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A development status evaluation is presented for moderate-temperature, single-unit, regenerative fuel cells using either alkaline or solid polymer proton-exchange membrane (PEM) electrolytes. Attention is given to the results thus far obtained for Pt, Ir, Rh, and Na(x)Pt3O4 catalysts. Alkaline electrolyte tests have been performed on a half-cell basis with a floating-electrode cell; PEM testing has been with complete fuel cells, using Nafion 117.
Sulfate reduction rates, dissolved iron and sulfide concentrations, and titration alkalinity were measured in salt marsh soils along a transect that included areas inhabited by both the tall and short forms of Spartina alterniflora and by Spartina patens. Pore waters were collected with in situ 'sippers' to acquire temporal data from the same location without disturbing plant roots. During 1984, data collected at weekly intervals showed rapid temporal changes in belowground biogeochemical processes that coincided with changes in S. alterniflora physiology. Rates of SO4(-2) reduction increased fivefold (to greater than 2.5 micromol ml(sup -1)d(sup -1)) when plants began elongating aboveground yet decreased fourfold upon plant flowering. This rapid increase in rates of SO4(-2) reduction must have been fueled by dissolved organic matter released from roots only during active growth. Once plants flowered, the supply of oxidants to the soil decreased and sulfide and alkalinity concentrations increased despite decreases in SO4(-2) reduction and increases in SO4(-2):Cl(-) ratios. Sulfide concentrations were highest in soils inhabited by tallest plants. During 1985, S. alterniflora became infested with fly larvae (Chaetopsis apicalis John) and aboveground growth ceased in late June. This cessation was accompanied by decreased rates of SO4(-2) reduction similar to those noted during the previous year when flowering occurred. After the fly infestation, the pore-water chemical profiles of these soils resembled profiles of soils inhabited by the short form of S. alterniflora. The SO4(-2) reduction rates in S. patens soils are the first reported. Rates were similar to those in S. alterniflora except that they did not increase greatly when S. patens was elongating. Tidal and rainfall events produced desiccation-saturation cycles that altered redox conditions in the S. patens soils, resulting in rapid changes in the dissolution and precipitation of iron and in the magnitude and spatial distribution of SO4(-2) reduction.
An ion exchange polymer comprised of an alkali metal or alkaline earth metal salt of a poly(carboxylic acid) in a poly(vinyl acetal) matrix is described. The polymer is made by treating a mixture made of poly(vinyl alcohol) and poly(acrylic acid) with a suitable aldehyde and an acid catalyst to cause acetalization with some cross-linking. The material is then subjected to an alkaline aqueous solution of an alkali metal salt or an alkali earth metal salt. All of the film forming and cross-linking steps can be carried out simultaneously, if desired.
In the early 1980's the NASA Lewis group addressed the topic of designing nickel hydrogen cells for LEO applications. As published in 1984, the design addressed the topics of gas management, liquid management, plate expansion, and the recombination of oxygen during overcharge. This design effort followed principles set forth in an earlier Lewis paper that addressed the topic of pore size engineering. At about that same time, the beneficial effect on cycle life of lower electrolyte concentrations was verified by Hughes Aircraft as part of a Lewis funded study. A succession of life cycle tests of these concepts have been carried out that essentially verified all of this earlier work. During these past two decades, some of the mysteries involved in the active material of the nickel electrode have been resolved by careful research efforts carried out at several laboratories. At The Aerospace Corporation, Dr. Zimmerman has been developing a sophisticated model of an operating nickel hydrogen cell which will be used to model certain mechanisms that have contributed to premature failures in nickel hydrogen and nickel cadmium cells. During the course of trying to understand and model abnormal nickel hydrogen cell behaviors, we have noted that not enough attention has been paid to the potassium ion content in these cells, and more recently batteries. Several of these phenomenon have been well known in the area of alkaline fuel cells, but only recently have they been examined as they might impact alkaline cell designs. This paper will review three general areas where the potassium ion content can impact the performance and life of nickel hydrogen and nickel cadmium devices, Once these phenomenon are understood conceptually, the impact of potassium content on a potential cell design can be evaluated with the aid of an accurate model of an operating cell or battery. All three of these areas are directly related to the volume tolerance and pore size engineering aspects of the components used in the cell or battery design: (1) The gamma phase uptake of potassium ion can result in a lowering of the electrolyte concentration. This leads to a higher electrolyte resistance as well as electrolyte diffusional limitations on the discharge rate. This phenomenon will also impact the response of the cell to a reconditioning cycle. (2) The impact of low level shunt currents in multi-cell con figurations will result in the movement of potassium ion from one part of the battery to another. This will impact the electrolyte volume/vapor pressure relationships within the cell or battery. (3) The transport of water vapor from place to place under the driving force of a tempetature gradient has already impacted cells for the case where water vapor is condensed on a colder cell wall. The paper will explore the convective and diffusive movement of gases saturated with water vapor from a warmer plate pack to a cooler one - both with and without liquid communication.
Fuel cells have a long history in space applications and may have potential application in aeronautics as well. A fuel cell is an electrochemical energy conversion device that directly transforms the chemical energy of a fuel and oxidant into electrical energy. Alkaline fuel cells have been the mainstay of the U.S. space program, providing power for the Apollo missions and the Space Shuttle. However, Proton Exchange Membrane (PEM) fuel cells offer potential benefits over alkaline systems and are currently under development for the next generation Reusable Launch Vehicle (RLV). Furthermore, primary and regenerative systems utilizing PEM technology are also being considered for future space applications such as surface power and planetary aircraft. In addition to these applications, the NASA Glenn Research Center is currently studying the feasibility of the use of both PEM and solid oxide fuel cells for low- or zero-emission electric aircraft propulsion. These types of systems have potential applications for high altitude environmental aircraft, general aviation and commercial aircraft, and high attitude airships. NASA Glenn has a unique set of capabilities and expertise essential to the successful development of advanced fuel cell power systems for space and aeronautics applications. NASA Glenn's role in past fuel cell development programs as well as current activities to meet these new challenges will be presented
The microorganisms of soda Mono Lake and other similar athalassic hypersaline alkaline soda lakes are of significance to Astrobiology. The microorganisms of these regimes represent the best known terrestrial analogs for microbial life that might have inhabited the hypersaline alkaline lakes and evaporites confined within closed volcanic basins and impact craters during the late Noachian and early Hesperian epochs (3.6 - 4.2 Gya) of ancient Mars. We have investigated the anaerobic microbiota of soda Mono Lake in northern California. In this paper we discuss the astrobiological significance of these ecosystems and describe several interesting features of two novel new species of anaerobic halo-alkaliphilic bacteria (Spirochaeta americana, sp. nov. and Desulfonatronum paiuteum, sp. nov) that we have isolated from Mono Lake.
The Fuel Cell has been used for manned space flight since the Gemini program. Its power output and water production capability over long durations for the mass and volume are critical for manned space-flight requirements. The alkaline fuel cell used on the Shuttle, while very reliable and capable for it s application, has operational sensitivities, limited life, and an expensive recycle cost. The PEM fuel cell offers many potential improvements in those areas. NASA Glenn Research Center is currently leading a PEM fuel cell development and test program intended to move the technology closer to the point required for manned space-flight consideration. This paper will address the advantages of PEM fuel cell technology and its potential for future space flight as compared to existing alkaline fuel cells. It will also cover the technical hurdles that must be overcome. In addition, a description of the NASA PEM fuel cell development program will be presented, and the current status of this effort discussed. The effort is a combination of stack and ancillary component hardware development, culminating in breadboard and engineering model unit assembly and test. Finally, a detailed roadmap for proceeding fiom engineering model hardware to qualification and flight hardware will be proposed. Innovative test engineering and potential payload manifesting may be required to actually validate/certify a PEM fuel cell for manned space flight.
The LiFeS2 test program was part of the study on state-of-the-art batteries/cells available in the commercial market. It was carried out in an effort to replace alkaline AA cells for Shuttle and Station applications. A large number of alkaline cells are used for numerous Shuttle and Station applications as loose cells. Other government agencies reported good performance and abuse tolerance of the AA LiFeS2 cells. In this study, only abuse testing was performed on the cells to determine their tolerance. The tests carried out were over-discharge, external short circuit, heat-to-vent, vibration and drop.
Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.
The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.
Ophiolite sequences, sections of lower oceanic crust and upper mantle that have been thrust onto continental craton, are located in northern and central California and provide easily accessible areas that serve as good analogs for similar, more extensive areas of the early Earth. We have begun investigating and characterizing these sites in order to understand better the processes that may be responsible for the water chemistry, mineralogy and biology of similar environments on the early Earth. The geophysical and geochemical processes in these terranes provide niches for unique communities of extremeophiles and likely provide a good analog to the location that first gave rise to life on Earth. The ophiolites found in northern and central California include the Trinity, Josephine, Coast Range and Point Sal, all of which are approximately 160 million years old. Fluids from serpentinizing springs are generally alkaline with high pH and H2 contents, indicating that the mafic rock compositions control the fluid composition through water-rock reactions during relatively low-grade hydrothermal processes. There are significant amounts of primary mineralogy remaining in the rocks, meaning that substantial alteration processes are still occurring in these terranes. The general reaction for serpentinization of olivine is given by one of the authors. olivine + H2O = serpentine + brucite + magnetite + H2. We have analyzed the mineralogical composition of several rock samples collected from the Coast Range Ophiolite near Clear Lake, CA by electron microprobe. The remnant primary mineralogy is fairly urnform in composition, with an olivine composition of Fo(sub 90), and with pyroxene compositions of En(sub 90) for orthopyroxene and En(sub 49)Wo(sub 48)Fs(sub 03) for the clinopyroxene. Other primary phases observed include chromites and other spinels. Examination of petrographic thin sections reveals that serpentinization reactions have occurred in these locations. The serpentine resulting from aqueous alteration of olivine resides in veins that are see to cross cut the primary mineral grains. There are several generations of alteration products, comprised mostly of serpentines that are magnesium rich, with magnetite, brucite and carbonates observed as accessory minerals. The formation of carbonates can be taken to indicate the presence of CO2 in the altering fluids. We collected samples from a spring in the Coast Range Ophiolite in order to determine whether the geochemical environment serves as a habitat for chemotrophic microorganisms. DNA was extracted from the sediment samples and the 16s rRNA gene was PCR amplified using universal Archaeal primers. Denaturing gradient gel electrophoresis (DGGE) was used to determine the community of Archaea thriving in these samples. Our results indicate that there were 8 different genera of Archaea from a single sample. A sequence was obtained from one of these eight. The sequence is of an organism similar to Halorubrum tibetense, and alkalophilic Archaeon. This result suggests that these environments are likely hosts for communities of organisms that are adapted for the unique chemistry provided by the alkaline spring.
Skeletal unloading in an animal hindlimb suspension model and microgravity experienced by astronauts or as a result of prolonged bed rest causes site-specific losses in bone mineral density of 1%-2% per month. This is accompanied by reductions in circulating levels of 1,25-(OH)(2)D(3), the active metabolite of vitamin D. 1,25-(OH)(2)D(3), the ligand for the vitamin D receptor (VDR), is important for calcium absorption and plays a role in differentiation of osteoblasts and osteoclasts. To examine the responses of cells to activators of the VDR in a simulated microgravity environment, we used slow-turning lateral vessels (STLVs) in a rotating cell culture system. We found that, similar to cells grown in microgravity, MG-63 cells grown in the STLVs produce less osteocalcin, alkaline phosphatase, and collagen Ialpha1 mRNA and are less responsive to 1,25-(OH)(2)D(3). In addition, expression of VDR was reduced. Moreover, growth in the STLV caused activation of the stress-activated protein kinase pathway (SAPK), a kinase that inhibits VDR activity. In contrast, the 1,25-(OH)(2)D(3) analog, EB1089, was able to compensate for some of the STLV-associated responses by reducing SAPK activity, elevating VDR levels, and increasing expression of osteocalcin and alkaline phosphatase. These studies suggest that, not only does simulated microgravity reduce differentiation of MG-63 cells, but the activity of the VDR, an important regulator of bone metabolism, is reduced. Use of potent, less calcemic analogs of 1,25-(OH)(2)D(3) may aid in overcoming this defect. Copyright 2002 Elsevier Science Inc.
Oligodeoxynucleotide hybridization probes were developed to complement specific regions of the small subunit (SSU) rRNA sequences of cultivated and uncultivated cyanobacteria and Chloroflexus-like bacteria, which inhabit hot spring microbial mats. The probes were used to investigate the natural distribution of SSU rRNAs from these species in mats of Yellowstone hot springs of different temperatures and pHs as well as changes in SSU rRNA distribution resulting from 1-week in situ shifts in temperature, pH, and light intensity. Synechococcus lividus Y-7c-s SSU rRNA was detected only in the mat of a slightly acid spring, from which it may have been initially isolated, or when samples from a more alkaline spring were incubated in the more acid spring. Chloroflexus aurantiacus Y-400-fl SSU rRNA was detected only in a high-temperature mat sample from the alkaline Octopus Spring or when lower-temperature samples from this mat were incubated at the high-temperature site. SSU rRNAs of uncultivated species were more widely distributed. Temperature distributions and responses to in situ temperature shifts suggested that some of the uncultivated cyanobacteria might be adapted to high-, moderate-, and low-temperature ranges whereas an uncultivated Chloroflexus-like bacterium appears to have broad temperature tolerance. SSU rRNAs of all uncultivated species inhabiting a 48 to 51 degrees C Octopus Spring mat site were most abundant in the upper 1 mm and were not detected below a 2.5-to 3.5-mm depth, a finding consistent with their possible phototrophic nature. However, the effects of light intensity reduction on these SSU rRNAs were variable, indicating the difficulty of demonstrating a phototrophic phenotype in light reduction experiments.
In the present study, we enumerate and characterize the proteins that comprise the integral spicule matrix of the Strongylocentrotus purpuratus embryo. Two-dimensional gel electrophoresis of [35S]methionine radiolabeled spicule matrix proteins reveals that there are 12 strongly radiolabeled spicule matrix proteins and approximately three dozen less strongly radiolabeled spicule matrix proteins. The majority of the proteins have acidic isoelectric points; however, there are several spicule matrix proteins that have more alkaline isoelectric points. Western blotting analysis indicates that SM50 is the spicule matrix protein with the most alkaline isoelectric point. In addition, two distinct SM30 proteins are identified in embryonic spicules, and they have apparent molecular masses of approximately 43 and 46 kDa. Comparisons between embryonic spicule matrix proteins and adult spine integral matrix proteins suggest that the embryonic 43-kDa SM30 protein is an embryonic isoform of SM30. An adult 49-kDa spine matrix protein is also identified as a possible adult isoform of SM30. Analysis of the SM30 amino acid sequences indicates that a portion of SM30 proteins is very similar to the carbohydrate recognition domain of C-type lectin proteins.
We have recently developed the ability to rapidly assess Surface inherent optical properties (IOP), oxygen concentration and pCO2 in estuarine-plume systems using flow-through instrumentation. During the summer of 2004, several estuarine-plume systems were surveyed which include the Pleasant (ME), Penobscot (ME), Kennebec-Androscoggin (ME), Merrimack (NH-MA) and Hudson (NY). Continuous measurements of surface chlorophyll and colored dissolved organic carbon (CDOM) fluorescence, beam attenuation, temperature, salinity, oxygen and pC02 were taken at each system along a salinity gradient from fresh water to near oceanic endmembers. CTD and IOP profiles were also taken at predetermined surface salinity intervals. These were accompanied by discrete determinations of chlorophyll (HPLC and fluorometric), total suspended solids (TSS), dissolved organic carbon (DOC) and alkalinity. IOP data were calibrated using chlorophyll, DOC and TSS data to enable the retrieval of these constituents from IOP data. Considerable differences in the data sets were observed between systems. These ranged from the DOC-enriched, strongly heterotrophic Pleasant River System to the high-chlorophyll autotrophic Merrimack River System. Using pCO2 and oxygen saturation measurements as proxies for water column metabolism, distinct relationships were found between trophic status and inherent optical properties. The nature of these relationships varies between systems and is likely a function of watershed and estuarine attributes including carbon and nutrient loading, in-situ production and related autochthonous inputs of DOC and alkalinity. Our results suggest that IOP data may contain significant information about the trophic status of estuarine and plume systems.
Humans reach peak bone mass at age 30. After this point, we lose 1 to 2 percent of bone mass each decade. In the microgravity environment of space, astronauts lose bone mass at an accelerated rate of 1 to 2 percent each month. When astronauts travel to Mars, they may be in space for as long as 3 years. During this time, they may lose about half of their bone mass from weight-bearing bones. This loss may be irreversible. The drastic loss in bone that astronauts experience in space makes them much more vulnerable to fractures. In addition, the corresponding removal of calcium from bone results in higher levels of calcium in the blood, which increases the risk of developing kidney stones. Currently, studies are being conducted which investigate factors governing bone adaptation and mechanotransduction. Bone is constantly adapting in response to mechanical stimuli. Increased mechanical loading stimulates bone formation and suppresses bone resorption. Reduction in mechanical loading caused by bedrest, disuse, or microgravity results in decreased bone formation and possibly increased bone resorption. Osteoblasts and osteoclasts are the two main cell types that participate in bone remodeling. Osteoblasts are anabolic (bone-forming) cells and osteoclasts are catabolic (bone-resorbing) cells. In microgravity, the activity of osteoblasts slows down and the activity of osteoclasts may speed up, causing a loss of bone density. Mechanotransduction, the molecular mechanism by which mechanical stimuli are converted to biochemical signals, is not yet understood. Exposure of cells to fluid flow imposes a shear stress on the cells. Several studies have shown that the shear stress that results from fluid flow induces a cellular response similar to that induced by mechanical loading. Thus, fluid flow can be used as an in vitro model to simulate the mechanical stress that bone cells experience in vivo. Previous in vitro studies have shown that fluid flow induces several responses in osteoblasts, including increased proliferation, osteoblastic differentiation, alkaline phosphatase activity, and production of nitric oxide, prostaglandins, and osteopontin. Several proteins have been implicated in osteoblastic mechanotransduction including Bone Morphogenetic Protein-2 (BMP-2), parathyroid hormone, 1,25-dihydroxyvitamin D3 receptor, osteopontin (OPN), osteoprotegerin (OPG), and alkaline phosphatase (AP). We will characterize relative levels of each protein in mineralizing or non-mineralizing MC3T3 osteoblastic cells that have been exposed to fluid flow compared to non-fluid flow using immunofluorescent staining and two- photon laser microscopy as well as western blotting. Because calcium-mediated pathways are important in osteoblastic signaling, we will transfect MC3T3 cells with cameleon probes for Ca2+ containing YFP and CFP. Results will be analyzed using FRET/FLIM to study differential release of intracellular Ca(2+) in response to fluid flow and conditions inducing matrix mineralization. In addition, we plan to conduct several microarray experiments to determine differential gene expression in MC3T3 cells in response to fluid flow and conditions inducing mineralization.
The information contained in the presentation covers development work carried out under SDS projects. The intent of the effort is to find chrome(VI) free alternates to our current chromated processing solutions. The information presented reports progress in work aimed to replace our alkaline cleaner (Turco 4215), conversion coat (Iridite 14-2) and chrome (VI) compounds used in LOx tank hydrostatic proof test solution. To date we have found candidates for use in the proof test solution and alkaline cleaner. These candidates are in the final stages of testing. Lab data is reported in the presentation.
Life-test data of Lithium-Ion battery cells is critical in order to establish their performance capabilities for NASA missions and Exploration goals. Lithium-ion cells have the potential to replace rechargeable alkaline cells in aerospace applications, but they require a more complex charging scheme than is typically required for alkaline cells. To address these requirements in our Lithium-Ion Cell Test Verification Program, a Lithium-Ion Cell Charge Control Unit was developed by NASA Glenn Research Center (GRC). This unit gives researchers the ability to test cells together as a pack, while allowing each cell to charge individually. This allows the inherent cell-to-cell variations to be addressed on a series string of cells and results in a substantial reduction in test costs as compared to individual cell testing. The Naval Surface Warfare Center at Crane, Indiana developed a power reduction scheme that works in conjunction with the Lithium-Ion Cell Charge Control Unit. This scheme minimizes the power dissipation required by the circuitry to prolong circuit life and improve its reliability.