriminate biomass classes and, in turn, to relate the biomass classes to the chemical status of the soil. Several preliminary studies have indicated that solar angle can be used to improve biomass predictions. This important observation also suggests that latitudinal extrapolation of the biomass predicting models will be possible if selected characteristics of the incident radiation are known.

Hardisky, M. A.↗

Sulfate reduction and other sedimentary biogeochemistry in a northern New England salt marsh

Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.

Hines, Mark E.↗

The group A3 chondrules of Krymka: Further evidence for major evaporative loss during the formation of chondrules

Like Semarkona (type 3.0), Krymka (type 3.1) contains two distinct types of chondrule (namely groups A and B) which differ in their bulk compositions, phase compositions, and CL properties. The group A chondrules in both meteorites show evidence for major loss of material by evaporation(i.e. elemental abundance patterns, size, redox state, olivine-pyroxene abundances). Group A and B chondrules probably formed from common or very similar precursors by the same processes acting with different intensities, group A suffering greater mass-loss by evaporation and reduction of FeO and SiO2. While Krymka chondrules share many primary mineralogical and compositional properties with Semarkona chondrules, the minimal metamorphism it has suffered has also had a significant effect on its chondrules.

Huang, S.↗

Earth's partial pressure of CO2 over the past 120 Ma; evidence from Ce anomalies in the deep (greater than 600 m) Pacific Ocean, 1

It was found that Ce serves as a chemical tracer of paleo-oceanic redox conditions. It was shown that the unoxidized and soluble Ce(3+) in modern seawater exhibits a negative anomaly relative to the other soluble REE(3+). An expression of soluble Ce(3+) in seawater that was approximately 1900X greater than the average observed in Ce in 600-5000 m Pacific seawater was derived. Since Ce(CO3)(+) and Ce(CO3)2(-) complexes greatly exceed the Ce(PO4) complexes in seawater, the formulations of using carbonate complexes were followed and it was found that the calculated Ce and observed concentrations in the deep 600-5000 m Pacific Ocean agree within the uncertainties of the thermodynamic data. As expected, the calculated Ce concentrations are a strong function of pH and found to be lesser functions of CO3(2-) activities.

Liu, Y.-G↗