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NASA NTRS1993

The mid-infrared transmission spectra of Antarctic ureilites

The mid-IR (4000-450/cm; 2.5-22.2 microns) transmission spectra of seven Antarctic ureilites and 10 Antarctic H-5 ordinary chondrites are presented. The ureilite spectra show a number of absorption bands, the strongest of which is a wide, complex feature centered near 1000/cm (10 microns) due to Si-O stretching vibrations in silicates. The profiles and positions of the substructure in this feature indicate that Mg-rich olivines and pyroxenes are the main silicates responsible. The relative abundances of these two minerals, as inferred from the spectra, show substantial variation from meteorite to meteorite, but generally indicate olivine is the most abundant (olivine:pyroxene = 60:40 to 95:5). Both the predominance of olivine and the variable olivine-to-pyroxene ratio are consistent with the known composition and heterogeneity of ureilites. The H-5 ordinary chondrites spanned a range of weathering classes and were used to provide a means of addressing the extent to which the ureilite spectra may have been altered by weathering processes. It was found that, while weathering of these meteorites produces some weak bands due to the formation of small amounts of carbonates and hydrates, the profile of the main silicate feature has been little affected by Antarctic exposure in the meteorites studied here. The mid-IR ureilite spectra provide an additional means of testing potential asteroidal parent bodies for the ureilites.

Sandford, Scott A.↗

NASA NTRS1994

Solubilities of nitrogen and noble gases in basalt melt

Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.

Miyazaki, A.↗

NASA NTRS1994

Supported transition metal catalysts for para- to ortho-hydrogen conversion

The main goal of this study was to develop and improve on existing catalysts for the conversion of ortho- to para-hydrogen. Starting with a commercially available Air Products nickel silicate, which had a beta value of 20, we were trying to synthesize catalysts that would be an improvement to AP. This was accomplished by preparing silicates with various metals as well as different preparation methods. We also prepared supported ruthenium catalysts by various techniques using several metal precursors to improve present technology. What was also found was that the activation conditions prior to catalytic testing was highly important for both the silicates and the supported ruthenium catalysts. While not the initial focus of the research, we made some interesting observations into the adsorption of H2 on ruthenium. This helped us to get a better understanding of how ortho- to para-H2 conversion takes place, and what features in a catalyst are important to optimize activity. Reactor design was the final area in which some interesting conclusions were drawn. As discussed earlier, the reactor catalyst bed must be constructed using straight 1/8 feet OD stainless steel tubing. It was determined that the use of 1/4 feet OD tubing caused two problems. First, the radius from the center of the bed to the wall was too great for thermal equilibrium. Since the reaction of ortho- to para-H2 is exothermic, the catalyst bed center was warmer than the edges. Second, the catalyst bed was too shallow using a 1/4 feet tube. This caused reactant blow-by which was thought to decrease the measured activity when the flow rate was increased. The 1/8 feet tube corrected both of these concerns.

Brooks, Christopher J.↗

NASA NTRS1995

Effect of KOH concentration and anions on the performance of Ni-H2 battery positive plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galavanostatic charging; and discharging in a flooded electrolyte cell. Three different concentrations of KOH (40 percent, 31 percent, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate or silicate were investigated. The end of charge voltage at C/10 charge and at 10 C showed the following order: 40 percent KOH is greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOE. The middischarge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without the added contaminants and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH where the capacity declined after 1000 cycles at 80 percent DOD. At the end of cycling the plate tested in the presence of sulfate and silicate experienced measurable weight loss as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the second oxidation peak that corresponds to the formation of a different phase of oxidized Ni has a lower peak current at -5 C compared to 25 C and oxygen evolution occurs a higher potential at -5 C. The reduction peak (discharge reaction) is more polarized at 25 C compared to -5 C. The presence of silicate alters the potentials only marginally. The implications of these results in plate treatment and low temperature operation are discussed.

Vaidyanathan, H.↗

NASA NTRS1995

Global climatology and variability of potential new production estimated from remote sensing of sea-surface temperature

During this project we have collected numerous shipboard data-bases of oceanic nitrate and silicate versus temperature for both equatorial and coastal upwelling regions. These cruises all have accompanying N-15 measurements of new production. The inverse relationships between nutrients and temperatures have been determined and are being used to obtain surface nutrient fields from sea surface temperatures measured remotely by satellite borne sensors- i.e. AVHRR data from NOAA satellites contained in the MCSST data set for the world ocean provided by the University of Miami. The images and data derived from space in this way show the strong seasonal fluctuations and interannual el Nino fluctuations of the nitrate field. the nitrate data has been used to make estimates of new production for the equatorial pacific which are compared with shipboard measurements when available. The importance of silicate as a nutrient driving new production and the ratio of nitrate to silicate has been discovered to be crucial to better understand the causes of new production variability, so we have added these parameters to our study and have begun to make estimates of these for the equatorial Pacific, derived from the weekly averaged sea surface temperatures (SSTs).

Dugdale, Richard C.↗

NASA NTRS1995

Ultraviolet extinction to 10.8 inverse microns

UV extinction curves that represent observed variations i diffuse clouds (Zeta Oph, Xi Per, and Sigma Sco) have been derived by combining IUE and Voyager data and have been modeled by a multicomponent size distribution of silicate and carbonaceous giants. We have used theoretical model atmospheres as our reddening-free standards, and, in the case of Zeta Oph, also compare with the use of a stellar standard. An attempt was made to classify the UV spectra via theoretical spectral indices, but still missing line opacity appears to limit the use of this method at the present. The modeling includes five possible grain ingrediants, largge (0.015-0.25 micrometers) and small (0.005 micrometers) silicate grains, similarly large and small carbonaceous grains, and polycyclic aromatic hydrocarbons (PAHs). The observed extinction curves are fitted by the model via nonlinear Chi-square-minimization, varying the fractional amount of cosmic Si and C that are locked up in each igredient. The observed variation from 'steep' to 'flat' UV extinction curves is found to correspond to a modest model variation in the lower limit of the power-law size distribution of the large grains. Graphite is found to be necessary grain ingredient that cannot be replaced by the laboratory amorphous carbon materials. Carbonaceous mantles on the larger silicate grains provide no good fits to the observed curves. Using absorption properties of neutral laboratory PAHs limits PAHs to a few percent of the cosmic C abundance for acceptable fits that also give values for R(sub V) close to the observed values.

Aannestad, Per A.↗

NASA NTRS1995

The galactic distribution of aliphatic hydrocarbons in the diffuse interstellar medium

The infrared absorption feature near 2950(exp -1) (3.4 micron), characteristic of dust in the diffuse interstellar medium (ISM), is attributed to C-H stretching vibrations of aliphatic hydrocarbons. We show here that the strength of the band does not scale linearly with visual extinction everywhere, but instead increases more rapidly for objects near the center of the Galaxy, a behavior that parallels that of the Si-O stretching band due to silicate materials in the diffuse ISM. This implies that the grains responsible for the diffuse medium aliphatic C-H and silicate Si-O stretching bands are different from those responsible for much of the observed visual extinction. It also suggests that the distribution of the carbonaceous component of the diffuse ISM is not uniform throughout the Galaxy, but instead may increase in density toward the center of the Galaxy. The similar behavior of the C-H and Si-O stretching bands suggests that these two components may be coupled, perhaps in the form of silicate-core, organic-mantle grains. Several possible models of the distribution of this material are presented and it is demonstrated that the inner parts of the Galaxy has a carrier density that is 5 to 35 times higher than in the local ISM. Depending on the model used, the density of aliphatic material in the local ISM is found to be about 1 to 2 -CH3 groups m(exp -3) and about 2 to 5 -CH2- groups m(exp -3). These densities are consistent with the strengths of the 2955 and 2925 cm(exp -1) (3.4 micron) band being described by the relations A(sub nu)/tau(sub 2955 cm(exp -1)) = 270 +/- 40 and A(sub nu)/tau(sub 2925 cm(exp -1)) = 250 +/- 40 in the local diffuse ISM.

Sandford, Scott A.↗

NASA NTRS1995

Dust in the small Magellanic Cloud. 2: Dust models from interstellar polarization and extinction data

We study the dust in the Small Magellanic Cloud using our polarization and extinction data (Paper 1) and existing dust models. The data suggest that the monotonic SMC extinction curve is related to values of lambda(sub max), the wavelength of maximum polarization, which are on the average smaller than the mean for the Galaxy. On the other hand, AZV 456, a star with an extinction similar to that for the Galaxy, shows a value of lambda(sub max) similar to the mean for the Galaxy. We discuss simultaneous dust model fits to extinction and polarization. Fits to the wavelength dependent polarization data are possible for stars with small lambda(sub max). In general, they imply dust size distributions which are narrower and have smaller mean sizes compared to typical size distributions for the Galaxy. However, stars with lambda(sub max) close to the Galactic norm, which also have a narrower polarization curve, cannot be fit adequately. This holds true for all of the dust models considered. The best fits to the extinction curves are obtained with a power law size distribution by assuming that the cylindrical and spherical silicate grains have a volume distribution which is continuous from the smaller spheres to the larger cylinders. The size distribution for the cylinders is taken from the fit to the polarization. The 'typical', monotonic SMC extinction curve can be fit well with graphite and silicate grains if a small fraction of the SMC carbon is locked up in the grain. However, amorphous carbon and silicate grains also fit the data well. AZV456, which has an extinction curve similar to that for the Galaxy, has a UV bump which is too blue to be fit by spherical graphite grains.

Rodrigues, C. V.↗

NASA NTRS1996

Effect of KOH Concentration and Anions on the Performance of a Ni-H2 Battery Positive Plate

The capacity and voltage behavior of electrochemically impregnated sintered nickel positive plates was examined by galvanostatic charging and discharging in a flooded electrolyte cell. Three different concentrations of potassium hydroxide (KOH) (40, 31, and 26 percent) and 31 percent KOH containing dissolved nitrate, sulfate, or silicate were investigated. The end-of-charge voltage at C/10 charge and at 10 degrees C showed the following order: 40 percent KOH greater than 31 percent KOH alone and in the presence of the anions greater than 26 percent KOH. The mid discharge voltage at C/2 discharge was higher in 26 percent KOH, almost the same for 31 percent KOH with and without added contaminants, and much lower for 40 percent KOH. The plate capacity was marginally affected by cycling in all cases except for 40 percent KOH, where the capacity declined after 1,000 cycles at 80 percent depth of discharge (DOD). At the end of cycling, all the plates tested experienced a weight loss, except in the case of 31 percent KOH, as a result of active material extrusion. Cyclic voltammetry of miniature electrodes in 31 percent KOH showed that the cathodic peak potentials are less polarized in the presence and absence of silicate at -5 degrees C compared to 25 degrees C indicating a slightly higher voltage during discharge in a Ni-H2 battery. Futhermore, the features of the current-potential profile were practically unchanged in the presence of silicate.

Vaidyanathan, Hari↗

NASA NTRS1993

The Mid-Infrared Transmission Spectra of Antarctic Ureilites

The mid-infrared (4000-450 1/cm; 2.5-22.2 micron) transmission spectra of seven Antarctic ureilites and 10 Antarctic H-5 ordinary chondrites are presented. The ureilite spectra show a number of absorption bands, the strongest of which is a wide, complex feature centered near 1000 1/cm (10 micron) due to Si-O stretching vibrations in silicates. The profiles and positions of the substructure in this feature indicate that Mg-rich olivines and pyroxenes are the main silicates responsible. The relative abundances of these two minerals, as inferred from the spectra, show substantial variation from meteorite to meteorite, but generally indicate olivine is the most abundant (olivine:pyroxene = 60:40 to 95:5). Both the predominance of olivine and the variable olivine-to-pyroxene ratio are consistent with the known composition and heterogeneity of ureilites. The H-5 ordinary chondrites spanned a range of weathering classes and were used to provide a means of addressing the extent to which the ureilite spectra may have been altered by weathering processes. It was found that, while weathering of these meteorites produces some weak bands due to the formation of small amounts of carbonates and hydrates, the profile of the main silicate feature has been little affected by Antarctic exposure in the meteorites studied here. The mid-infrared ureilite spectra provide an additional means of testing potential asteroidal parent bodies for the ureilites. At present, the best candidates include the subset of S-type asteroids having low albedos and weak absorption features in the near infrared.

Sandford, Scott A.↗

NASA NTRS1997

Laboratory Measurements of Celestial Solids

Our experimental study has focused on laboratory measurements of the low temperature optical properties of a variety of astronomically significant materials in the infrared and mm-wave region of the spectrum. Our far infrared measurements of silicate grains with an open structure have produced a variety of unusual results: (1) the low temperature mass opacity coefficient of small amorphous 2MgO(central dot)SiO2 and MgO(central dot)2SiO2 grains are many times larger than the values previously used for interstellar grain material; (2) all of the amorphous silicate grains studied possess the characteristic temperature dependent signature associated with two level systems in bulk glass; and (3) a smaller but nonzero two level temperature dependence signature is also observed for crystalline particles, its physical origin is unclear. These laboratory measurements yield surprisingly large and variable values for the mm-wave absorption coefficients of small silicate particles similar to interstellar grains, and suggest that the bulk absorptivity of interstellar dust at these long wavelengths will not be well known without such studies. Furthermore, our studies have been useful to better understand the physics of the two level absorption process in amorphous and crystalline grains to gain confidence in the wide applicability of these results.

Sievers, A. J.↗

NASA NTRS1996

Trace element and isotope studies in oxide/phosphate/silicate inclusions of iron meteorites

Under the above grant research was funded in the following areas: 1. Pallasites: Rare earth element measurements in phosphates to determine if all pallasites fit into only two trace element groups. This work has been completed. 2. HIAB irons: To complete work on the only known silicate inclusion in a IIIAB iron meteorite. This work has been completed. 3. IIIAB irons: To continue the search for Cr-53 excesses in IIIAB iron meteorite phosphates. A part of this work has been completed 4. IIIAB irons: To complete the identification of the phosphate minerals in IIIAB iron meteorites and try to determine the phase relations and chemical history of trace element distributions during the core formation process. Work on this has been largely completed and preliminary results have been reported. The final work is being assessed prior to preparation of a manuscript for publication. 5. IIE irons: To complete work on the unique silicate assemblage in the IIE iron meteorite. Work on this was completed and a paper published. 6. Ungrouped irons: A partially devitrified silicate glass inclusion has been found in the ungrouped iron meteorite. Preliminary work on this has been reported. All the work on this has been now completed and a manuscript has been prepared and submitted for publication.

Olsen, Edward J.↗

NASA NTRS1999

Accreting Gas and Dust in Pre-Main Sequence Disk Systems

Infrared spectroscopy of pre-main sequence stars with dusty protostellar disks provide information about the evolution of refractory materials in such systems. These systems exhibit varying degrees of strength and structure in the silicate emission band situated at 10 microns wavelength. Band strength is affected by the mean grain size, while band structure is determined by the chemical composition and degree of crystallinity. In some objects, the silicate band is strong and featureless, similar to that seen in the interstellar medium. In others, the band is often weaker, and exhibits structure consistent with the presence of crystalline olivine. In these latter objects, the band is similar to that of some solar system comets. The strength and structure of the silicate band may be related to the processing history of the system.

Sitko, M. L.↗

NASA NTRS1999

The Beta Pictoris Phenomenon in Young Stars With Accreting Gas

Program Hae2BPIC resulted in usable ISO spectra of three young, Herbig Ae stars: HR 5999 (A7e, t=0.6 Myr), SV Cep (al-2e, t=1-3 Myr), and MW Vul (Al-2e, t=1-3 Myr). While too small a sample to pursue our original goal of surveying the silicate emission in these young, protoplanetary disk systems, comparison of these data with ground-based IR spectra, and published ISO observations of other HAe stars (especially the posters at PPIV) reveals the following: The known binary stars in the sample show signatures of partially crystal line silicate features by t=0.6 Myr, at an epoch when ostensibly single Herbig Ae stars have substantially stronger silicate emission dominated by amorphous grains. The known binary stars also show deficits in the optically thick continuum flux relative to coeval single stars. Comparison of ISO spectra indicates that the flux deficit seen in WD 163296 over 10-100 microns relative to AB Aur reflects a real deficit of material interior to 300.

Grady, Carol A.↗

NASA NTRS1999

The Thermal Emission Imaging System (THEMIS) Instrument for the Mars 2001 Orbiter

The primary objective of the Thermal Emission Imaging System (THEMIS) on the Mars Surveyor '01 Orbiter is to study the composition of the Martian surface at high spatial resolution. THEMIS will map the surface mineralogy using multi-spectral thermal infrared images in 8 spectral bands from 6.5 to 14.5 microns. In addition, a band centered at 15 microns will be used to map atmospheric temperatures and provide an important aid in separating the surface and atmospheric components. The entire planet will be mapped at 100 m resolution within the available data volume using a multi-spectral, rather than hyperspectral, imaging approach. THEMIS will also acquire 20 m resolution visible images in up to 5 spectral bands using a replica of the Mars 98 Orbiter (MARCI) and Lander (MARDI) cameras. Over 15,000 panchromatic (3,000 5-color), 20 x 20 km images will be acquired for morphology studies and landing site selection. The thermal-infrared spectral region contains the fundamental vibrational absorption bands of most minerals which provide diagnostic information on mineral composition. All geologic materials, including carbonates, hydrothermal silica, sulfates, phosphates, hydroxides, silicates, and oxides have strong absorptions in the 6.5-14.5 micron region. Silica and carbonates, which are key diagnostic minerals in thermal spring deposits, are readily identified using thermal-IR spectra. In addition, the ability to identify all minerals allows the presence of aqueous minerals to be interpreted in the proper geologic context. An extensive suite of studies over the past 35 years has demonstrated the utility of vibrational spectroscopy for the quantitative determination of mineralogy and petrology. The fundamental vibrations within different anion groups, such as C03, S04, P04, and SiO4, produce unique, well separated spectral bands that allow carbonates, sulfates, phosphates, silicates, oxides, and hydroxides to be readily identified. Additional stretching and bending modes involving major cations, such as Mg, Fe, Ca, and Na, allow Further mineral identification, such as the excellent discriminability of minerals within the silicate and carbonate groups.

Christensen, P. R.↗

NASA NTRS1999

Administrative Report on Training Awards

During the tenure of this award, the recipient (David Harker) conducted areas of research which resulted in the award of a doctorate degree (August 1999) from the University of Wyoming. The primary science activity was investigation of silicate dust mineralogy in comets, particularly comet C/1995 O1 (Hale-Bopp). Determination of the dust mineralogy permits us to address an important astrophysical question of relevance to the origins and evolution of solar systems, "Do comets contain relic interstellar dust grains? Since, comets represent the frozen reservoirs of primitive proto-solar dust and ice, we can gain insight into the problem of understanding the formation of protoplanetesimals in the. early solar nebula. Mid-infrared spectrophotometry (7 - 14 micron, R approx. = 180 - 360) of Hale-Bopp was obtained with the NASA/Ames HIFOGS at four distinct epochs pre- and post- perihelion ion from 1996 October through 1997 June. These observations were conducted at the Wyoming Infrared Observatory and the NASA Infrared Telescope Facility, and were supported by funds from this training grant. The emission at mid-IR wavelengths in cometary comae arises from carbon grains, and small silicate grains which produce resonance features. Hale-Bopp had the strongest silicate feature observed from any comet to date. Theoretical calculations utilizing Mie Scattering Theory were employed to construct Synthetic cometary spectra to fit with the observed HIFOGS 10 microns spectral feature of Hale-Bopp. Our analysis suggests that the observed spectra can be modeled with the Hanner grain size distribution peaked at alpha((sub p) = 0.2 microns of fractal porous grains with porosity parameter D = 2.5. This model spectrum also fits photometry points in the 3 - 5 microns region. Comparison with the ISO SWS spectrum of Hale-Bopp obtained 1996 October reveals that the crystalline olivine grains must be at it temperature hotter than computed from Mie theory.

Woodward, Charles E.↗

NASA NTRS1999

X-Ray Fingerprinting Techniques for Recognizing A Hydrological Role in the Formation of Minerals on the Surface of Mars

Previous work has demonstrated the ability of a miniaturized XRD-XRF instrument to perform in-situ analyses without sample preparation or acquisition. Deployment of this instrument on a Martian rover will allow a large number of rapid qualitative analyses, which will maximize the diversity of samples studied and selected for possible return. As a first step in designing a decision tree for recognizing minerals in complex mixtures, d spacings were plotted against intensity for several mineral groups comprising rock and soil types inferred for the surface of Mars (weathered basalt, playa and hydrothermal deposits, clay-rich soils). In all groups, d spacings cluster in a range from about 1-4 angstroms, which can under certain circumstances obscure patterns for individual phases. However, within the silicate family, minerals containing either bound OH- or molecules of H20 (clays, micas, amphiboles, zeolites) are characterized by a shift of peaks to higher d spacings. Large d spacings (greater than about 7 angstroms) thus act as a first-order filter for distinguishing hydrous from anhydrous silicates. The ability to quickly verify the presence of silicates that have interacted with water has important implications for using mineral chemistry and structure to help decipher the hydrologic and atmospheric history of Mars. This represents a beginning for developing more sophisticated methods of pattern recognition. These will combine XRD and XRF analyses with optical data to rapidly7 discern environmentally diagnostic assemblages without the necessity of identifying every peak individual mineral phase.

Metzger, Ellen P.↗

NASA NTRS2000

The Formation Age of Comets: Predicted Physical and Chemical Trends

Dust grains in Herbig Ae/Be stars are continuously replenished by infalling comets. The IR spectra of these cometary grains appear to evolve temporally from initially amorphous astronomical silicates in young protostars to crystalline olivine in much older sources. Crystalline olivine can only be produced from amorphous silicates on a time scale of months-to-years via thermal annealing at temperatures near 1000 K. Since such sustained high temperatures only occur near the central star, dust annealed at 1000 K in inner nebular regions must be continuously transported beyond the nebular snowline to be incorporated into the next generation of cometesimals. The average formation age of a comet can therefore be measured as a ratio of the annealed crystalline olivine dust component to the total dust content of the comet. Comets formed from nearly pristine interstellar materials early in the protostellar nebula stage will contain very little crystalline dust whereas comets formed towards the end of the accretion period will incorporate a much higher percentage of annealed silicate. It is unlikely that only dust grains circulate from the inner to the outer nebula; the gas associated with such dust should also find its way beyond the snowline. Since this gas and dust will have equilibrated in the higher pressure-temperature regime of the inner nebula, it will contain a much higher proportion of hydrocarbons and ammonia than more pristine interstellar ices. Therefore, in addition to a higher fraction of crystalline dust, later forming comets should also contain higher ratios of hydrocarbons to CO and ammonia to N2 than do those formed early in the history of the nebula.

Nuth, Joseph A., III↗