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Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such a hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.
Global measurements of the hydroxyl mesospheric airglow over an extended period of time have been made possible by the NASA SABER infrared sensor aboard the TIMED satellite which has been functioning since December of 2001. The orbital mission has continued over a significant portion of a solar cycle. Experimental data from SABER for several years have exhibited equatorial enhancements of the nighttime mesospheric OH (delta v = 2) airglow layer consistent with the high average diurnal solar flux. The brightening of the OH airglow typically means more H + O3 is being reacted. At both the spring and autumn seasonal equinoxes when the equatorial solar UV irradiance mean is greatest, the peak volume emission rate (VER) of the nighttime Meinel infrared airglow typically appears to be both significantly brighter plus lower in altitude by several kilometres at low latitudes compared with midlatitude findings.
The Apollo and Russian missions during 1970's were reviewed to rediscover the type and distribution of minerals on the Moon. This study revealed that the Moon is a relatively barren place in mineral content when compared with the Earth. Results from the Lunar minerals brought back to Earth, indicate that the Moon lacks water, hydroxyl ions, and carbon based minerals. Our approach to prospecting utilizes a vehicle with sensors embedded in a wheel that allow measurements while the vehicle is in motion. Once a change in soil composition is detected, decision making software stops the vehicle and analytical instruments perform a more definitive analysis of the soil. The focus of this paper is to describe the instrumentation and data from the wheel-based sensors.
Alumina scale adhesion to high temperature alloys is known to be affected primarily by sulfur segregation and reactive element additions. However, adherent scales can become partially compromised by excessive strain energy and cyclic cracking. With time, exposure of such scales to moisture can lead to spontaneous interfacial decohesion, occurring while the samples are maintained at ambient conditions. Examples of this Moisture-Induced Delayed Spallation (MIDS) are presented for NiCrAl and single crystal superalloys, becoming more severe with sulfur level and cyclic exposure conditions. Similarly, delayed failure or Desk Top Spallation (DTS) results are reviewed for thermal barrier coatings (TBCs), culminating in the water drop failure test. Both phenomena are discussed in terms of moisture effects on bulk alumina and bulk aluminides. A mechanism is proposed based on hydrogen embrittlement and is supported by a cathodic hydrogen charging experiment. Hydroxylation of aluminum from the alloy interface appears to be the relevant basic reaction.
Alumina scale adhesion to high temperature alloys is known to be affected primarily by sulfur segregation and reactive element additions. However adherent scales can become partially compromised by excessive strain energy and cyclic cracking. With time, exposure of such scales to moisture can lead to spontaneous interfacial decohesion, occurring while the samples are maintained at ambient conditions. Examples of this Moisture-Induced Delayed Spallation (MIDS) are presented for NiCrAl and single crystal superalloys, becoming more severe with sulfur level and cyclic exposure conditions. Similarly, delayed failure or Desk Top Spallation (DTS) results are reviewed for TBC s, culminating in the water drop failure test. Both phenomena are discussed in terms of moisture effects on bulk alumina and bulk aluminides. A mechanism is proposed based on hydrogen embrittlement and is supported by a cathodic hydrogen charging experiment. Hydroxylation of aluminum from the alloy interface appears to be the relevant basic reaction.
As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties in a global 3-D chemical transport model (GEOS4-Chem CTM). GEOS-Chem was driven with a series of meteorological archives (GEOS1-STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system, which have significantly different cloud optical depths (CODs) and vertical distributions. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. Model simulations with each of the three cloud distributions all show that the change in the global burden of O3 due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied by -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the UV wavelength. Our results have important implications for model intercomparisons and climate feedback on tropospheric photochemistry.
The decision to return humans to the moon by 2020 makes it imperative to understand the effects of lunar dust on human and mechanical systems.( Bush 2004; Gaier 2005; Mendell 2005) During the Apollo missions, dust was found to cause numerous problems for various instruments and systems. Additionally, the dust may have caused health issues for some of the astronauts.(Gaier 2005; Rowe 2007) It is necessary, therefore, for studies to be carried out in a variety of disciplines in order to mitigate the effects of the dust as completely as possible. Due to the lack of an atmosphere, there is nothing to protect the lunar soil from ultraviolet radiation, solar wind, and meteorite impacts. These processes could all serve to "activate" the soil, or produce reactive surface species. In order to understand the possible toxic effects of the reactive dust, it is necessary to "reactivate" the dust, as samples returned during the Apollo missions were exposed to the atmosphere of the Earth. We have used grinding and exposure to UV radiation in order to mimic some of the processes occurring on the lunar surface. To monitor the reactivity of the dust, we have measured the ability of the dust to produce hydroxyl radicals in solution. These radicals have been measured using a novel fluorescent technique developed in our laboratory,(Wallace et al. 2008) as well as using electron paramagnetic resonance (EPR).
The National Aeronautics and Space Administration (NASA) Ares Projects Office (APO) is continuing to make progress toward the final design of the first stage propulsion system for the Ares I crew launch vehicle and the Ares V cargo launch vehicle. Ares I and Ares V will provide the space launch capabilities needed to fulfill NASA' s exploration strategy of sending human beings to the Moon, Mars, and beyond. As primary propulsion for the Ares launch vehicles, the Space Shuttle-derived Reusable Solid Rocket Motor (RSRM) is one of the first and most important components to be tested. The first flight of Ares I, called Ares I-X, will occur in April 2009, with booster integration to begin at Kennedy Space Center (KSC) by autumn 2008. The Ares I-X flight will use a combination of flight and simulation hardware to obtain data on controlling the long and narrow crew launch vehicle configuration. The test will use a four-segment RSRM from the Shuttle inventory and a fifth spacer segment to simulate the size and weight of the operational five-segment motor to be used on later flights. The upper stage, Orion crew exploration vehicle, and launch abort system will all be replaced with simulator hardware. Manufacturing work has begun on the spacer segment, as well as the new forward hardware for the booster. Atlas V avionics will be adapted to control Ares I-X' s first stage. That hardware is undergoing hardware-in-the-loop testing in a contractor-provided systems integration laboratory (SIL); a critical design review (CDR) was completed in December 2007. Drogue and main parachute drop tests have also been conducted successfully at Yuma Proving Grounds, allowing the First Stage team to begin fabricating parachutes for Ares I-X. The Ares I-X flight test will be the first flight test for the parachutes. A series of preliminary design technical interchange meetings is being conducted prior to the Ares I-X CDR in January 2007 to ensure readiness for the flight. Much of the First Stage activity in 2007 has focused on a series of preliminary design (PDR) activities associated with each booster subsystem. These events will culminate in a formal preliminary design review in 2008, where subsystems and component specifications will be developed and associated analyses and drawings will be evaluated for technical adequacy. The first stage also has been undergoing a series of trade studies to determine means for upgrading booster performance and reducing operational costs. Performance improvement studies have included changing from polybutadiene acrylonitrile (PBAN) propellant to hydroxyl-terminated polybutadiene (HTPB); replacing aluminum with composite motor casings; and optimizing or upgrading the propellant grain and nozzle structures. Some or all of these changes could result in a block upgrade to the Ares I first stage, after becoming the standard configuration for the Ares V. The cost reduction studies included a change from reusable or recoverable boosters to completely expendable boosters; changing from hydrazine-powered to more environmentally friendly electrohydrostatic actuators (EHAs) on the thrust vector control (TVC) system; and changing the location of the separation plane to reduce the likelihood of recontact upon booster separation. The expendability trade study resulted in a decision to keep the recoverable boosters, as the new hardware costs significantly outweighed the potential operational cost savings due to reduced ground operations. Likewise, due to cost considerations, the team continued using existing hydrazine-powered actuators for the TVC system. The separation plane location for Ares I is still being studied, with results to be announced in 2008. In short, the Ares launch vehicles' first stage is building upon NASA's close familiarity with this Shuttle-derived system, while continuing to seek out improvements for long-term exploration.
Lunar dust causes a variety of problems for spacecraft. It can obscure vision, clog equipment, cause seal failures and abrade surfaces. Additionally, lunar dust is potentially toxic and therefore hazardous to astronauts. Lunar dust can be activated by meteorites, UV radiation and elements of solar wind and, if inhaled, could produce reactive species in the lungs (freshly fractured quartz). Methods of lunar dust deactivation must be determined before new lunar missions. This requires knowledge of how to reactivate lunar dust on Earth - thus far crushing/grinding, UV activation and heating have been tested as activation methods. Grinding of lunar dust leads to the production of hydroxyl radicals in solution and increased dissolution of lunar simulant in buffers of different pH. Decreases in pH lead to increased lunar simulant leaching. Additionally, both ground and unground lunar simulant and unground quartz have been shown to promote the production of IL-6 and IL-8, pro-inflammatory cytokines, by alveolar epithelial cells. The results suggest the need for further studies on lunar dust and simulants prior to returning to the lunar surface.
Measurement of Raman and native fluorescence emission using ultraviolet (UV) sources (<400 nm) on targeted materials is suitable for both sensitive detection and accurate identification of explosive materials. When the UV emission data are analyzed using a combination of Principal Component Analysis (PCA) and cluster analysis, chemicals and biological samples can be differentiated based on the geometric arrangement of molecules, the number of repeating aromatic rings, associated functional groups (nitrogen, sulfur, hydroxyl, and methyl), microbial life cycles (spores vs. vegetative cells), and the number of conjugated bonds. Explosive materials can be separated from one another as well as from a range of possible background materials, which includes microbes, car doors, motor oil, and fingerprints on car doors, etc. Many explosives are comprised of similar atomic constituents found in potential background samples such as fingerprint oils/skin, motor oil, and soil. This technique is sensitive to chemical bonds between the elements that lead to the discriminating separability between backgrounds and explosive materials.
The chemically assisted photocatalytic oxidation system (CAPOS) has been proposed for destroying microorganisms and organic chemicals that may be suspended in the air or present on surfaces of an air-handling system that ventilates an indoor environment. The CAPOS would comprise an upstream and a downstream stage that would implement a tandem combination of two partly redundant treatments. In the upstream stage, the air stream and, optionally, surfaces of the air-handling system would be treated with ozone, which would be generated from oxygen in the air by means of an electrical discharge or ultraviolet light. In the second stage, the air laden with ozone and oxidation products from the first stage would be made to flow in contact with a silica-titania photocatalyst exposed to ultraviolet light in the presence of water vapor. Hydroxyl radicals generated by the photocatalytic action would react with both carbon containing chemicals and microorganisms to eventually produce water and carbon dioxide, and ozone from the first stage would be photocatalytically degraded to O2. The net products of the two-stage treatment would be H2O, CO2, and O2.
This project developed self-cleaning photocatalytic coatings that remove contamination without human intervention. The coatings chemically remove organic contaminants and leave no residue. The photocatalyst will not negatively affect other coating properties, especially corrosion resistance. Titanium dioxide, TiO2, is an extremely popular photocatalyst because of its chemical stability, nontoxicity, and low cost. TiO2 is commonly used in the photocatalytic oxidation of organic matter or pollutants in the gas and liquid phases. However, TiO2 does have some drawbacks. It has limited light absorption because of its large band-gap and suffers from a photonic efficiency of less than 10 percent for organic degradation. Dopants can lower the band-gap and improve efficiency. Since the photocatalytically active form of TiO2 is a nanocrystalline powder, it can be difficult to make a robust coating with enough catalyst loading to be effective. Photocatalysts become active when certain light energy is absorbed. When photons with an energy greater than the band-gap, Eg, (wavelengths shorter than 400 nm) impinge upon the surface of the TiO2, an electron-hole pair is formed. The electron-hole pair oxidizes adsorbed substances either directly or via reactive intermediates that form on the surface, such as hydroxyl radicals (OH) or superoxide ions (O2-). Several factors can influence the band-gap energy of TiO2, two of which are crystal structure and impurities. TiO2 exists as three crystal structures brookite, anatase, and rutile that can be controlled via heat treatment. Anatase is the most photocatalytically active crystal form of TiO2. Doping TiO2 with impurities can alter its band-gap energy, as well as its effectiveness as a catalyst. Depending on their size, dopant atoms can occupy either the substitutional or interstitial lattice positions. Atoms that are relatively large will assume the interstitial positions and create a much greater energy disturbance in the crystal than will smaller atoms that take on the substitutional positions. This energy disturbance narrows the band-gap and thus allows photons with longer wavelengths and smaller energies (such as those in the visible-light spectrum) to create electron-hole pairs. Raman spectroscopy was performed for the purpose of determining the crystal structure and the degree of crystallinity of the TiO2 particles. Reflectance measurements indicated the wavelengths of light absorbed by the different catalysts.
Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH3 concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the ultraviolet wavelengths.
Presently, it is not well understood how to best model nitrogen oxides (NOx) emissions from lightning because lightning is highly variable. Peak current, channel length, channel altitude, stroke multiplicity, and the number of flashes that occur in a particular region (i.e., flash density) all influence the amount of lightning NOx produced. Moreover, these 5 variables are not the same for ground and cloud flashes; e.g., cloud flashes normally have lower peak currents, higher altitudes, and higher flash densities than ground flashes [see (Koshak, 2009) for additional details]. Because the existing satellite observations of lightning (Fig. 1) from the Lightning Imaging Sensor/Optical Transient Detector (LIS/OTD) do not distinguish between ground and cloud fashes, which produce different amounts of NOx, it is very difficult to accurately account for the regional/global production of lightning NOx. Hence, the ability to partition the LIS/OTD lightning climatology into separate ground and cloud flash distributions would substantially benefit the atmospheric chemistry modeling community. NOx indirectly influences climate because it controls the concentration of ozone and hydroxyl radicals in the atmosphere. The importance of lightning-produced NOx is empasized throughout the scientific literature (see for example, Huntrieser et al. 1998). In fact, lightning is the most important NOx source in the upper troposphere with a global production rate estimated to vary between 2 and 20 Tg (N)yr(sup -1) (Lee et al., 1997), with more recent estimates of about 6 Tg(N)yr(sup -1) (Martin et al., 2007). In order to make accurate predictions, global chemistry/climate models (as well as regional air quality modells) must more accurately account for the effects of lightning NOx. In particular, the NASA Goddard Institute for Space Studies (GISS) Model E (Schmidt et al., 2005) and the GEOS-CHEM global chemical transport model (Bey et al., 2001) would each benefit from a partitioning of the LIS/OTD lightning climatology. In this study, we introduce a new technique for retrieving the ground flash fraction in a set of N lightning observed from space and that occur within a specific latitude/longitude bin. The method is briefly described and applied to CONUS lightning that have already been partitioned into ground and cloud flashes using independent ground-based observations, in order to assess the accuracy of the retrieval method. The retrieval errors are encouragingly small.
Lunar dust has been of significant concern due to various problems observed on the Apollo missions. Reports from astronauts have shown that the dust may have caused eye and nasal irritation as well as possible hay fever like symptoms. As NASA hopes to go to the Moon within the next few years, we hope to understand the possible toxic effects the dust might have. In these studies, we are looking at the effect of "re-activated" lunar dust stimulant on human bronchial cells. A simple grinding analog as a method of simulating micrometeorite crushing on the moon is used to "activate" the dust stimulant, i.e. capable of producing hydroxyl radicals. These radicals could then interact with human cells and may lead to a loss in membrane integrity and cell death. (Castranova, 1994) Cells are exposed to the dust for 6 and 24 hour intervals to assess cytotoxicity. Cytotoxicity is measured by looking at the production of inflammatory cytokines. Cells are exposed to ground and unground stimulant and compared to cytokine production from cells exposed to quartz which have a known toxicity. Here we look at the cytotoxicity of the lunar dust stimulant relative to quartz by measuring the production of inflammatory cytokines.
Elastomers are reinforced with functionalized, single-walled carbon nanotubes (SWNTs) giving them high-breaking strain levels and low densities. Cross-linked elastomers are prepared using amine-terminated, poly(dimethylsiloxane) (PDMS), with an average molecular weight of 5,000 daltons, and a functionalized SWNT. Cross-link densities, estimated on the basis of swelling data in toluene (a dispersing solvent) indicated that the polymer underwent cross-linking at the ends of the chains. This thermally initiated cross-linking was found to occur only in the presence of the aryl alcohol functionalized SWNTs. The cross-link could have been via a hydrogen-bonding mechanism between the amine and the free hydroxyl group, or via attack of the amine on the ester linage to form an amide. Tensile properties examined at room temperature indicate a three-fold increase in the tensile modulus of the elastomer, with rupture and failure of the elastomer occurring at a strain of 6.5.
Water appears to be essential to all life on Earth. For this reason, "Follow the Water" has been adopted as a mantra for the search for Life in the Cosmos. Expeditions have helped to establish the limits and biodiversity of life in the most extreme environments on Earth. Microbial extremophiles inhabit acidic streams; hypersaline and hyperalkaline lakes and pools; the cold deep sea floor, permafrost, rocks, glaciers, and perennially ice-covered lakes of the polar environments; geysers, volcanic fumaroles, hydrothermal vents and hot rocks deep within the Earth's crust. The ESA Venus Express Spacecraft entered Venusian Orbit in 2006 and continues to produce exciting results. The Visible and Infrared Thermal Imaging Spectrometer (VIRTIS) instrument made the first detection of hydroxyl in the atmosphere of Venus, indicating it is much more similar to Earth and Mars than previously thought. Huge hurricane-like vortices have been found above the poles of the planet and as yet unidentified UV absorbers that form mysterious dark bands in the upper atmosphere. At 70 km and below, water vapor and sulfur dioxide combine to form sulfuric acid droplets that create a haze above the cloud tops. Thermophilic acidophiles, such as have recently been discovered on Earth, could possibly survive in the hot sulfuric acid droplets that exist in the upper atmosphere of Venus. In order to understand how to search for life elsewhere in the Solar System, over 40 VIRTIS images of Earth from Venus have been obtained to search for evidence of life on Earth. The signatures of water and molecular Oxygen were detected in the Earth s atmosphere, but the atmosphere of Venus also exhibits these signatures. The water and water ice are far more abundant on comet, the polar caps and permafrost of Mars and the icy moons of Jupiter and Saturn. These "frozen worlds" of our Solar System, are much more promising regimes where extant or extinct microbial life may exist. The ESA Mars Advanced Radar for Subsurface and Ionospheric Sounding (MARSIS) probe has found that both the North and South Polar Caps of Mars are approximately 3.5 km thick and are composed almost entirely of water ice. In winter, a thin dry ice layer covers the caps, but it sublimates directly to CO2 in the spring. The ESA Mars Express Orbiter images reveal Rupes Tenuis to be a vast snow-laden region on the southern edge of the Martian North Polar Cap. The Mars Exploration Rover Spirit found alkaline volcanic rocks in the Gusev Crater and the Phoenix Mars Lander has shown that the soil of Mars is much more alkaline than previously expected. The Phoenix Mars Lander has also made direct observations of frozen and liquid water on Mars. It is known that microorganisms from Alaska, Siberia and Antarctica can remain alive frozen in permafrost or ice for long periods of time. These discoveries increase the possibility that the Labeled Release Experiment may have discovered life on Mars during the Viking Mission and provide strong impetus for the return of life detection experiments to Mars. Changes in the spin rate of Saturn's moon Titan indicate that it may also harbor a 300 km thick liquid water ocean beneath its icy crust. The NASA/ESA/Italian Space Agency Cassini Spacecraft has imaged geysers containing water vapor, methane, carbon dioxide and organics erupting from the "tiger stripe" regions near the South Pole of Saturn's moon Enceladus. The high temperatures observed, the water vapor and large number of ice particles expelled suggest that a liquid water lake may exist beneath the "tiger stripe" ice cracks of Enceladus. The NASA Deep Impact probe found the surface temperature of comet 9P/Temple 1 at 1.5 AY was slightly above the ice/water phase change temperature (273 K). This suggests melting of water ice near the comet surface. A spectrometer the spacecraft detected a mixture of clay and carbonate minerals (that form in the presence of liquid water) streaming off the comet after the collision with the pactor. The study of chemical and mineral biomarkers, chiral amino acids and possible indigenous microfossils in SNC and carbonaceous meteorites continues. These results suggest that comets should be considered prime targets in the search for Life in the Cosmos. The ESA Rosetta mission is on track to rendezvous with comet 67P/Churyumov-Gerasimenko. The recent space observations combined with new information about the ability of microbial extremophiles to thrive in polar environments suggest that life may be far more widely distributed in the Cosmos than previously thought possible. The Panelists will review recent discoveries and provide their own insights about Life in the Cosmos -- followed by a question and answer session with the audience.
A method of generating hydrogen includes the steps of providing an amine borane (AB) complex, at least one hydrogen generation catalyst, and a solvent, and mixing these components Hydrogen is generated. The hydrogen produced is high purity hydrogen suitable for PEM fuel cells. A hydrolytic in-situ hydrogen generator includes a first compartment that contains an amine borane (AB) complex, a second container including at least one hydrogen generation catalyst, wherein the first or second compartment includes water or other hydroxyl group containing solvent. A connecting network permits mixing contents in the first compartment with contents in the second compartment, wherein high purity hydrogen is generated upon mixing. At least one flow controller is provided for controlling a flow rate of the catalyst or AB complex.