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At least 1,117 records · Page 62
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NASA NTRS1992

Experimental studies of the far-infrared spectra of cosmic-type ices

Work performed during the period is reported. The abstract of a paper presented at the Second International Workshop on the Nature of Cometary Organic Matter is included. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation is presented. Also, a study of clathrate hydrates was conducted in which a methanol (CH3OH) clathrate hydrate was prepared and its far-infrared spectrum investigated. This paper is also included.

Hudson, Reggie L.↗
NASA NTRS1993

Comparison of total body water estimates from O-18 and bioelectrical response prediction equations

Identification of an indirect, rapid means to measure total body water (TBW) during space flight may aid in quantifying hydration status and assist in countermeasure development. Bioelectrical response testing and hydrostatic weighing were performed on 27 subjects who ingested O-18, a naturally occurring isotope of oxygen, to measure true TBW. TBW estimates from three bioelectrical response prediction equations and fat-free mass (FFM) were compared to TBW measured from O-18. A repeated measures MANOVA with post-hoc Dunnett's Test indicated a significant (p less than 0.05) difference between TBW estimates from two of the three bioelectrical response prediction equations and O-18. TBW estimates from FFM and the Kushner & Schoeller (1986) equation yielded results that were similar to those given by O-18. Strong correlations existed between each prediction method and O-18; however, standard errors, identified through regression analyses, were higher for the bioelectrical response prediction equations compared to those derived from FFM. These findings suggest (1) the Kushner & Schoeller (1986) equation may provide a valid measure of TBW, (2) other TBW prediction equations need to be identified that have variability similar to that of FFM, and (3) bioelectrical estimates of TBW may prove valuable in quantifying hydration status during space flight.

Barrows, Linda H.↗
NASA NTRS1993

Petrologic study of the Belgica 7904 carbonaceous chondrite - Hydrous alteration, oxygen isotopes, and relationship to CM and CI chondrites

The genetic relationships between the petrology, hydration reactions, and isotopic oxygen composition in the Belgica 7904 (B7904) carbonaceous chondrite, and the relationship between B7904 and the CM and CI chondrites were investigated by characterizing seven components separated from B7904. The seven specimens included two partially altered chondrules, two phylosilicate clasts, two olivine fragments, and one matrix sample. The results of the analyses and thermodynamic calculations suggest that CI chondrites may have been produced in a two-stage alteration process from materials similar to that of the B7904 matrix, by reactions with liquid water in their parent body. The common CM chondrites may have undergone aqueous alteration in the parent body, in addition to hydration in the nebula, resulting in two-stage alterations; the parent body may have been different from that of B7904.

Ikeda, Y.↗
NASA NTRS1993

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Molina, M. J.↗
NASA NTRS1993

K/T spherules from Haiti and Wyoming: Origin, diagenesis, and similarity to some microtektites

Spherules with relict glass cores in the K/T boundary bed of Haiti allow for a comparison of these bodies with hollow goyazite shells in the K/T boundary claystone of Wyoming and with younger microtektites of the Ivory Coast strewn field. Samples of the Haitian beds from undisturbed sections at Beloc, as determined by Jehanno et al., contain both hollow shells and relict glass cores rimmed by palagonite that has been partially converted to smectite. These palagonite rims developed from hydration zones formed when hot, splash-form droplets of andesitic impact glass were deposited into water. Mutual collisions between these droplets in the ejecta curtain may have formed point-source stresses on their surfaces. Initiation of hydration would be facilitated at these surface stress points and propagated radially into the glass. The inner surface of these merged hemispherical fronts appears mammillary, which is reflected as scalloping in Haitian relict glass cores.

Bohor, B. F.↗
NASA NTRS1993

Oxygen isotopic relationships between the LEW85332 carbonaceous chondrite and CR chondrites

LEW85332, originally described as a unique C3 chondrite, was shown to be a C2 chondrite with important linkages to the CR clan. An important petrologic aspect of LEW85332 is that it contains anhydrous chondrules and hydrated matrix, and new oxygen isotopic data on chondrules, matrix and whole rock are consistent with the petrology. Chondrules fall on the equilibrated chondrite line (ECL), with a slope near 1, which goes through ordinary chondrite chondrules. This contrasts with the CR chondrule line which has a lower slope due to hydrated components. LEW85332 chondrules define a new carbonaceous chondrite chondrule line, parallel to the anhydrous CV chondrule line (CCC), consistent with the well-established concept of two oxygen isotopic reservoirs. Matrix and whole rock fall on the CR line. The whole rock composition indicates that the chondrite is dominated by chondrules, and that most of them contain light oxygen similar to that of anhydrous olivine and pyroxene separates in the Renazzo and Al Rais CR chondrites.

Prinz, M.↗
NASA NTRS1994

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

Zahniser, Mark S.↗
NASA NTRS1994

Storage and recycling of water and carbon dioxide in the earth

The stabilities and properties of water- and carbon-bearing phases in the earth have been determined from phase equilibrium measurements, combined with new data on the equations of state of water, carbon dioxide, carbonates and hydrates. The data have then been used to predict the fate of calcite and hydrous phases in subducting oceanic lithosphere. From the compositions of MORB's one can estimate concentrations of water and carbon of around 200 ppm and 80 ppm respectively in the upper mantle. Lower mantle estimates are very uncertain, but 1900 ppm water and 2000 ppm C are plausible concentrations. Measurements of the density of supercritical water to 3 GPa demonstrate that this phase is less compressible than anticipated from the equations of state of Haar et al. or Saul and Wagner and is closer to predictions based on molecular dynamics simulations. Conversely, fugacity measurements on carbon dioxide to 7 GPa show that this fluid is more compressible than predicted from the MRK equation of state. The results imply that hydrates are relatively more stable and carbonates less stable at pressures greater than 5 GPa than would be predicted from simple extrapolation of the low pressure data. Nevertheless, carbonates remain extremely refractory phases within both the upper and lower mantle.

Wood, Bernard J.↗
NASA NTRS1995

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Hallett, John↗
NASA NTRS1994

Real refractive indices of infrared-characterized nitric-acid/ice films: Implications for optical measurements of polar stratospheric clouds

The infrared spectra of nitric-acid/ice films representative of polar stratospheric clouds (PSCs) were collected with simultaneous optical interference measurements to determine the real refractive indices at lambda = 632 nm. Ice and amphorous nitric-acid/ice films were prepared by condensation of water and nitric acid vapors onto a wedged Al2O3 substrate. The real refractive indices of these films were determined from the optical interference of a reflected helium-neon laser during film growth. The indices of the amphorous films varied smoothly from n = 1.30 for ice to n = 1.49 for nitric acid, similar to observations in previous work. We were unable to obtain the refractive index of crystlline films during adsorption because of optical scattering caused by surface roughness. Therefore crystlline nitric acid hydrate films were prepared by annealing amphorous nitric-acid/ice films. Further heating caused desorption of the crystalline hydrate films. During desorption, the refractive indices for ice, NAM (nitric acid monohydrate), alpha- and beta-NAT (nitric acid trihydrate) films were measured using the optical interference technique. In agreement with earlier data, the real refractive indices for ice and NAM determined in desorption were n = 1.30 +/- 0.01 and n = 1.53 +/- 0.03, respectively. The real refractive indices for alpha- and beta-NAT were found to be n = 1.51 +/- 0.01 and n greater than or equal to 1.46, respectively. Our measurements also suggest that the shape of crystalline nitric acid particles may depend on whether they nucleate from the liquid or by vapor deposition. If confirmed by future studies, this observation may provide a means of distinguishing the nucleation mechanism of crystalline PSCs.

Middlebrook, Ann M.↗
NASA NTRS1995

CD4(+)/CD8(+) T-lymphocyte Ratio: Effects of Rehydration before Exercise in Dehydrated Men

Effects of fluid ingestion on CD4+/CD8+ T-lymphocyte cell ratios were measured in four dehydrated men (ages 30-46 yr) before and after 70 min of supine submaximal (71 % VO(sub 2max) lower extremity cycle exercise. Just before exercise, Evans blue dye was injected for measurement of plasma volume. The subjects then drank one of six fluid formulations (12 ml/kg) in 3-4 min. All six mean post-hydration (pre-exercise) CD4+/CD8+ ratios (Becton-Dickinson Fluorescence Activated Cell Sorter and FACScan Consort-30 software program were below the normal range of 1.2-1.5; mean (+/- SE) and range were 0.77 +/- 0.12 and 0.39-1.15, respectively. The post-exercise ratios increased: mean = 1.36 =/- 0.15 (P less than 0.05) and range = 0.98-1.98. Regression of mean CD4+/CD8+ ratios on mean plasma osmolality resulted in pre- and post-exercise correlation coefficients of -0.76 (P less than 0.10) and -0.92 (P less than 0.01), respectively. The decreased pre-exercise ratios (after drinking) were probably not caused by the Evans blue dye but appeared to be associated more with the stress (osmotic) of dehydration. The increased post-exercise ratios to normal levels accompanied the rehydration and were not due to the varied electrolyte and osmotic concentrations of the ingested fluids or to the varied vascular volume shifts during exercise. Thus, the level of subject hydration and plasma osmotality may be factors involved in the mechanism of immune system modulation induced by exercise.

Greenleaf, John E.↗
NASA NTRS1999

Near-Infrared Hyperspectral Image Cubes of Mars during the 1999 Opposition

We used the Goddard Space Flight Center, Acousto-Optic Tunable Filter (AOTF) Camera to obtain near-IR spectral image sets of Mars over the 1.6-3.6 micron region during the April 1999 opposition. A complete image set consists of 280 images with a spectral full-width-half maximum of 10 wavenumbers (fixed in frequency), 90 images in H-band (1.55-1.80 micron), 115 images in K-band (1.95-2.50 micron) and 75 images in L-band (2.90-3.70 micron). The short-wavelength limit is set by transmission of AOTF cell and long-wavelength limit is imposed by sensitivity of PICNIC, 256x256, HgCdTe array detector. We will discuss the new array performance and provide preliminary interpretations of some of these results. These measurements were part of a 4-observatory coordinated effort whose overall objective was to assemble a photometrically calibrated, spectrally complete ground-based image cube over the visible and near-IR spectral region. To accomplish this, four observing teams conducted the investigations with instruments spanning 0.4 to 5.0 micron. The instruments and observing facilities were (a) AOTF camera at Apache Point Observatory, 3.5m, f/10, Nasymth focus (this abstract). Primary science targets included the 3 micron water-of hydration feature and CO2, H2O ice (polar regions and clouds); (b) Visible/NIR interference-filter (24 filters) camera at Lowell Observatory, 72" telescope. 430-1050 nm. Science targets were Fe(2+), Fe(3+) mineralogy and coarse grain hematite search; (c) NMSU Tortugas Mountain Observatory, 60 cm telescope, CCD photometry with same filter set as Lowell; (d) KPNO cryogenic grating/slit spectrometer (CRSP/SALLY) at KPNO 2.1 m, f/15 Cassegrain focus (see abstract by D. Glenar, et. al., this meeting). Selected wavelengths in 3-5 micron region (L, M band). Science targets included water-of-hydration feature (3-4 micron long wave extension) and sulfate mineralogy. Observers participating in this campaign included Dave Glenar, John Hillman, Gordon Bjoraker and Fred Espenak from GSFC, Nancy Chanover, Jim Murphy and A. S. MurTell from NMSU, Leslie Young from BU, Diana Blaney from JPL and Dick Joyce from KPNO.

Hillman, John J.↗
NASA NTRS1999

Renal Stone Risk During Space Flight

Space flight produces a number of metabolic and physiological changes in the crewmembers exposed to microgravity. Following launch, body fluid volumes, electrolyte levels, and bone and muscle undergo changes as the human body adapts to the weightless environment. Changes in the urinary chemical composition may lead to the potentially serious consequences of renal stone formation. Previous data collected immediately after space flight indicate changes in the urine chemistry favoring an increased risk of calcium oxalate and uric acid stone formation (n = 323). During short term Shuttle space flights, the changes observed include increased urinary calcium and decreased urine volume, pH and citrate resulting in a greater risk for calcium oxalate and brushite stone formation (n = 6). Results from long duration Shuttle/Mir missions (n = 9) followed a similar trend and demonstrated decreased fluid intake and urine volume and increased urinary calcium resulting in a urinary environment saturated with the calcium stone-forming salts. The increased risk occurs rapidly upon exposure to microgravity, continues throughout the space flight and following landing. Dietary factors, especially fluid intake, or pharmacologic intervention can significantly influence the urinary chemical composition. Increasing fluid intake to produce a daily urine output of 2 liters/day may allow the excess salts in the urine to remain in solution, crystals formation will not occur and a renal stone will not develop. Results from long duration crewmembers (n = 2) who had urine volumes greater than 2.5 L/day minimized their risk of renal stone formation. Also, comparisons of stone-forming risk in short duration crewmembers clearly identified greater risk in those who produced less than 2 liters of urine/day. However, hydration and increased urine output does not correct the underlying calcium excretion due to bone loss and only treats the symptoms and not the cause of the increased urinary salts. Dietary modification and promising pharmacologic treatments may also be used to reduce the potential risk for renal stone formation. Potassium citrate is being used clinically to increase the urinary inhibitor levels to minimize the development of crystals and the growth of renal stones. Bisphosphonates are a class of drugs recently shown to help in patients with osteoporosis by inhibiting the loss of bones in elderly patients. This drug could potentially prevent the bone loss observed in astronauts and thereby minimize the increase in urinary calcium and reduce the risk for renal stone development. Results of NASA's renal stone risk assessment program clearly indicate that exposure to microgravity changes the urinary chemical environment such that there is an increased risk for supersaturation of stone-forming salts, including calcium oxalaie and brushite. These studies have indicated specific avenues for development of countermeasures for the increased renal stone risk observed during and following space flight. Increased hydration and implementation of pharmacologic countermeasures should largely mitigate the in-flight risk of renal stones.

Whitson, Peggy A.↗
NASA NTRS2001

Stratospheric Polar Freezing Belt Causes Denitrification

Trajectory cloud model calculations are presented to show that homogeneous freezing of nitric acid hydrates can produce a polar freezing belt in both hemispheres that can cause denitrification. While hydrate cloud microphysical properties are similar over both poles, the shorter persistence of clouds in the Arctic prevents the depth of the denitrified layers from growing beyond a few kilometers. The 1999-2000 Arctic winter is unique in showing a distinct denitrification profile with a depth of approx. 4.5 km that is nearly half as deep as that computed for a typical Antarctic winter.

Tabazadeh, A.↗
NASA NTRS1995

Measurements of Holographic Properties of Bacteriorhodopsin Films

Several different bacteriorhodopsin (BR) films are characterized with respect to general holographic properties. Experimental measurements include diffraction efficiency and sensitivity as functions of writing intensity and grating frequency, hologram thermal decay behavior, diffraction efficiency as a function of grating tilt within the film and modulation depth, and estimates of the refractive index change from the diffraction efficiency data. The films studied include those made from wildtype BR and the genetic variants D96N and D96N/T46V. The maximum diffraction efficiency measured was just over 3% for a hydrated wildtype BR film. The films' holographic properties were found to be relatively insensitive to grating frequency and grating tilt angle. The diffraction efficiency dropped off more sharply as a function of modulation depth than a purely linear medium, and only the hydrated wildtype film exhibited significant behavior variation with different writing intensities.

Downie, John D.↗
NASA NTRS2001

Vibrational Spectroscopy and Astrobiology

Role of vibrational spectroscopy in solving problems related to astrobiology will be discussed. Vibrational (infrared) spectroscopy is a very sensitive tool for identifying molecules. Theoretical approach used in this work is based on direct computation of anharmonic vibrational frequencies and intensities from electronic structure codes. One of the applications of this computational technique is possible identification of biological building blocks (amino acids, small peptides, DNA bases) in the interstellar medium (ISM). Identifying small biological molecules in the ISM is very important from the point of view of origin of life. Hybrid (quantum mechanics/molecular mechanics) theoretical techniques will be discussed that may allow to obtain accurate vibrational spectra of biomolecular building blocks and to create a database of spectroscopic signatures that can assist observations of these molecules in space. Another application of the direct computational spectroscopy technique is to help to design and analyze experimental observations of ice surfaces of one of the Jupiter's moons, Europa, that possibly contains hydrated salts. The presence of hydrated salts on the surface can be an indication of a subsurface ocean and the possible existence of life forms inhabiting such an ocean.

Chaban, Galina M.↗
NASA NTRS2001

Investigating Type I Polar Stratospheric Cloud Formation Mechanisms with POAM Satellite Observations

Type Ia PSCs are believed to be composed of nitric acid hydrate particles. Recent results from the SOLVE/THESEO 2000 campaign showed evidence that this type of PSC was composed of a small number of very large particles capable of sedimentary denitrification of regions of the stratosphere. It is unknown whether homogeneous or heterogeneous nucleation is responsible for the formation of these PSCs. Arctic winters are tending to be colder in response to global tropospheric warming. The degree to which this influences ozone depletion will depend on the freezing mechanism of nitric acid hydrate particles. If nucleation is homogeneous it implies that the freezing process is an inherent property of the particle, while heterogeneous freezing means that the extent of PSCs will depend in part on the number of nuclei available. The Polar Ozone and Aerosol Measurement (POAM)II and III satellites have been making observations of stratospheric aerosols and Polar Stratospheric Clouds (PSCs) since 1994. Recently, we have developed a technique that can discriminate between Type Ia and Ib PSCs using these observations. A statistical approach is employed to demonstrate the robustness of this approach and results are compared with lidar measurements. The technique is used to analyze observations from POAM II and II during Northern Hemisphere winters where significant PSC formation occurred with the objective of exploring Type I PSC formation mechanisms. The different PSCs identified using this method exhibit different growth curve as expressed as extinction versus temperature.

Strawa, Anthony W.↗
NASA NTRS2004

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗