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NASA NTRS1994

Bench-scale synthesis of nanoscale materials

A novel flow-through hydrothermal method used to synthesize nanoscale powders is introduced by Pacific Northwest Laboratory. The process, Rapid Thermal Decomposition of precursors in Solution (RTDS), uniquely combines high-pressure and high-temperature conditions to rapidly form nanoscale particles. The RTDS process was initially demonstrated on a laboratory scale and was subsequently scaled up to accommodate production rates attractive to industry. The process is able to produce a wide variety of metal oxides and oxyhydroxides. The powders are characterized by scanning and transmission electron microscopic methods, surface-area measurements, and x-ray diffraction. Typical crystallite sizes are less than 20 nanometers, with BET surface areas ranging from 100 to 400 sq m/g. A description of the RTDS process is presented along with powder characterization results. In addition, data on the sintering of nanoscale ZrO2 produced by RTDS are included.

Buehler, M. F.↗

NASA NTRS1993

The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

Plumlee, G. S.↗

NASA NTRS1994

Exopaleontology and the search for a fossil record on Mars

Although present Martian surface conditions appear unfavorable for life as we know it, there is compelling geological evidence that the climate of early Mars was much more Earth-like, with a denser atmosphere and abundant surface water. The fact that life developed on the Earth within the first billion years of its history makes it quite plausible that life may have also developed on Mars. If life did develop on Mars, it is likely to have left behind a fossil record. This has led to the development of a new subdiscipline of paleontology, herein termed 'exopaleontology', which deals with the exploration for fossils on other planets. The most important factor enhancing microbial fossilization is the rapid entombment of microorganisms by fine-grained, stable mineral phases, such as silica, phosphate, or carbonate. The oldest body fossils on Earth are preserved in this way, occurring as permineralized cells in fine-grained siliceous sediments (cherts) associated with ancient volcanic terranes in Australia and South Africa. Modern terrestrial environments where minerals may precipitate in the presence of microorganisms include subaerial thermal springs and shallow hydrothermal systems, sub-lacustrine springs and evaporitic alkaline lakes, zones of mineralization within soils where 'hardpans' (e.g. calcretes, silcretes) form, and high latitude frozen soils or ground ice.

Farmer, Jack D.↗

NASA NTRS1994

Carbonates in the Kaidun chondrite

Kaidun is a remarkable chondrite breccia fall containing lithic clasts that span a wide range of chondrite groups including C and E chondrites, as well as having clasts with characteristics not yet found in existing chondrite samples. The dominant lithology in Kaidun appears to be CR chondritic, consonant with recent O isotope data. The carbonates in Kaidun are presented as one mineralogical basis for comparing it to the other hydrated chondrites and to better understand its relative alteration history. The four polished thin sections of Kaidun studied contained a variety of lithologies that we classified into four groups -- CR, E, CM-like, and dark inclusions (DIs). DIs contain sulfide and magnetite morphologies that superficially resemble CI chondrites, and some of the previously reported CI lithologies in Kaidun may be what we term DIs. Carbonates were found in all lithologies studied. Carbonates in Kaidun are similar in composition to those in CR chondrites. Some of the DIs in Kaidun, previously characterized as CI, have carbonates similar to those in CR chondrites and are unlike those in CI or CM chondrites. Most carbonates in Kaidun and CR chondrites are calcites, some of which formed at temperatures above 250 C. Dolomite is less common and some may be metastable. Alteration temperatures in the Renazzo CR chondrite were estimated to be approximately 300 C, based on O isotope fractionation between phyllosilicates and magnetite. Temperatures of up to 450 C were proposed for the alteration of a CR-like dark inclusion in Kaidun, based on the presence of hydrothermal pentlandite veins. The alteration temperatures for Kaidun and the other CR chondrites are considerably higher than those suggested for CI or CM parent bodies.

Weisberg, M. K.↗

NASA NTRS1994

Hydrous carbonates on Mars? Evidence from Mariner 6/7 infrared spectrometer and ground-based telescopic spectra

Absorption features at 2.28 and 5.4 micrometers identified in Mariner 6/7 infrared spectrometer and terrestrial telescopic spectra are consistent with the spectra of hydrous magnesium carbonates such as hydromagnesite and artinite. Spectral characteristics of these hydrous carbonates are different from those of the anhydrous carbonates, as the former do not have the strong spectral features typically associated with anhydrous carbonates such as calcite and siderite. Theoretical mixing indicates that, depending on the type of hydrous carbonate, 10-20 wt % can be incorporated into the regolith without contradicting the spectral observations or the Viking x ray fluorescence chemical analysis. Hydrous carbonates form as weathering products of mafic minerals in the presence of H2O and CO2, even in the Antarctic. Their formation as evaporite minerals from either original magmas or hydrothermally altered rocks is consistent with the Martian environment, provided liquid water is or has been at least transiently present. On Earth, formation of hydrous Mg carbonates is associated with the production of amorphous iron oxides, which is consistent with both the environment and the inferred surface mineralogy of Mars. These minerals are about 60 wt % H2O, CO3, and OH; if they are abundant everywhere at the 10% level, then about 6% of the surface weight could be volatiles bound in this type of mineral. Although the spectroscopic evidence for anhydrous carbonates is scant, the possible presence of hydrous carbonates provides an appealing mechanism for the existence of carbonates on Mars.

Calvin, Wendy M.↗

NASA NTRS1993

Assumptions about the presence of natural glasses on Mars

Natural glasses occur not only on Earth but also in lunar rocks and in some meteorites. On geological grounds, natural glasses could be expected on the surface of Mars and their presence would have important implications for the weathering and alteration of the near-surface layer. Ultramafic and mafic magmatism rich in iron and some volatiles appears to have been important on Mars as has been impact cratering, volcanism, and possibly hydrothermal alteration. Available data indicate that we can presume the past or present existence of volcanic basaltic glasses, impact glasses formed by thermal fusion of meteorite-impact targets, and diaplectic (mainly maskelynite) glasses. Conditions appear unsuitable for the formation of tektites on the Martian surface, and the production of measurable amounts of fulgurite or combustion glass seems improbable. Prospects for the remote and in-situ identification of Martian glasses and their subsequent weathering products are discussed and include orbital reflectance and thermal emission spectroscopic measurements and Mossbauer spectroscopy from a surface lander.

Bouska, Vladimir↗

NASA NTRS1995

ISSOL Meeting, Barcelona, Spain, 1993

Topics in a conference on the origins of life and the evolution of the biosphere include the origin of chirality, prebiotic chemistry of small biomolecules, primitive polymer formation, RNA regulation and control. Early origins of life and the ecology of hydrothermal systems such as ocean floor vents and their simple organisms are examined. The process of mineral catalysis in Montmorillonite as a model for early metabolism is used. The origin of the genetic code and the development of branching in molecular structures of amino acids is described. Studies are reported of the effects of meteorite impact on early Earth life.

Ferris, James P.↗

NASA NTRS1995

Environmentally Sound Processing Technology: JANNAF Safety and Environmental Protection Subcommittee and Propellant Development and Characterization Subcommittee Joint Workshop

Topics covered include: Risk assessment of hazardous materials, Automated systems for pollution prevention and hazardous materials elimination, Study design for the toxicity evaluation of ammonium perchlorate, Plasma sprayed bondable stainless surface coatings, Development of CFC-free cleaning processes, New fluorinated solvent alternatives to ozone depleting solvents, Cleaning with highly fluorinated liquids, Biotreatment of propyleneglycol nitrate by anoxic denitrification, Treatment of hazardous waste with white rot fungus, Hydrothermal oxidation as an environmentally benign treatment technology, Treatment of solid propellant manufacturing wastes by base hydrolysis, Design considerations for cleaning using supercritical fluid technology, and Centrifugal shear carbon dioxide cleaning.

Pickett, Lorri A.↗

NASA NTRS1995

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

Formation of zincophosphates from zinc and phosphate containing reverse micelles (water droplets in hexane) has been examined. The frameworks formed resemble that made by conventional hydrothermal synthesis. Dynamics of crystal growth are however quite different, and form the main focus of this study. In particular, the formation of zincophosphate with the sodalite framework was examined in detail. The intramicellar pH was found to have a strong influence on crystal growth. Crystals with a cubic morphology were formed directly from the micelles, without an apparent intermediate amorphous phase over a period of four days by a layer-bylayer growth at the intramicellar pH of 7.6. At a pH of 6.8, an amorphous precipitate rapidly sediments in hours. Sodalite was eventually formed from this settled phase via surface diffusion and reconstruction within four days. With a rotating cell, it was possible to minimize sedimentation and crystals were found to grow epitaxially from the spherical, amorphous particles. Intermediate pH's of 7.2 led to formation of aggregated sodalite crystals prior to settling, again without any indication of an intermediate amorphous phase. These diverse pathways were possible due to changes in intramicellar supersaturation conditions by minor changes in pH. In contrast, conventional syntheses in this pH range all proceeded by similar crystallization pathways through an amorphous gel. This study establishes that synthesis of microporous frameworks is not only possible in reverse micellar systems, but they also allow examination of possible crystallization pathways.

Dutta, Prabir K.↗

NASA NTRS1994

Petrology of Impact-Melt Rocks at the Chicxulub Multiring Basin, Yucatan, Mexico

Compositions and textures of melt rocks from the upper part of the Chicxulub structure are typical of melt rocks at other large terrestrial impact structures. Apart from variably elevated iridium concentrations (less than 1.5 to 13.5 +/- 0.9 ppb) indicating nonuniform dissemination of a meteoritic component, bulk rock and phenocryst compositions imply that these melt rocks were derived exclusively from continental crust and platform-sediment target lithologies. Modest differences in bulk chemistry among samples from wells located approximately 40 km apart suggest minor variations in relative contributions of these target lithologies to the melts. Subtle variations in the compositions of early-formed pyroxene and plagioclase also support minor primary differences in chemistry between the melts. Evidence for pervasive hydrothermal alteration of the porous mesostasis includes albite, K-feldspar, quartz, epidote, chlorite, and other phyllosilicates, as well as siderophile element-enriched sulfides, suggesting the possibility that Chicxulub, like Sudbury, may host important ore deposits.

Schuraytz, Benjamin C.↗

NASA NTRS1997

Meteorites, Microfossils and Exobiology

The discovery of evidence for biogenic activity and possible microfossils in a Martian meteorite may have initiated a paradigm shift regarding the existence of extraterrestrial microbial life. Terrestrial extremophiles that live in deep granite and hydrothermal vents and nanofossils in volcanic tuffs have altered the premise that microbial life and microfossils are inconsistent with volcanic activity and igneous rocks. Evidence for biogenic activity and microfossils in meteorites can no longer be dismissed solely because the meteoritic rock matrix is not sedimentary. Meteorite impact-ejection and comets provide mechanisms for planetary cross-contamination of biogenic chemicals, microfossils, and living microorganisms. Hence, previously dismissed evidence for complex indigenous biochemicals and possible microfossils in carbonaceous chondrites must be re-examined. Many similar, unidentifiable, biological-like microstructures have been found in different carbonaceous chondrites and the prevailing terrestrial contaminant model is considered suspect. This paper reports the discovery of microfossils indigenous to the Murchison meteorite. These forms were found in-situ in freshly broken, interior surfaces of the meteorite. Environmental Scanning Electron Microscope (ESEM) and optical microscopy images indicate that a population of different biological-like forms are represented. Energy Dispersive Spectroscopy reveals these forms have high carbon content overlaying an elemental distribution similar to the matrix. Efforts at identification with terrestrial microfossils and microorganisms were negative. Some forms strongly resemble bodies previously isolated in the Orgueil meteorite and considered microfossils by prior researchers. The Murchison forms are interpreted to represent an indigenous population of the preserved and altered carbonized remains (microfossils) of microorganisms that lived in the parent body of this meteorite at diverse times during the past 4.5 billion years (Gy).

Hoover, Richard B.↗

NASA NTRS1997

Large Meteorite Impacts and Planetary Evolution

Topics considered include: Petrography, geochemistry and geochronology; impact-induced hydrothermal base metal mineralization; nickel-and platinum group element -enriched quartz norite in the latest jurassic morokweng impact structure, south Africa; extraterrestrial helium trapped in fullerenes in the sudbury; synthetic aperture radar characteristics of a glacially modified meltsheet; the chicxulub seismic experiment; chemical compositions of chicxulub impact breccias; experimental investigation of the chemistry of vaporization of targets in relation to the chicxulub impact; artificial ozone hole generation following a large meteoroid impact into an oceanic site; three dimensional modeling of impactite bodies of popigai impact crater, Russia.

Source record↗

NASA NTRS1996

Surveying Dead Trees and CO2-Induced Stressed Trees Using AVIRIS in the Long Valley Caldera

Since 1980 the Long Valley Caldera in the eastern Sierra Nevada (California) has shown signs of renewed volcanic activity. Frequent earthquakes, a re-inflation of the caldera, hydrothermal activity and gas emissions are the outer symptoms of this renewed activity. In 1990 and 1991 several areas of dying trees were found around Mammoth Mountain. The cause of the die off of the trees was first sought in the persistent drought in the preceding years. However, the trees died regardless of age and species. Farrar et al. (1995) started a soil-gas survey in 1994 in the dead-tree areas and found carbon dioxide concentrations ranging from 30 to 96% at soil depths between 30 and 60 cm. CO2 concentrations in the atmosphere are usually around 0.03% and in the soil profile CO2 levels do commonly not exceed 4 to 5%. Although not much is known about the effect of high levels of carbon dioxide in the soil profile on roots, it is most likely that the trees are dying due to oxygen deprivation: the CO2 drives the oxygen out of the soil. So far, four sites of dead trees have been mapped around Mammoth Mountain. The two largest dying trees sites are located near Horseshoe Lake and near Mammoth Mountain Main Lodge covering approximately an area of 10 and 8 ha respectively. Analysis of the gas composition regarding the He-3/He-4 ratio and the percentage biogenic carbon reveals the source of the gas: the magma body beneath the Long Valley Caldera. Until recently it was not known that volcanoes release abundant carbon dioxide from their flanks as diffuse soil emanations. As a result of the magma gas emission around Mammoth Mountain there is an excellent sequence of dead trees, stressed trees, healthy trees and bare soil surfaces. This research site provides excellent opportunities to: (1) Study the capabilities of imaging spectrometry to map stressed (and dead) pine and fir species; (2) Study methods to separate the vivid vegetation, stressed vegetation and dead vegetation from the soil background of glacial deposits and crystalline rocks. The dead tree areas are located on the flanks of Mammoth Mountain (N:37 deg 37' 45" and W:119 deg 02' 05") at an elevation between 2600 and 3000 meters. The area is covered by an open type of Montane Forest. The dominant tree species are Lodgepole Pine (Pinus contorta), the Red Fir (Abies magnifica) and the Jeffrey Pine (Pinus jeffreyi). The soil surface near Horseshoe Lake is generally fairly bright. The surface is covered by glacial deposits (till) consisting mainly of weathered granitic rocks.

deJong, Steven M.↗

NASA NTRS1996

Mapping Volcanic Gas Emissions in the Mammoth Mountain Area Using AVIRIS

The Long Valley Caldera located in the eastern Sierra Nevada (California) shows new signs of volcanic activity. This renewed activity is expressed by gas emissions, hydrothermal activity and frequent earthquakes. Analysis of the gas composition regarding the percentage biogenic carbon and the He-3/He-4 ratio revealed that the gas source is the magma body approximately 7 km beneath the Long Valley Caldera. The gas from the magma body surfaces not only via the fumaroles but also emerges along geological faults. Some of the spots where gas surfaces are marked by dead or stressed trees. Other spots may not yet be identified. It is only recently known, from research at 'Vulcano Island' in southern Italy, that volcanoes release abundant carbon dioxide from their flanks as diffuse soil emanations. Mammoth Mountain seems to behave in a similar manner. The research described in this paper is designed to determine whether AVIRIS (Airborne Visible/Infrared Imaging Spectrometer) can be used to identify areas of volcanic gas emissions.

deJong, Steven M.↗

NASA NTRS1993

The RNA World: Life Before DNA and Protein

All of the life that is known, all organisms that exist on Earth today or are known to have existed on Earth in the past, are of the same life form: a life form based on DNA and protein. It does not necessarily have to be that way. Why not have two competing life forms on this planet? Why not have biology as we know it and some other biology that occupies its own distinct niche? Yet that is not how evolution has played out. From microbes living on the surface of antarctic ice to tube worms lying near the deep-sea hydrothermal vents, all known organisms on this planet are of the same biology. Looking at the single known biology on Earth, it is clear that this biology could not have simply sprung forth from the primordial soup. The biological system that is the basis for all known. life is far too complicated to have arisen spontaneously. This brings us to the notion that something else something simpler, must have preceded life based on DNA and protein. One suggestion that has gained considerable acceptance over the past decade is that DNA and protein-based life was preceded by RNA-based life in a period referred to as the 'RNA world'. Even an RNA-based life form would have been fairly complicated - not as complicated as our own DNA- and protein-based life form - but far too complicated, according to prevailing scientific thinking, to have arisen spontaneously from the primordial soup. Thus, it has been argued that something else must have preceded RNA-based life, or even that there was a succession of life forms leading from the primordial soup to RNA-based life. The experimental evidence to support this conjecture is not strong because, after all, the origin of life was a historical event that left no direct physical record. However, based on indirect evidence in both the geological record and the phylogenetic record of evolutionary history on earth, it is possible to reconstruct a rough picture of what life was like before DNA and protein.

Joyce, Gerald F.↗

NASA NTRS1999

Spectroscopic Properties of Metamorphosed Mafic Rocks: Remote Sensing Applications on Mars

Reflectance spectroscopy in the visible and near-infrared wavelengths, between 420 mn to 2588 nm. was utilized on a suite of hydrothermally metamorphosed mafic rocks from the Smartville complex in the northern Sierra Nevada mountains in California. A detailed data base of 102 samples was compiled in order to distinguish differences in mineralogy, petrology, and degree of metamorphism for remote sensing applications. Study was limited to metaigneous and metasedimentary rocks in an attempt to spectrally characterize terrestrial rocks analogous to the possible surface of Mars, for a better understanding and possible detection of the geologic features on the remote surface. Diagnostic absorption bands of iron, water, and hydroxyl produced the majority of discernible features in this study. Mossbauer spectroscopy was performed in order to determine specific iron sites. The resulting spectral data base along with thin section mineral identification, metamorphic zone, rock type and location were recorded and available for future application and research. Continued exploration of Mars in the advancing years, will further advance our understanding of the geology of Mars. Spectroscopic techniques will undoubtedly be integral parts of these future missions. Work on terrestrial analogs to the Martian surface must continue, in order to produce extensive data bases and broaden our knowledge of spectral features.

Graff, Trevor G.↗

NASA NTRS1999

Growth of Homoepitaxial ZnO Semiconducting Films

As a high temperature semiconductor, ZnO has been used for many applications such as wave-guide, solar cells, and surface acoustic wave devices. Since the ZnO material has an energy gap of 3.3 eV at room temperature and an excitonic binding energy (60 meV) that is possible to make excitonic lasering at room temperature a recent surge of interest is to synthesize ZnO films for electro-optical devices. These applications require films with a smooth surface, good crystal quality, and low defect density. Homoepitaxial films have been studied in terms of morphology, crystal structure, and electrical and optical properties. ZnO single crystals are grown by the hydrothermal method. Substrates are mechanically polished and annealed in air for four hours before deposited films. The annealing temperature-dependence of ZnO substrates is studied. Films are synthesized by the off-axis reactive sputtering deposition. The films have very smooth surface with a roughness </= 5 nm on a 5 micrometers x 5 micrometers area. The full width at half maximum of film theta rocking curves measured by the x-ray diffraction is slightly larger than the crystal substrate. The film quality is determined by measuring the film resistivity, the Hall mobility, carrier densities and the energy band gap. The properties of ZnO films grown of (0001) ZnO and (0001) sapphire substrates will be also compared and discussed in the presentation.

Zhu, Shen↗

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.↗