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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Luminescence and ESR studies of relationships between O(-)-centres and structural iron in natural and synthetically hydrated kaolinites

Luminescence, induced by dehydration and by wetting with hydrazine and unsymmetrically substituted hydrazine, and related ESR spectra have been observed from several kaolinites, synthetically hydrated kaolinites, and metahalloysites. The amine-wetting luminescence results suggest that intercalation, not a chemiluminescence reaction, is the luminescence trigger. Correlation between hydration-induced luminescence and g = 2 ESR signals associated with O(-)-centres in several natural halloysites, and concurrent diminution of the intensity of both these signal types as a function of aging in two 8.4 angstroms synthetically hydrated, kaolinites, confirm a previously-reported relationship between the luminescence induced by dehydration and in the presence of O(-)-centres (holes, i.e., electron vacancies) in the tetrahedral sheet. Furthermore, the ESR spectra of the 8.4 angstroms hydrate showed a concurrent change in the line shape of the g = 4 signal from a shape usually associated with structural Fe in an ordered kaolinite, to a simpler one typically observed in more disordered kaolinite, halloysite, and montmorillonite. Either structural Fe centres and the O(-)-centres interact, or both are subject to factors previously associated with degree of order. The results question the long-term stability of the 8.4 angstroms hydrate, although XRD does not indicate interlayer collapse over this period. Complex inter-relationships are shown between intercalation, stored energy, structural Fe, and the degree of hydration which may be reflected in catalytic as well as spectroscopic properties of the clays.

NASA Center ARC↗
NASA NTRS1991

Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

NASA Discipline Number 52-20↗
NASA NTRS1971

Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

Jackson, T. A.↗
NASA NTRS1979

Prebiotic nucleotide oligomerization in a fluctuating environment - Effects of kaolinite and cyanamide

The clay kaolinite was tested for its ability to promote nucleotide oligomerization in model prebiotic systems. Heterogeneous mixtures of clay, water and nucleotide were repeatedly evaporated to dryness at 60 C and redissolved in water in cyclic fashion in the presence or absence of cyanamide and/or ammonium chloride. With or without cycling, kaolinite alone did not promote the oligomerization of nucleotides at detectable levels. Cycling of clay in combination with cyanamide, however, promoted high levels of condensation to a mixture of oligonucleotides and dinucleotide pyrophosphate without requiring ammonium chloride. Although cycling with clay favored synthesis of dinucleotide pyrophosphate, cycling without clay enhanced formation of oligonucleotides. These results support the hypothesis that the presence of clays in fluctuating environments would have influenced the course of prebiotic condensation reactions.

Odom, D. G.↗
NASA NTRS1985

Characterization of dehydration-induced luminescence of kaolinite

The dehydration-induced luminescence of a colloidal kaolinite is investigated experimentally, with particular attention given to the effect of various treatments on the luminescence characteristics. It is found that the total photon count of the emitted light is linearly related to the film thickness up to a thickness of 30 microns; mechanical stress in the form of grinding increases the photon output and produces extensive changes in the emission kinetics. A direct check of the emission wavelength dependence (by using color filters) indicates that roughly 75 percent of the emission occurs in the wavelength range below 410 nm. It is also found that incorporation of fluorescent molecules into the kaolinite paste increases the photon output and may indicate the transfer of ultraviolet photons to the fluorescent probe.

Lahav, N.↗
NASA NTRS1991

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Coyne, L. M.↗
NASA NTRS1991

Surface activation of air oxidation of hydrazine on kaolinite. 2. Consideration of oxidizing/reducing entities in relationship to other compositional, structural, and energetic factors

The rates (previously reported) for the air oxidation of hydrazine on kaolinite and substituent oxides of kaolinite showed a complex dependence on the relative amounts of several structural oxidizing/reducing entities within the reaction-promoting solids. The rates indicated an important role of the clay but no dominant role of any one of the oxidizing/reducing entities. In this paper we review (a) the reaction-promoting activity of these centers as studied in other systems, (b) various spectroscopic results showing interaction between these entities in clays, and (c) reported spectroscopic studies of the complexation between hydrazine and aluminosilicate surfaces as a whole, in an effort to propose a mechanism for the reaction. Whereas some uncertainties remain, the present synthesis concludes that a mechanism operating through single electron/hole transfers and hydrogen atom transfers by discrete centers is adequate to explain the observed rate behaviors including the observed second order dependence of the oxidation rate on catalyst amount. The effects of these operations on the catalyst can result in no alteration of, or complete or partial electronic relaxation of its contingent of trapped separated charge pairs. The degree to which surface complexation as a whole, intercalation, or luminescent processes may also be associated with the reaction cannot be adequately assessed with the information in hand.

NASA Program Exobiology↗
NASA NTRS2007

Enhancement of Hydrophilic Characteristics of Non-Wetting Porous Substrates by Kaolinite Treatment

The use of porous media has enormous potential for thermal management and phase separation in terrestrial, micro, Lunar and Marian gravity environments. Recently, a porous media based gravity insensitive condensing heat exchanger for humidity control has been proposed and successfully demonstrated by the authors. A strongly hydrophilic porous substrate is essential for condensing and trapping water vapor from the airstreams. However, most porous media which have good thermal characteristics are poorly wetting to water. This poses a significant obstacle in the development of the porous media based condensing heat exchanger. In response to this problem, a clay based process was developed for improving the wettability of non-wetting and partially wetting porous media. It was demonstrated that poorly wetting porous graphite as well as porous stainless steel could be converted to a completely wetting porous substrate by kaolinite treatment. The process enhances the wettability of both the surface and the interior pores. The paper presents experimental results of enhanced wettability of the treated substrate in terms of imbibition rate and capillary pressure as a function of saturation. The long term stability of the treated surface is also investigated and discussed.

Khan, Lutful I.↗
NASA NTRS1988

The Western North American Cretaceous-Tertiary (K-T) boundary interval and its content of shock-metamorphosed minerals: Implications concerning the K-T boundary impact-extinction theory

At 20 sites in the Raton Basin of Colorado and New Mexico, and at several other sites in Wyoming, Montana, and Canada, a pair of claystone units, an Ir abundance anomaly, and a concentration of shock-metamorphosed minerals mark the palynological K-T boundary. The K-T boundary claystone, which is composed of kaolinite and small amounts of illite/smectite mixed-layer clay, is similar in most respects to kaolinite tonstein layers in coal beds. At some, but not all, K-T boundary localities, the boundary claystone contains solid kaolinite and hollow and solid goyazite spherules, 0.05 to 1.2 mm in diameter. The upper unit, the K-T boundary impact layer, consists chiefly of kaolinite and various amounts of illite/smectite mixed-layer clay. The impact layer and boundary claystone are similar chemically, except that the former has slightly more Fe, K, Ba, Cr, Cu, Li, V, and Zn than the latter. The facts that the boundary claystone and impact layer contain anomalous amounts of Ir, comprise a stratigraphic couplet at Western North American sites, and form thin, discrete layers, similar to air-fall units (volcanic or impact), suggest that the claystone units are of impact origin. Significantly, the impact layer contains as much as 2 percent clastic mineral grains, about 30 percent of which contain multiple sets of shock lamellae. Only one such concentration of shocked minerals has been found near the K-T boundary. The type of K-T boundary shock-metamorphosed materials (quartzite and metaquartzite) in the impact layer and the lack of shock lamellae in quartz and feldspar of pumice lapilli and granitic xenoliths in air-fall pumice units of silicic tuffs, such as the Bishop Tuff, eliminate the possibility that the shock-metamorphosed minerals in the K-T impact layer are of volcanic origin. The global size distribution and abundance of shock-metamorphosed mineral grains suggest that the K-T impact occurred in North America.

Izett, G. A.↗
NASA NTRS1982

Prolonged triboluminescence in clays and other minerals

Samples of various clays and minerals were ground or fractured and monitored with a liquid scintillation spectrometer in order to obtain triboluminescent decay curves. Kaolinite samples displayed several million counts/min after grinding, with a surface area emission estimated at tens of billions of photons/sq cm of surface. The photon production rates varied with the origin of the sample, and kaolinite continually yielded higher production rates than bentonite. The addition of water to the samples slightly increased the count rate of emitted light, while the addition of the fluorescent molecule substance tryptofan significantly enhanced the count rate. Freezing smears of kaolinite and montmorillonite in liquid nitrogen and in a salt ice mixture also induced triboluminescence in the montmorillonite. A possible connection between powdery triboluminescent materials formed in mining industries and respiratory disorders among miners is suggested.

Lahav, N.↗
NASA NTRS1982

Interaction between ATP, metal ions, glycine, and several minerals

Interactions between ATP, glycine and montmorillonite and kaolinite clay minerals in the presence of various metal cations are investigated. The adsorption of adenine nucleotides on clays and Al(OH)3 was measured as a function of pH, and glycine condensation was followed in the presence of ATP, ZnCl2, MgCl2 and either kaolinite or montmorillonite. The amounts of ATP and ADP adsorbed are found to decrease with increasing Ph, and to be considerably enhanced in experiments with Mg(2+)- and Zn(2+)-montmorillonite with respect to Na(+)-montmorillonite. The effects of divalent cations are less marked in kaolinite. Results for Al(OH)3 show the importance of adsorption at clay platelet edges at high pH. The decomposition of ATP during drying at high temperature is observed to be inhibited by small amounts of clay, vacuum, or Mg(2+) or Zn(2+) ions, and to be accompanied by peptide formation in the presence of glycine. Results suggest the importance of Zn(2+) and Mg(2+) in chemical evolution.

Rishpon, J.↗
NASA NTRS1988

Discrimination of hydrothermal alteration mineral assemblages at Virginia City, Nevada, using the airborne imaging spectrometer

The purpose of this study is to use airborne imaging spectrometer data to discriminate hydrothermal alteration mineral assemblages associated with silver and gold mineralization at Virginia City, NV. The data is corrected for vertical striping and sample gradients, and converted to flat-field logarithmic residuals. Log residual spectra from areas known to be altered are compared to field spectra for kaolinitic, illitic, sericitic, and propylitic alteration types. The areal distributions of these alteration types are estimated using a spectral matching technique. Both visual examination of spectra and the matching techniques are effective in distinguishing kaolinitic, illitic, and propylitic alteration types from each other. However, illitic and sericitic alteration cannot be separated using these techniques because the spectra of illite and sericite are very similar. A principal components analysis of 14 channels in the 2.14-2.38 micron wavelength region is also successful in discriminating and mapping illitic, kaolinitic, and propylitic alteration types.

Hutsinpiller, Amy↗
NASA NTRS1982

Mineral identification from orbit - Initial results from the Shuttle multispectral infrared radiometer

The Shuttle multispectral IR radiometer (SMIRR) was designed to obtain surface reflectance data in ten spectral bands in order to evaluate the usefulness of a future imaging system for remote mineral identification. Attention was given to the 2.0-2.4 micron region, which has a wealth of spectral absorption features and appeared to have potential for the identification of CO3- and OH-bearing minerals such as the kaolinite and montmorillonite clays. SMIRR radiances were normalized by using a spectrum for dune sand collected in the Kharga Depression in Egypt. Direct identifications have been made of kaolinite-containing and carbonate material, indicating an exceptional potential for future orbital platform narrowband spectral imaging systems for mineralogical mapping.

Goetz, A. F. H.↗
NASA NTRS1983

Preliminary analysis of Shuttle multispectral radiometer data for southern Egypt

The Shuttle Multispectral Infrared Radiometer (SMIRR) is a spectroradiometer covering the region from 0.5 to 2.5 microns in 10 channels that acquired data from spots 100 m in diameter along the subspacecraft ground track. It was flown aboard the second flight of the Space Shuttle Columbia, November 12-14, 1981. Data collected during orbit 16 over southern Egypt show that carbonate rocks, kaolinite, and possibly montmorillonite can be identified by their SMIRR spectral signatures and limited knowledge of the lithologic units present. Detailed analysis of SMIRR data for this area indicates that calcite, kaolinite, and montmorillonite rocks give rise to absorption features that result in characteristic 10 channel spectra.

Rowan, L. C.↗
NASA NTRS1986

Identification of hydrothermal alteration assemblages using airborne imaging spectrometer data

Airborne Imaging Spectrometer (AIS) data, field and laboratory spectra and samples for X-ray diffraction analysis were collected in argillically altered Tertiary volcanic rocks in the Hot Creek Range, Nevada. From laboratory and field spectral measurements in the 2.0 to 2.4 micron range and using a spectroradiometer with a 4 nm sampling interval, the absorption band centers for kaolinite were loacted at 2.172 and 2.215 microns, for montmorillonite at 2.214 micron and for illite at 2.205. Based on these values and the criteria for resolution and separtion of spectral features, a spectral sampling interval of less than 4 nm is necessary to separate the clays. With an AIS spectral sampling interval of 9.3 nm, a spectral matching algorithm is more effective for separating kaolinite, montmorillonite, ad illite in Hot Creek Range than using the location of absorption minima alone.

Feldman, S. C.↗
NASA NTRS1986

Detection of hydrothermal alteration at Virginia City, Nevada using Airborne Imaging Spectrometry (AIS)

Airborne Imaging Spectrometer (AIS) data were collected over Virginia City, Nevada; an area of gold and silver mineralization with extensive surface exposures of altered volcanic rocks. The data were corrected for atmospheric effects by a flat-field method, and compared to library spectra of various alteration minerals using a spectral analysis program SPAM. Areas of strong clay alteration were identified on the AIS images that were mapped as kaolinitic, illitic, and sericitic alterations zones. Kaolinitic alteration is distinguishable in the 2.1 to 2.4 and 1.2 to 1.5 micrometer wavelength regions. Montmorillonite, illite, and sericite have absorption features similar to each other at 2.2 micrometer wavelength. Montnorillonite and illite also may be present in varying proportions within one Ground Instantaneous Field of View (GIFOV). In general AIS data is useful in identifying alteration zones that are associated with or lie above precious metal mineralization at Virginia City.

Hutsinpiller, A.↗
NASA NTRS1992

Mars surface weathering products and spectral analogs: Palagonites and synthetic iron minerals

There are several hypotheses regarding the formation of Martian surface fines. These surface fines are thought to be products of weathering processes occurring on Mars. Four major weathering environments of igneous rocks on Mars have been proposed; (1) impact induced hydrothermal alterations; (2) subpermafrost igneous intrusion; (3) solid-gas surface reactions; and (4) subaerial igneous intrusion over permafrost. Although one or more of these processes may be important on the Martian surface, one factor in common for all these processes is the reaction of solid or molten basalt with water (solid, liquid, or gas). These proposed processes, with the exception of solid-gas surface reactions, are transient processes. The most likely product of transient hydrothermal processes are layer silicates, zeolites, hydrous iron oxides and palagonites. The long-term instability of hydrous clay minerals under present Martian conditions has been predicted; however, the persistence of such minerals due to slow kinetics of dehydration, or entrapment in permafrost, where the activity of water is high, can not be excluded. Anhydrous oxides of iron (e.g., hematite and maghemite) are thought to be stable under present Martian surface conditions. Oxidative weathering of sulfide minerals associated with Martian basalts has been proposed. Weathering of sulfide minerals leads to a potentially acidic permafrost and the formation of Fe(3) oxides and sulfates. Weathering of basalts under acidic conditions may lead to the formation of kaolinite through metastable halloysite and metahalloysite. Kaolinite, if present, is thought to be a thermodynamically stable phase at the Martian surface. Fine materials on Mars are important in that they influence the surface spectral properties; these fines are globally distributed on Mars by the dust storms and this fraction will have the highest surface area which should act as a sink for most of the absorbed volatiles near the surface of Mars. Therefore, the objectives of this study were to: (1) examine the fine fraction mineralogy of several palagonitic materials from Hawaii; and (2) compare spectral properties of palagonites and submicron sized synthetic iron oxides with the spectral properties of the Martian surface.

Golden, D. C.↗
NASA NTRS1986

Comparative isosteric ion adsorption for minerals

A comparative isosteric ion adsorption study for minerals (kaolinite, rutile, and quartz) was performed in aqueous solutions of CaCl2, LaCl3, and Th(NO3)4 in the presence of the neutral salt NaCl. It was observed that the concentration of Ca(2+) ions required to produce a standard reduction in the electrophoretic mobility of mineral particles was always appreciably greater than the concentration required for the Th(4+) ions. The effectiveness of adsorption of the cations differed from particle to particle and showed that ion adsorption on a mineral surface depends, among other things, on the nature of the mineral surface and on the particular adsorbed cation. The number of cation binding sites on mineral surfaces and the electrochemical free energies of cation adsorption were calculated. It was found that the adsorption energy of La(3+) and Th(4+) ions on rutile, kaolinite, and quartz was greater than that of Ca(2+) on these minerals.

Omenyi, Samuel N.↗