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At least 199 records · Page 11

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NASA NTRS1994

Measurement of atmospheric OH by titration of near-IR fluorescent dyes

Recent research has shown that certain polymethine dyes can be detected at ultratrace levels (greater than or equal to 6x10(exp -14) M) in solution by fluorimetry. These detection limits are possible because of the inherent sensitivity of fluorescence techniques, because the dyes fluoresce in the near infrared region where background interference is negligible, and because powerful infrared diode lasers are now available to improve the signal to noise ratio. Other work has shown that the hydroxyl radical destroys the ability of polymethine dyes to fluoresce. These observations form the basis for a new hydroxyl radical detector that is essentially a fluorometric titrator. Theoretically, the detector should show an acceptable sensitivity and response time. Assuming that the atmospheric HO concentration is about 10(exp -11) moles m(exp -3) (i.e. 10(exp 6) molecules cm(exp -3)), then 10 L of air 'titrated' with 20 mL of 10(exp -11) M dye solution (an easily detected concentration) should result in a drop in the fluorescent signal of 50 percent - a readily detectable change. At a flow rate of 3 L min(exp -1) the sampling time would be 3 minutes. The biggest potential problem is selectivity: other oxidants may also cause the fluorescence signal to be lost. The chemistry of polymethine dyes has not been studied in detail and so no quantitative data are available. However, a survey of the literature suggests that in general HO should react up to six orders of magnitude faster than HO2 and other radicals such as RO2 and RO. It should also react much more rapidly than H2O2 and O3. Thus it may be possible to discriminate kinetically against potential interfering substances. It was shown in the laboratory that 10(exp -4) M H2O2 has little effect on the absorption spectrum of the dye IR125 over a period of hours but that the band at 780 nm is slowly lost in water over a period of days even under argon in the dark. By contrast, DMSO solutions of IR125 are stable.

Betterton, Eric A.↗

NASA NTRS1995

Seasonal variations in the atmospheric distribution of a reactive chlorine compound, tetrachloroethene (CCl2 = CCl2)

Tropospheric mixing ratios of CCl2 = CCl2 were measured at remote surface locations in the Pacific between 71 deg N and 47 deg S during September and December of 1989, and March and June of 1990. The observed gradient of decreasing concentrations from the northern to the southern hemisphere, and very low concentrations in the southern hemisphere throughout the year, indicates a predominant input from the northern hemisphere. Seasonal measurements in the northern hemisphere showed maximum CCl2 = CCl2 concentrations occurring in the late summer. This distinct seasonal variation is strongly coupled to the atmompheric abundance of hydroxyl radical, the only important species responsible for CCl2 = CCl2 removal. With the estimated global CCl2 =CCl2 emissions, the lifetime is calculated to be about 5.4 months which is in good agreement with the 4.0 month estimate obtained from the inverse ratio of its measured hydroxyl reaction rate constant compared with that of methyl-chloroform CH3CCl3.

Wang, Charles J.-L.↗

NASA NTRS1995

Annual and Semi-Annual Temperature Oscillations in the Upper Mesosphere

Fourier transform spectrometer observations of the mesosphere have been performed at the University of Michigan (latitude: 42.5 N) on a long term basis. A database of near infrared Meinel hydroxyl spectra has been accumulated from which rotational temperatures have been determined. Harmonic analysis of one-day averaged temperatures for the period 1992.0 to 1994.5 has shown a distinct annual and semi-annual variation. Subsequent fitting of a five term periodic function characterizing the annual and semi-annual temperature oscillations to the daily averaged temperatures was performed. The resultant mean temperature and the amplitudes and phases of the annual and semi-annual variations are shown to coincide with an emission height slightly above 85 km which is consistent with the mean rocket derived altitude for peak nocturnal hydroxyl emission.

Niciejewski, R. J.↗

NASA NTRS2002

Laboratory Studies of the Photochemistry of Peroxynitric Acid

Observations of odd hydrogen radicals at high SZA in the lower stratosphere have demonstrated that our understanding of the HO(x) chemistry is incomplete [Wennberg et al., 1994a; Salawitch et al., 1994; Wennberg et al., 1999]. In particular, the concentrations of the HO(x) radicals are significantly larger than expected under weak photolytic conditions. Donaldson et al. [1997] have speculated that excitation of overtones of the OH stretching frequency in molecules such as HNO3 and HO2NO2 may be significant sources of HO(x) under these conditions. Although weak, vibrationally mediated photolysis may be important because it occurs in the near IR and visible and can provide energy in excess of the dissociation energy (D(o)): HONO2 + hv yields OH + NO (D(o) approx. 600 nm) and HOONO2 + hv yields OH + NO3 (D(o) approx. 735 nm) HOONO2 + hv yields HO2 + NO2 (D(o) approx. 1250 nm). In this project we developed instrumentation to characterize the photodissociation yields of hydroxyl containing compounds in the visible and near IR. This effort has involved coupling a tunable photolysis optical parametric oscillator (OPO) laser system with precise determination of the hydroxyl radical. The OPO system [Wu et al., 1997] was developed with support from the NSF Major Research Instrumentation Fund in a proposal entitled "Development of Novel, Compact Light Sources for Advanced Spectroscopy in Atmospheric Science and Materials Research" (Geoffrey A. Blake, P.I. California Institute of Technology).

Wennberg, Paul O.↗

NASA NTRS2002

Hydrogen in rocks: an energy source for deep microbial communities

To survive in deep subsurface environments, lithotrophic microbial communities require a sustainable energy source such as hydrogen. Though H2 can be produced when water reacts with fresh mineral surfaces and oxidizes ferrous iron, this reaction is unreliable since it depends upon the exposure of fresh rock surfaces via the episodic opening of cracks and fissures. A more reliable and potentially more voluminous H2 source exists in nominally anhydrous minerals of igneous and metamorphic rocks. Our experimental results indicate that H2 molecules can be derived from small amounts of H2O dissolved in minerals in the form of hydroxyl, OH- or O3Si-OH, whenever such minerals crystallized in an H2O-laden environment. Two types of experiments were conducted. Single crystal fracture experiments indicated that hydroxyl pairs undergo an in situ redox conversion to H2 molecules plus peroxy links, O3Si/OO\SiO3. While the peroxy links become part of the mineral structure, the H2 molecules diffused out of the freshly fractured mineral surfaces. If such a mechanism occurred in natural settings, the entire rock column would become a volume source of H2. Crushing experiments to facilitate the outdiffusion of H2 were conducted with common crustal igneous rocks such as granite, andesite, and labradorite. At least 70 nmol of H2/g diffused out of coarsely crushed andesite, equivalent at standard pressure and temperature to 5,000 cm3 of H2/m3 of rock. In the water-saturated, biologically relevant upper portion of the rock column, the diffusion of H2 out of the minerals will be buffered by H2 saturation of the intergranular water film.

Hydrogen/analysis↗

NASA NTRS1999

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Review↗

NASA NTRS2007

U-937 Toxicity Testing of Lunar Dust Stimulant (JSC-1A-vf)

With NASA planning to extend the human presence to the moon by 2020, the dangers of the lunar environment must be assessed and appropriate countermeasures must be developed. Possible toxic effects of the lunar dust are of particular importance to human health because of the dust's chemical composition, reactivity, and small size. This project focuses on the toxicity of lunar dust stimulant (JSC-1A-vf), in both its active and passive forms, using U-937 human monocyte cells. Simulant was mechanically activated from its passive form by grinding, and its ability to produce hydroxyl radicals was determined. To test for toxicity, active and passivated simulant was diluted in media and applied to the cells for various time periods. Toxicity was then estimated using flow cytometry on the Guava Personal Cell Analysis system. Preliminary results suggest that passivated stimulant is slightly toxic, with an increase in toxicity for activated stimulant. Toxicity results may be affected by cell lysing behavior and quenching of hydroxyl radical production by the cell media.

Bales, Kristyn↗

NASA NTRS2009

Luna: What Did We Learn and What Should We Expect?

This presentation presents a look at the space program's background prior to lunar exploration and highlights the Apollo program and lessons learned from lunar exploration. The possibilities of exposures and difficulties attributed to lunar dust are described, including obscured vision, clogged equipment, coated surfaces, and inhalation, among others. A lunar dust simulant is proposed to support preliminary studies. Lunar dust is constantly activated by meteorite lunar dust, UV radiation and elements of solar wind - this active dust could produce reactive species. Methods of deactivation must be determined before new lunar missions, but first we must understand how to reactivate dust on Earth. Activation methods tested and described here include crushing/grinding or UV activation. Grinding time has a direct effect on amount of hydroxyl radicals produced upon addition of ground quartz to a solution. An increase in hydroxyl production was also seen for a lunar simulant with increased grinding.

Wallace, William T.↗

NASA NTRS2008

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Gwo, Dz-Hung↗

NASA NTRS2010

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas↗

NASA NTRS2012

Fluorescence-Based Sensor for Monitoring Activation of Lunar Dust

This sensor unit is designed to determine the level of activation of lunar dust or simulant particles using a fluorescent technique. Activation of the surface of a lunar soil sample (for instance, through grinding) should produce a freshly fractured surface. When these reactive surfaces interact with oxygen and water, they produce hydroxyl radicals. These radicals will react with a terephthalate diluted in the aqueous medium to form 2-hydroxyterephthalate. The fluorescence produced by 2-hydroxyterephthalate provides qualitative proof of the activation of the sample. Using a calibration curve produced by synthesized 2-hydroxyterephthalate, the amount of hydroxyl radicals produced as a function of sample concentration can also be determined.

Wallace, William T.↗

NASA NTRS2012

Highly porous and mechanically strong ceramic oxide aerogels

Leventis, Nicholas↗

NASA NTRS2014

Hydrogen-Bonding Surfaces for Ice Mitigation

Ice formation on aircraft, either on the ground or in-flight, is a major safety issue. While ground icing events occur predominantly during the winter months, in-flight icing can happen anytime during the year. The latter is more problematic since it could result in increased drag and loss of lift. Under a Phase I ARMD NARI Seedling Activity, coated aluminum surfaces possessing hydrogen-bonding groups were under investigation for mitigating ice formation. Hydroxyl and methyl terminated dimethylethoxysilanes were prepared via known chemistries and characterized by spectroscopic methods. These materials were subsequently used to coat aluminum surfaces. Surface compositions were based on pure hydroxyl and methyl terminated species as well as mixtures of the two. Coated surfaces were characterized by contact angle goniometry. Receding water contact angle data suggested several potential surfaces that may exhibit reduced ice adhesion. Qualitative icing experiments performed under representative environmental temperatures using supercooled distilled water delivered via spray coating were inconclusive. Molecular modeling studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition. Chain mobility resulted from the creation of "pockets" of increased free volume for longer chains to occupy.

Smith, Joseph G., Jr.↗

NASA NTRS2012

On-Going Laboratory Efforts to Quantitatively Address Clay Abundance on Mars

Data obtained at visible and near-infrared wavelengths by OMEGA on MarsExpress and CRISM on MRO provide definitive evidence for the presence of phyllosilicates and other hydrated phases on Mars. A diverse range of both Fe/Mg-OH and Al-OH-bearing phyllosilicates were identified including the smectites, nontronite, saponite, and montmorillonite. In order to constrain the abundances of these phyllosilicates spectral analyses of mixtures are needed. We report on our on-going effort to enable the quantitative evaluation of the abundance of hydrated-hydroxylated silicates when they are contained in mixtures. We include two component mixtures of hydrated/hydroxylated silicates with each other and with two analogs for other martian materials; pyroxene (enstatite) and palagonitic soil (an alteration product of basaltic glass). For the hydrated-hydroxylated silicates we include saponite and montmorillonite (Mg- and Al- rich smectites). We prepared three size separates of each end-member for study: 20-45, 63-90, and 125-150 μm. As the second phase of our effort we used scanning electron microscopy imaging and x-ray diffraction to characterize the grain size distribution, and structural nature, respectively, of the mixtures. Visible and near-infrared reflectance spectra of the 63-90 micrometers grain size of the mixture samples are shown in Figure 1. We discuss the results of our measurements of these mixtures.

Mars↗

NASA NTRS2014

Experimental and Theoretical Study of Thermodynamics of the Reaction of Titania and Water at High Temperatures

The transpiration method was used to determine the volatility of titanium dioxide (TiO2) in water vapor-containing environments at temperatures between 1473 and 1673 K. Water contents ranged from 0 to 76 mole % in oxygen or argon carrier gases for 20 to 250 hr exposure times. Results indicate that oxygen is not a key contributor to volatilization and the primary reaction for volatilization in this temperature range is: TiO2(s) + H2O(g) = TiO(OH)2(g). Data were analyzed with both the second and third law methods to extract an enthalpy and entropy of formation. The geometry and vibrational frequencies of TiO(OH)2(g) were computed using B3LYP density functional theory, and the enthalpy of formation was computed using the coupled-cluster singles and doubles method with a perturbative correction for connected triple substitutions [CCSD(T)]. Thermal functions are calculated using both a structure with bent and linear hydroxyl groups. Calculated second and third heats show closer agreement with the linear hydroxyl group, suggesting more experimental and computational spectroscopic and structural work is needed on this system.

equilibrium↗

NASA NTRS2015

The Effect of Surface Chemical Functionality Upon Ice Adhesion

In nature, anti-freeze proteins present in fish utilize specific organic functionalities to disrupt ice crystal formation and propagation. Based on these structures, surfaces with controlled chemical functionality and chain length were evaluated both experimentally and computationally to assess the effect of both parameters in mitigating ice formation. Linear aliphatic dimethylethoxysilanes terminated with methyl or hydroxyl groups were prepared, characterized, and used to coat aluminum. The effect upon icing using a microdroplet freezing apparatus and the Adverse Environment Rotor Test Stand found hydroxyl-terminated materials exhibited a greater propensity for ice formation and adhesion. Molecular dynamics simulations of a silica substrate bearing functionalized species of similar composition were brought into contact with a pre-equilibrated ice crystal. Several parameters including chain mobility were monitored to ascertain the size of a quasi-liquid layer. The studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition.

Smith, Joseph G., Jr.↗

NASA NTRS2017

Remotely Distinguishing and Mapping Endogenic Water on the Moon

Water and/or hydroxyl detected remotely on the lunar surface originates from several sources: (i) comets and other exogenous debris; (ii) solar wind implantation; (iii) the lunar interior. While each of these sources is interesting in its own right, distinguishing among them is critical for testing hypotheses for the origin and evolution of the Moon and our Solar System. Existing spacecraft observations are not of high enough spectral resolution to uniquely characterize the bonding energies of the hydroxyl molecules that have been detected. Nevertheless, the spatial distribution and associations of H, OH- or H2O with specific lunar lithologies provide some insight into the origin of lunar hydrous materials. The global distribution of OH-/H2O as detected using infrared spectroscopic measurements from orbit is here examined, with particular focus on regional geological features that exhibit OH-/H2O absorption band strengths that differ from their immediate surroundings.

Klima, Rachel L.↗

NASA NTRS2018

Solar Wind Implantation Into the Lunar Regolith: Monte Carlo Simulations of H Retention in a Surface With Defects and the H2 Exosphere

The solar wind implants protons into the top 20–30 nm of lunar regolith grains, and the implanted hydrogen will diffuse out of the regolith but also interact with oxygen in the regolith oxides. We apply a statistical approach to estimate the diffusion of hydrogen in the regolith hindered by forming temporary bonds with regolith oxygen atoms. A Monte Carlo simulation was used to track the temporal evolution of bound OH surface content and the H2 exosphere. The model results are consistent with the interpretation of the Chandrayaan‐1 M3 observations of infrared absorption spectra by surface hydroxyls as discussed in Li and Milliken (2017, https://doi.org/10.1126/sciadv.1701471). The model reproduced the latitudinal concentration of OH by using a Gaussian energy distribution of f(U(sub 0) = 0.5 eV, U(sub W) = 0.078–0.1 eV) to characterize the activation energy barrier to the diffusion of hydrogen in space weathered regolith. In addition, the model results of the exospheric content of H2 are consistent with observations by the Lyman Alpha Mapping Project on the Lunar Reconnaissance Orbiter. Therefore, we provide support for hydroxyl formation by chemically trapped solar wind protons.

Tucker, O. J.↗