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At least 109 records · Page 6

Coherent optical array receiver experiment : design, implementation and BER performance of a multichannel coherent optical receiver for PPM signals under atmospheric turbulence

The performance of a coherent free-space optical communication system operating in the presence of turbulence is investigated. Maximum Likelihood Detection techniques are employed to optimally detect Pulse Position Modulated signals with a focal-plane detector array, and reconstruct the turbulence-degraded signals. The experimental demonstration of this project and results may be divided in three parts; two of which have already been explained in previous publications (1,2). This latest paper shows the final experimental results, including investigation of performance of the Coherent Optical Receiver Experiment (CORE) performed at the laboratory facilities at JPL. Bit Error Rate (BER) is presented for single and multichannel optical receivers, where quasi-shot noise limited performance is achieved, under simulated turbulence conditions using non-coherent post-detection processing techniques.

Hassibi, Babak↗

Acute, 2-week, and 13-week inhalation toxicity studies on dimethylethoxysilane vapor in Fischer 344 rats

Dimethylethoxysilane (DMES), a volatile liquid, is used by NASA to waterproof the heat-protective silica tiles and blankets on the Space Shuttle. Acute, 2-wk, and 13-wk inhalation exposures to DMES vapor were conducted in male and female Fischer 344 rats. In the acute study, rats were exposed to 4000, 2000, 1000, 500, or 0 (control) ppm DMES for 4 h and observed for 14 days. There were no deaths. Narcosis and ataxia were observed in rats of the two highest concentrations only. These signs disappeared within 1 h following exposure. There were no DMES-related gross or microscopic tissue lesions in rats of all exposure groups. In the 2-wk study, rats were exposed for 6 h/day, 5 days/wk to 3000, 1000, 300, 100, or 0 ppm DMES. During exposure, narcosis was observed in rats of the 3000 and 1000 ppm groups. There was a mild decrease in body weight gain in rats of the 3000 ppm group. A decrease in platelet count, an increase in bile acids, and reduced weights of the thymus, testis, and liver were observed in rats of the 3000 ppm group. Microscopically, hypospermatogenesis and spermatid giant cells were observed in the seminiferous tubules of the testes of rats exposed to 3000 ppm DMES. In the 13-wk study, rats were exposed 6 h/day, 5 days/wk to 2000, 600, 160, 40, or 0 ppm DMES. During exposure, rats of the 2000 ppm group exhibited mild narcosis and loss of startle reflex. Recovery from these central nervous system signs was rapid. Body weights were mildly decreased for rats of the 2000 ppm group. There were no exposure-related effects in hematology, serum chemistry, or urinalysis. Female rats of the 2000 ppm group had delayed estrous cycles (6 days compared to 5 days in control rats). Noteworthy organ weight changes in rats of the 2000 ppm group included decreases in thymus, liver, and testicular weights; however, pathologic lesions were observed in the testes only. Sperm motility, epididymal sperm count, and testicular spermatid count were dramatically reduced. Microscopic lesions included degeneration of the seminiferous tubular cells, pyknosis or absence of germ cells, and hypospermia in the epididymis. Rats of the 600 ppm group had a slight decrease in thymic weight and a transient decrease in body weight. Results of the acute, 2-wk, and 13-wk inhalation studies indicate DMES concentrations of 1000 ppm and higher produce narcosis that rapidly disappears following exposure. Repeated exposure of rats to DMES at either 3000 ppm for 2 wk or 2000 ppm for 13 wk caused testicular atrophy and hypospermia in male rats. Female rats exposed to 2000 ppm for 13 wk had delayed estrous cycles. Toxicological effects in rats of the 600 ppm group were minimal and equivocal. The 160 ppm concentration was a no-observable-effect level (NOEL) for 13 wk of exposure to DMES.

NASA Discipline Number 04-10↗

Sulfur, Chlorine and Fluorine Degassing and Atmospheric Loading by the Roza eruption, Columbia River Basalt Group, Washington

In this study we attempt to quantify the amount of S, Cl and F released by the 1300 cu km Roza member (approximately 14.7 Ma) of the Columbia River Basalt Group, which was produced by a moderate-size flood basalt eruption in the mid-Miocene. Our results are the first indication of the potential atmospheric SO2 yield from a flood basalt eruption, and indicate the mechanism by which flood basalt eruptions may have seriously affected the environment. Glass inclusions in phenocrysts and quenched glass in products from various stages of the eruption were analyzed for concentrations of S, Cl and F and major elements. Glass inclusions contain 1965 +/- 110 ppm S, 295 +/- 65 ppm Cl and 1310 +/- 110 ppm F. Groundmass glass of Roza dike selvages contains considerably lower concentrations: 1110 +/- 90 ppm S, 245 +/- 30 ppm Cl and 1020 +/- 25 ppm F. Scoria clasts from near vent deposits contain 665 +/- 75 ppm S, 175 +/- 5 ppm Cl and 950 +/- 20 ppm F, and the groundmass glass of lava selvages contains 520 +/- 30 ppm S, 190 +/- 30 ppm Cl and 890 +/- 55 ppm F. In crystalline lava, the concentrations are 195 ppm S, 100 ppm Cl and 830 ppm F. Volatile element concentrations in these samples represent the progress of degassing through the eruption and can be used to estimate the potential amount of the volatiles S, Cl and F released by the magma into the atmosphere, as well as to evaluate the amount liberated by various phases of the eruption. The total amount of volatiles released by the Roza eruption is estimated to have been approximately 12,420 MtSO2, approximately 710 MtHCI and approximately 1780 MtHF. The Roza magma liberated approximately 9620 MtSO, (77% of the total volatile mass released), approximately 400 MtHCI (56%) and approximately 1450 MtHF (81%) at the vents and lofted by the eruption columns to altitudes of 7-13 km. Degassing of the lava is estimated to have released an additional approximately 2810 MtSO2, approximately 310 MtHCI and approximately 330 MtHF. The Roza eruption is likely to have lasted for approximately 10 years, indicating an annual H2SO4-mass loading of approximately 1800 Mt. Thus, the atmospheric perturbations associated with the Roza eruption may have been of the magnitude predicted for a severe "nuclear" or "volcanic" winter, but lasting up to a decade or more.

Thordarson, Th.↗

Detection of hydrazine (H) and (MMH) using cyranose E-nose

The Cyranose electronic nose (e-nose) has been used for the first time to detect hydrazine (H) and monomethyl hydrazine (MMH). The concentrations of hydrazine chosen in this study were 52 ppm (parts per million), 18 ppm, and 1.1 ppm and the concentrations of MMH was 14 ppm and 1 ppm. The Cyranose E-nose has detected hydrazine of 52 ppm and 18 ppm with a good response. The response of the E-Nose for 1.1 ppm hydrazine was insignificant. The response of E-Nose for 14 ppm MMH was significant and 1 ppm MMH was reasonably identifiable. The Cyranose E-Nose may be used to detect hydrazine and MMH with concentrations of at least 18 ppm and 1 ppm, respectively.

cyranose↗

Rare Earth Elements (REE) and Critical Minerals (CM) in Middle Pennsylvanian-Age Coals and Associated Sediments in the Central Appalachian Basin, Eastern U.S.A.

The Central Appalachian Basin (CAB) of Kentucky, Tennessee, West Virginia and Virginia has a long history of coal mining and oil and gas extraction that has empowered the regional and national economies, the development of infrastructure, and a highly trained energy resources work force. As our societal demands for advanced technologies have rapidly increased in recent years, coal-related materials are viewed as an important new unconventional domestic source of critical minerals (CM) that are required for telecommunications, aerospace and transportation industries, electronics, the transition to low-carbon emissions energy production, and many consumer products. Coal-related materials encompass coal, associated sediments, coal mining waste materials, produced waters, and ash residues from coal-fired power plants. An important objective of the Evolve Central Appalachia Project (Evolve CAPP), sponsored by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL) is to assess the quantity and distribution of CM resources in the CAB region. The rare earth elements (REE) are considered highest priority, although other important CM such as niobium, gallium, and zirconium are known to occur in the Middle Pennsylvanian-age coals and sediments. Working with coal industry partners who provided access to drill cores, coal-related sediments and waste materials, over 600 samples have been collected for laboratory analysis, and over 730 materials have been scanned using portable x-ray fluorescence (pXRF) equipment. The application of pXRF provides the means for real-time semiquantitative analysis of CM content at very close spacings (typically 2-3 inch intervals) along drill core and in-situ channel samples that span the roof, coal seam, and floor rock. The comparison of pXRF geochemical data with laboratory results, geologic data, and downhole spectral gamma logs can provide high resolution input to lithologic and depositional models for future CM resource evaluations. The preliminary findings show that pXRF is capable of accurately measuring low concentrations of many of the CM with a high level of confidence (Ba, Cr, Ga, K, Nb, Rb, Sr, Th, Y), whereas for others (La, Ce, Co, Mn, Nd, Ni, Sc, Ti, V) the detection limits are very high or spectral interferences increase the uncertainty. Notably, the mean abundances of Y (34 ppm), La (86 ppm), Ga (40 ppm), and V (146 ppm) in coal underclays in the CAB region are up to 7X enriched compared with the overlying coal. These values also exceed the reported concentrations in published reference materials for upper continental crustal rocks (Rudnick and Gao, 2003), North American Shale Composite (Gromet et al., 1984), and North American coal (Finkelman, 1993). The pXRF data are in part verified by laboratory results that indicate the mean Y abundance (36 ppm) is highly correlated (R2 = 0.807) with total REE (ΣREE). The correlation is even higher (R2 = 0.957) with heavy REE (ΣHREE). Applying these correlations to the pXRF data for the coal underclays, the mean estimated values for ΣREE+Y and ΣHREE+Y are 270 ppm and 58 ppm, respectively. Although these average values are not considered high, the range of Y measured by pXRF in the coal underclays extended as high as 114 ppm, which would suggest ΣREE+Y equal to 847 ppm. The mean abundances of Zr (192 ppm) and Th (21 ppm) in coal underclays are also enriched compared with the overlying coal and these results likely reflect the presence of resistant detrital heavy minerals such as monazite, xenotime, and zircon in the underclay matrix. Several of the profiled coal seams and associated wall rocks contained thin volcanic ash layers up to 4-5 inches in thickness. The extent to which these ash fall layers provided a source for CM under the paleoenvironmental conditions that resulted in coal deposits in the CAB remains to be fully studied. Continuing investigations in the Evolve CAPP study area will include laboratory determinations of mineralogic and clay compositions, and evaluations of CM geochemical mobility in the coal and coal underclays.

Lassetter, Billy↗

Thorium Enrichment within the Procellarum KREEP Terrane: The Record in Surface Deposits and Significance for Thermal Evolution

The nearside-farside structural and compositional asymmetry of the Moon was recognized during the early days of Apollo and the suggestion was made that the migration of mantle melts to the nearside would have been favored by early Earth-Moon orbital dynamics and nonuniform planetesimal bombardment. Recent global geochemical mapping by Lunar Prospector has provided additional data, particularly in the Th distribution, that strongly supports the notion of global, preferential melt migration, which led in part to the development of the Procellarum KREEP Terrane (PKT) [2-5]. The surface distribution of Th was then reshaped by basin-forming impacts into the PKT, especially the Imbrium impact, which was the last and largest to strike in that region. The Imbrium event probably excavated material from a partially molten zone deep in the crust and delivered Th-rich ejecta Moon-wide. A fundamentally important but poorly understood aspect of the global Th distribution is the concentration of Th in the subsurface rocks of the PKT crustal section. For example, depending on what assumptions are made, the PKT crustal section, which is about 12% of the crust and only about 1.2% of the whole Moon, may contain as much as 40% of the Moon's entire Th budget. Such a distribution of Th and related heat-producing elements would have had a profound effect on melting, mixing, and the thermal evolution of the PKT and the underlying mantle. In this abstract, we examine the compositions of terra formations within the PKT and relate them to some of the Th-bearing rock types known from the Apollo samples. It appears that the existence of the PKT may be a unifying concept for a number of petrologic and geochemical observations. From the initial Lunar Prospector gamma-ray spectrometer data(-about 5 deg. resolution) and from the preliminary low-orbit data, there appears to be a number of relatively hotter "spots" within the PKT in terms of Th concentration. Some of the hotter spots correspond to intermediate-sized craters that penetrated volcanic flows and excavated Th-rich, submare material, such as Aristarchus, Aristillus, and Kepler. Other spots, however, correspond to surficial formations that constitute mainly rough topography associated with Imbrium ejecta or circum-Imbrium ring mountains and do not necessarily imply the presence of exposed KREEP basalts. The Fra Mauro Formation south of Copernicus toward the Apollo 14 site and regions of the Alpes Formation southwest of Copernicus in the vicinity of Reinhold lie within the most prominent hotspot; here them concentration is consistent with that found in the Apollo 14 soils (about 12-13 ppm) when the proportions of Fra Mauro Formation and mare basalt are considered. The area between Copernicus and Kepler and northwest of Copernicus in terra extending to the Carpathians is similarly enriched in Th. The Apennines from Eratosthenes toward the Apollo 15 site contain elevated Th concentrations, as does the northwestern quadrant of circum-Imbrium terra, especially between (but not including) La Condamine and Plato, and in the region northwest of the Jura mountains extending southward past Mairan to the Gruithuisen-Domes region. Within the main topographic rim of Imbrium, the Apennine Bench formation south of Archimedes appears to have relatively elevated Th concentration. Comparing the map of Th distribution to a digital-elevation map derived from Clementine altimetry, it appears that most of the areas richest in Th occur where the surface is elevated relative to the majority of PKT volcanic plains. Not all rough topography within the PKT has such elevated Th, however. Based on an analysis of the 5 deg. data, and using the calibration of, the mean Th concentrations for mainly volcanic-resurfaced terrain and rugged terrain are similar (about 5.5 ppm). This occurs in part because craters that penetrated mare basalt excavated Th-rich material. Even so, there appear to be extensive areas of volcanic resurfacing that have no obvious extrinsic source of Th-rich material, suggesting that the basalts, themselves, may contain as much as 5-6 ppm Th. High-FeO concentrations (18 to >20 wt%) indicate that these are not KREEP basalts but mare basalts. If so, this is surprising because most of the Apollo-sampled mare basalts have very low-Th (typically <2 ppm). A variety of Th-rich materials occur in the sample collection, particularly in the samples from the Apollo 12,14, and 15 sites. The most abundant Th-rich rock types are the mafic impact-melt breccias, which although found at all sites, are most abundant at Apollo 14, where they dominate the rock samples and make up some 40% of the rock particles in the soil. These have Th concentrations ranging up to about 30 ppm and averaging about 18 ppm. The Apollo 14 soils contain about 13 ppm Th, reflecting the high abundance of this melt-breccia component. At the nearby Apollo 12 site, the rocks consist mainly of mare basalts, and these have low-Th concentrations, mostly <1 ppm. Among the nonmare rocks, however, a few such as complex breccia 12013 contain a variety of evolved lithologies and represent potential sources of Th-rich components ranging from 17 to 50 ppm. A single fragment of KREEP basalt from the Apollo 12 soil contains about 50 ppm Th. Despite the identification of highly Th-enriched lithologic components at the Apollo 12 site, the soils there vary linearly in composition so as to extrapolate to a moderate Th KREEP-basalt component or a composition like that of the Fra Mauro formation as reflected by Apollo 14 soil (14 ppm Th at 10 wt% FeO). The nearby Lansberg Crater (39-km diameter) is a likely candidate to have delivered submare material such as buried Fra Mauro or Alpes material to the Apollo 12 site. Additional information contained in the original.

Jolliff, B. L.↗

UO2 microstructural evolutions induced by Ni, Mo, and W dopants for intentional forensics

The concept of tagging nuclear fuel with a chemical barcode to enable forensics analysis across the nuclear fuel cycle is an area of active investigation, particularly to ensure fabrication viability without disrupting current fuel performance. This study explored the feasibility of using Ni, Mo, and W isotopic double-spikes as dopants in UO2 fuel from the perspective of fuel fabrication. Doped UO2 pellets were produced using conventional fuel fabrication processes, including powder mixing, sieving, pressing, and sintering in a reductive atmosphere. Two composition levels, 100 and 1000 ppm, were evaluated for each dopant element with isotopic double-spike configurations. For the Ni system, additional dopant concentrations of 250 and 500 ppm were produced with nonperturbed isotopic ratios. The results demonstrated that successful incorporation of Ni, Mo, and W double-spikes into UO2 pellets occurred with minimal shift in final density or dopant loss during pellet fabrication. Isotopic analysis confirmed the presence of the double-spike signature even when diluted with natural isotopic material in ratio of 1:5 in the fabrication process. Microstructural examinations revealed different impacts on grain size compared with undoped UO2. This study showed that Ni incorporation up to ∼500 ppm promoted moderate grain growth, whereas the Mo and W systems caused grain size reduction at all concentrations. Changes in the UO2 lattice parameter as a function of composition were detected exclusively for Ni up to 500 ppm, indicating that the Ni solid solution was the main factor for the observed grain growth. Insoluble (Mo and W) or supersaturated (Ni > 500 ppm) conditions produced grain size reduction. The Ni-doped pellets in the solution range resulted in a final microstructure within fuel specifications, demonstrating its potential benefits of employing complex dopant systems for potential nuclear forensic applications.

36 MATERIALS SCIENCE↗

Sample Diluter for Detecting Hypergolic Propellants and Other Toxic or Hazardous Gases

Hardware was developed to dilute vapor samples of purged hypergolic propellants (with air) into the range of existing instruments for detection of such toxic vapors. Since these detectors are normally used to monitor at the threshold limit value (TLV), most do not have quantitative capability at percent levels which relate to lower explosion limit (LEL) and fire hazards. For example, the upper limits of Energetic Sciences (ESI) 6000 series detectors used at KSC are 200 parts per million (ppm) for monomethyl hydrazine (MMH) and 500 ppm for nitrogen dioxide (NO2) arising from decomposition of nitrogen tetroxide (N2O4). Orbiter Processing Facility (OPF) personnel servicing Shuttle thrusters need to measure up to 250 ppm MMH and 7,500 ppm NO2 with portable, intrinsically safe instruments. Our objective was to quickly fabricate a sample diluter out of existing materials as a temporary measure while other parallel efforts were conducted to provide a commercial or in-house-developed instrument to detect high propellant levels. A 3 to 1 diluter would bring 500 ppm MMH into the range of the existing fuel ESI, and a 30 to 1 diluter would do the same for NO2. In this way, familiar equipment already available would be used, resulting in minimal paperwork, safety, and training impacts and low cost. An MMH vapor sample-diluter was constructed from a 1/4-inch Kynar tee, along with specially designed lengths of sample and dilution tubing. The sample line was 3 feet of Bev-A-Line 4, 1/4-inch tube leading to the straight run of the tee. The side run of the tee had a 17-inch length of Bev-A-Line 4, 1/4-inch tube, for nominal 3 to 1 dilution. A gas sample bag was prepared and assayed at 113 ppm ppm MMH, and diluted vapor samples were assayed at 39.5 ppm, or a measured dilution of 2.9 to 1. For NO2, a 316 stainless steel (SS) 1/8-inch tee with 49.5 inches of coiled, 1/8-inch outside diameter (OD) 316 SS tubing was used as the sampling end of the dilution system. The side run of the tee was open. The measured dilution ratio, based on the input value of 6,480 ppm NO2, and the average output value of 233 ppm, was 28 to 1. Thus, sample-diluters were successful in diluting concentrated hypergolic propellant vapors, both MMH and N2O4 into the ranges of existing TLV detectors.

Barile, R. G.↗

Sample Diluter for Detecting Hypergolic Propellants and Other Toxic or Hazardous Gases

Hardware was developed to dilute vapor samples of purged hypergolic propellants (with air) into the range of existing instruments for detection of such toxic vapors. Since these detectors are normally used to monitor at the threshold limit value (TLV), most do not have quantitative capability at percent levels which relate to lower explosion limit (LEL) and fire hazards. For example, the upper limits of Energetic Sciences (ESI) 6000 series detectors used at KSC are 200 parts per million (ppm) for monomethyl hydrazine (MMH) and 500 ppm for nitrogen dioxide (NO2) arising from decomposition of nitrogen tetroxide (N2O4). Orbiter Processing Facility (OPF) personnel servicing Shuttle thrusters need to measure up to 250 ppm MMH and 7500 ppm NO2 with portable, intrinsically safe instruments. Our objective was to quickly fabricate a sample diluter out of existing materials as a temporary measure while other parallel efforts were conducted to provide a commercial or in-house-developed instrument to detect high propellant levels. A 3 to 1 diluter would bring 500 ppm MMH into the range of the existing fuel ESI, and a 30 to 1 diluter would do the same for NO2. In this way, familiar equipment already available would be used, resulting in minimal paperwork, safety, and training impacts and low cost. An MMH vapor sample-diluter was constructed from a 1/4-inch Kynar tee, along with specially designed lengths of sample and dilution tubing. The sample line was 3 feet of Bev-A-Line 4, 1/4 inch tube leading to the straight run of the tee. The side run of the tee had a 17-inch length of Bev-A-Line 4, 1/4-inch tube, for nominal 3 to 1 dilution. A gas sample bag was prepared and assayed at 113 ppm MMH, and diluted vapor sarnples were assayed at 39.5 ppm, or a measured dilution of 2.9 to 1. For NO2, a 316 stainless steel (SS) 1/8-inch tee with 49.5 inches of coiled, 1/8-inch outside diameter (OD) 316 SS tubing was used as the sarnpling end of the dilution system. The side run of the tee was open. The measured dilution ratio, based on the input value of 6,480 ppm NO2 and the average output value of 233 ppm, was 28 to 1. Thus, sample-diluters were successful in diluting concentrated hypergolic propellant vapors, both MMH and N2O4, into the ranges of existing TLV detectors.

Barile, R. G.↗

Fatigue Testing and Characterization of Pre-hydrided Zircaloy-4 Cladding Tubes

The solubility of hydrogen in Zircaloy-4 (Zry-4) at the cladding operating temperature is near 100 wt. ppm. Above this solubility limit, excess hydrogen precipitates as δ-hydride platelets in the cladding material. Because of the effect of the thermal gradient across the cladding thickness on the migration and precipitation of hydrogen, hydride rims are often observed at the cladding outer surface; under excessive corrosion conditions hydride blisters are possible. It is well known that the fatigue of metal alloys, especially high cycle fatigue, is sensitive to the status of surface including the microstructure, roughness, and residual stress. Thus, the question considered herein, is whether excessive hydrogen pickup modifies the microstructure such that it has a degradation effect on the fatigue performance of cladding during operation. This report describes the evaluation of fatigue performance of a pre-hydrided Zry-4 cladding. A commercial Zry-4 was polished and pre-hydrided to 800 ppm and 1300 ppm H contents. The fatigue testing was conducted under strain control at 5 Hz with fully-reversed bending by using a cyclic integrated reversible bending fatigue tester (CIRFT). Six specimens with 1300 ppm and one specimen with 800 ppm were tested. Significant variation in test results were observed. While two of the 1300 ppm specimens failed with less than 1 ×10 5 cycles (at 0.32% and 0.41%), the four other samples did not fail over the strain amplitude range of 0.25% to 0.38%. Interestingly, the fracture initiation site of the failed samples was on the outside diameter (OD) surface rather than on the inside diameter (ID) surface as is typical for the as-polished cladding. This suggested a degrading effect of the hydriding process. Subsequently, three of the unfailed specimens were then further tested at ~0.43% to observe where failure initiation occurred. Significant variation was also observed in these three specimens. One specimen failed at ~9000 cycles while the two others failed at 43000 and 1.06 ×10 5 cycles. The performance here correlated to the location of failure initiation; failure initiated on the OD in the sample that failed after 9000 cycles while it initiated on the ID in the sample that failed after 43000 and 1.06 ×10 5 cycles. Flat features at the OD initiation sites suggest a brittle hydride feature on the surface of those samples was the cause of the degradation in fatigue performance, though the overall hydrogen levels in all samples was similar. A summary of all the observations is provided below: • The un-failed specimens with 1300 ppm H were cycled to failure with a higher amplitude near 0.43%. In addition, the fatigue-treated specimen tended to have a longer fatigue at the same induced amplitude. • Fractography revealed a mixed failure mode for the pre-hydrided specimen. Particularly, the specimen with fracture initiation site (FIS) located on the outer diameter surface of tube tended to have a shorter fatigue life than that of FIS on the inner diameter surface. • Etched cross section was shown to have hydride platelets aligned with tube longitudinal axis as expected, and the density of hydrides is at the similar level as in literature data. Meanwhile, a LECO procedure was applied for hydrogen concentration measurement, which showed the measured hydrogen contents are close to the nominal value. • With the polished cladding tube as baseline, O’Donnell-Lager (O-L) analysis showed that a decrease of about 50% in reduction-of-area (RA) would be needed for the O-L fitting to the fatigue data of 1300 ppm cladding. The suggestion for the next steps is provided.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Water Content of Lunar Alkali Fedlspar

Detection of indigenous hydrogen in a diversity of lunar materials, including volcanic glass, melt inclusions, apatite, and plagioclase suggests water may have played a role in the chemical differentiation of the Moon. Spectroscopic data from the Moon indicate a positive correlation between water and Th. Modeling of lunar magma ocean crystallization predicts a similar chemical differentiation with the highest levels of water in the K- and Th-rich melt residuum of the magma ocean (i.e. urKREEP). Until now, the only sample-based estimates of water content of KREEP-rich magmas come from measurements of OH, F, and Cl in lunar apatites, which suggest a water concentration of < 1 ppm in urKREEP. Using these data, predict that the bulk water content of the magma ocean would have <10 ppm. In contrast, estimate water contents of 320 ppm for the bulk Moon and 1.4 wt % for urKREEP from plagioclase in ferroan anorthosites. Results and interpretation: NanoSIMS data from granitic clasts from Apollo sample 15405,78 show that alkali feldspar, a common mineral in K-enriched rocks, can have approx. 20 ppm of water, which implies magmatic water contents of approx. 1 wt % in the high-silica magmas. This estimate is 2 to 3 orders of magnitude higher than that estimated from apatite in similar rocks. However, the Cl and F contents of apatite in chemically similar rocks suggest that these melts also had high Cl/F ratios, which leads to spuriously low water estimates from the apatite. We can only estimate the minimum water content of urKREEP (+ bulk Moon) from our alkali feldspar data because of the unknown amount of degassing that led to the formation of the granites. Assuming a reasonable 10 to 100 times enrichment of water from urKREEP into the granites produces an estimate of 100-1000 ppm of water for the urKREEP reservoir. Using the modeling of and the 100-1000 ppm of water in urKREEP suggests a minimum bulk silicate Moon water content between 2 and 20 ppm. However, hydrogen loss was likely very significant in the evolution of the lunar mantle. Conclusions: Lunar granites crystallized between 4.3-3.8 Ga from relatively wet melts that degassed upon crystallization. The formation of these granites likely removed significant amounts of water from some mantle source regions, e.g. later mare basalts predicting derivation from a mantle with <10 ppm water. However, this would have been a heterogeneous pro-cess based on K distribution. Thus some, if not most of the mantle may not have been devolatilized by this process; as seen by water in volcanic glasses and melt inclusions.

Mills, R. D.↗

Long cycle and calendar life of Si-based Li-ion batteries enabled by localized high-concentration electrolytes and their surprising water tolerance

Silicon-based anodes promise an increase in energy density for Li-ion batteries, yet they suffer from a poor calendar life. Researchers have posited that fluorinated lithium salt forms reactive side products that destroy the solid electrolyte interphase (SEI), even without cycling. HF is one such reactive side product formed from trace water contamination in the electrolyte. Some electrolytes, such as localized high concentration electrolytes (LHCEs) may improve cell stability in highly reactive systems, such as Li metal and Si. In the present study, LHCEs containing 200-300 ppm of water retained up to 8% greater capacity (1200-1300 mAh/g Si) in calendar life tests over 200 days compared to dried electrolytes (< 20 ppm water). Calendar aging took place at 100% state of charge. Cells with 200-300 ppm water performed comparably to cells with 20 ppm water in cycle life tests (900-1000 mAh/g Si) . Even adding 1000 ppm water did not lead to rapid capacity fade in cells undergoing cycle life tests. Nano-FTIR spectroscopy revealed chemical and structural differences in the SEI for cells with 1000 ppm water compared to 200-300 ppm water. The SEI differences, including increased Li2O concentration, may have contributed to improved calendar life. This research reveals the capabilities of LHCEs to improve the calendar and cycle life of Si-based Li-ion batteries, despite the presence of a highly reactive contaminant.

25 ENERGY STORAGE↗

EPCAPE-PT-LANL Measurements: Gas Monitors

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: G2401 Gas Concentration Analyzer (Picarro) Data Notes: The Picarro G2401 gas concentration analyzer provides simultaneous, precise measurement of carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) at parts-per-billion (ppb), and water (H2O) vapor at parts per-million (ppm) sensitivity with negligible drift for atmospheric science, air quality, and emissions quantification. Header: - CO[ppm]: Concentration of carbon monoxide (CO) measured at the time of sampling, expressed in parts per million (ppm). - CO2[ppm]: Concentration of carbon dioxide (CO2) measured at the time of sampling, expressed in parts per million (ppm). - CH4[ppm]: Concentration of methane (CH4) measured at the time of sampling, expressed in parts per million (ppm). - H2O[%]: Water vapor content in the air at the time of the measurement, expressed as a percentage

54 ENVIRONMENTAL SCIENCES↗

Continuous animal exposure to dichloromethane

Continuous exposures of dogs, monkeys, rats and mice to 5000 ppm and 1000 ppm of dichloromethane vapor (CH2Cl2) produced severe toxic effects on dogs, rats and mice. Dogs died after 3 weeks exposure to 1000 ppm and after 6 weeks exposure to 5000 ppm. Thirty percent of the mice also succumbed during four weeks exposure to 5000 ppm CH2Cl2. Although rats survived 14 weeks exposure to 5000 ppm, they experienced subnormal weight gains. Significant gross and histopathological hepatic lesions were noted in all 3 species at death or experimental termination in 14 weeks. In addition, rats showed abnormal kidney histopathology. Fat stains disclosed mild fatty increase in monkey livers after 14 weeks exposure to 1000 ppm CH2Cl2.

Macewen, J. D.↗

Airborne Observations of Aerosol Emissions from F-16 Aircraft

We presented results from the SASS Near-Field Interactions Flight (SNIF-III) Experiment which was conducted during May and June 1997 in collaboration with the Vermont and New Jersey Air National Guard Units. The project objectives were to quantify the fraction of fuel sulfur converted to S(VI) species by jet engines and to gain a better understanding of particle formation and growth processes within aircraft wakes. Size and volatility segregated aerosol measurements along with sulfur species measurements were recorded in the exhaust of F-16 aircraft equipped with F-100 engines burning fuels with a range of fuel S concentrations at different altitudes and engine power settings. A total of 10 missions were flown in which F-16 exhaust plumes were sampled by an instrumented T-39 Sabreliner aircraft. On six of the flights, measurements were obtained behind the same two aircraft, one burning standard JP-8 fuel and the other either approximately 28 ppm or 1100 ppm S fuel or an equal mixture of the two (approximately 560 ppm S). A pair of flights was conducted for each fuel mixture, one at 30,000 ft altitude and the other starting at 35,000 ft and climbing to higher altitudes if contrail conditions were not encountered at the initial flight level. In each flight, the F-16s were operated at two power settings, approx. 80% and full military power. Exhaust emissions were sampled behind both aircraft at each flight level, power setting, and fuel S concentration at an initial aircraft separation of 30 m, gradually widening to about 3 km. Analyses of the aerosol data in the cases where fuel S was varied suggest results were consistent with observations from project SUCCESS, i.e., a significant fraction of the fuel S was oxidized to form S(VI) species and volatile particle emission indices (EIs) in comparably aged plumes exhibited a nonlinear dependence upon the fuel S concentration. For the high sulfur fuel, volatile particle EIs in 10-second-old-plumes were 2 to 3 x 10 (exp 17) / kg of fuel burned and exhibited no obvious trend with engine power setting or flight altitude. In contrast, about 8-fold fewer particles were observed in similarly aged plumes from the same aircraft burning fuel with 560 ppm S content and EIs of 1 x 10(exp 15)/ kg of fuel burned were observed in the 28 ppm S fuel case. Moreover, data recorded as a function of plume age indicates that formation and growth of the volatile particles proceeds more slowly as the fuel S level is reduced. For example, ultrafine particle concentrations appear to stabilize within 5 seconds after emission in the 1100 ppm S cases but are still increasing in 20-second old plumes produced from burning the 560 ppm S fuel.

Anderson, B. E.↗

Water Content of the Oceanic Lithosphere at Hawaii from FTIR Analysis of Peridotite Xenoliths

Although water in the mantle is mostly present as trace H dissolved in minerals, it has a large influence on its melting and rheological properties. The water content of the mantle lithosphere beneath continents is better constrained by abundant mantle xenolith data than beneath oceans where it is mainly inferred from MORB glass analysis. Using Fourier transform infrared (FTIR) spectrometry, we determined the water content of olivine (Ol), clinopyroxene (Cpx) and orthopyroxene (Opx) in spinel peridotite xenoliths from Salt Lake Crater, Oahu, Hawaii, which are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. Only Ol exhibits H diffusion profiles, evidence of limited H loss during xenolith transport to the surface. Water concentrations (Ol: 9-28 ppm H2O, Cpx: 246-566 ppm H2O, Opx: 116-224 ppm H2O) are within the range of those from continental settings but higher than those from Gakkel ridge abyssal peridotites. The Opx H2O contents are similar to those of abyssal peridotites from Atlantic ridge Leg 153 (170-230 ppm) but higher than those from Leg 209 (10- 14 ppm). The calculated bulk peridotite water contents (94 to 144 ppm H2O) are in agreement with MORB mantle source water estimates and lower than estimates for the source of Hawaiian rejuvenated volcanism (approx 540 ppm H2O) . The water content of Cpx and most Opx correlates negatively with spinel Cr#, and positively with pyroxene Al and HREE contents. This is qualitatively consistent with the partitioning of H into the melt during partial melting, but the water contents are too high for the degree of melting these peridotites experienced. Melts in equilibrium with xenolith minerals have H2O/Ce ratios similar to those of OIB

Peslier, Anne H.↗

Atmospheric CO2 Variability Observed From ASCENDS Flight Campaigns

Significant atmospheric CO2 variations on various spatiotemporal scales were observed during ASCENDS flight campaigns. For example, around 10-ppm CO2 changes were found within free troposphere in a region of about 200x300 sq km over Iowa during a summer 2014 flight. Even over extended forests, about 2-ppm CO2 column variability was measured within about 500-km distance. For winter times, especially over snow covered ground, relatively less horizontal CO2 variability was observed, likely owing to minimal interactions between the atmosphere and land surface. Inter-annual variations of CO2 drawdown over cornfields in the Mid-West were found to be larger than 5 ppm due to slight differences in the corn growing phase and meteorological conditions even in the same time period of a year. Furthermore, considerable differences in atmospheric CO2 profiles were found during winter and summer campaigns. In the winter CO2 was found to decrease from about 400 ppm in the atmospheric boundary layer (ABL) to about 392 ppm above 10 km, while in the summer CO2 increased from 386 ppm in the ABL to about 396 ppm in free troposphere. These and other CO2 observations are discussed in this presentation.

Lin, Bing↗