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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRSDate not supplied

Hunga Tonga-Hunga Ha’apai Water Vapour and Composition of the Stratospheric Polar Vortices

We investigate the impacts of water vapor from the Hunga Tonga-Hunga Ha'apai (HTHH) eruption on the Antarctic stratospheric vortices in 2022 and 2023 and the Arctic stratospheric vortex in 2022/2023. Trace gas abundances from the Aura Microwave Limb Sounder (MLS) and the Modern Era Retrospective-analysis for Research and Applications (MERRA-2) Stratospheric Composition REanalysis with Aura MLS (M2-SCREAM), along with meteorological fields from the longer MERRA-2 record, are used to detail the evolution of the stratospheric polar vortex and its composition during these winter/spring seasons. Through austral winter and spring 2022, HTHH water vapor was effectively excluded from the Antarctic vortex until it broke up. The 2022 Antarctic vortex itself was large, strong, and long-lived, but not exceptionally so. By austral fall 2023, HTHH stratospheric water vapor had spread globally, and Antarctic vortex values in the lower through middle stratosphere were over 2 ppmv higher than usual when the vortex formed; these record-shattering water vapor concentrations led to earlier polar stratospheric cloud formation and chlorine activation, especially at levels that are typically the highest altitudes for polar processing. In the 2022/2023 Arctic winter/spring, HTHH water vapor reached the Arctic vortex region after the vortex had formed and was largely excluded until a major sudden stratospheric warming in mid-February 2023 eroded the vortex and mixed midlatitude and vortex air throughout the hemisphere.

Gloria L Manney↗
NASA NTRSDate not supplied

Hunga Tonga-Hunga Ha’apai Water Vapour and Composition of the Stratospheric Polar Vortices

We investigate the impacts of water vapor from the Hunga Tonga-Hunga Ha'apai (HTHH) eruption on the Antarctic stratospheric vortices in 2022 and 2023 and the Arctic stratospheric vortex in 2022/2023. Trace gas abundances from the Aura Microwave Limb Sounder (MLS) and the Modern Era Retrospective-analysis for Research and Applications (MERRA-2) Stratospheric Composition REanalysis with Aura MLS (M2-SCREAM), along with meteorological fields from the longer MERRA-2 record, are used to detail the evolution of the stratospheric polar vortex and its composition during these winter/spring seasons. Through austral winter and spring 2022, HTHH water vapor was effectively excluded from the Antarctic vortex until it broke up. The 2022 Antarctic vortex itself was large, strong, and long-lived, but not exceptionally so. By austral fall 2023, HTHH stratospheric water vapor had spread globally, and Antarctic vortex values in the lower through middle stratosphere were over 2 ppmv higher than usual when the vortex formed; these record-shattering water vapor concentrations led to earlier polar stratospheric cloud formation and chlorine activation, especially at levels that are typically the highest altitudes for polar processing. In the 2022/2023 Arctic winter/spring, HTHH water vapor reached the Arctic vortex region after the vortex had formed and was largely excluded until a major sudden stratospheric warming in mid-February 2023 eroded the vortex and mixed midlatitude and vortex air throughout the hemisphere.

Gloria L Manney↗
DOE OSTI2021

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗
NASA NTRS1992

Upper-atmosphere Aerosols: Properties and Natural Cycles

The middle atmosphere is rich in its variety of particulate matter, which ranges from meteorite debris, to sulfate aerosols, to polar stratospheric ice clouds. Volcanic eruptions strongly perturb the stratospheric sulfate (Junge) layer. High-altitude 'noctilucent' ice clouds condense at the summer mesopause. The properties of these particles, including their composition, sizes, and geographical distribution, are discussed, and their global effects, including chemical, radiative, and climatic roles, are reviewed. Polar stratospheric clouds (PSCs) are composed of water and nitric acid in the form of micron-sized ice crystals. These particles catalyze reactions of chlorine compounds that 'activate' otherwise inert chlorine reservoirs, leading to severe ozone depletions in the southern polar stratosphere during austral spring. PSCs also modify the composition of the polar stratosphere through complex physiocochemical processes, including dehydration and denitrification, and the conversion of reactive nitrogen oxides into nitric acid. If water vapor and nitric acid concentrations are enhanced by high-altitude aircraft activity, the frequency, geographical range, and duration of PSCs might increase accordingly, thus enhancing the destruction of the ozone layer (which would be naturally limited in geographical extent by the same factors that confine the ozone hole to high latitudes in winter). The stratospheric sulfate aerosol layer reflects solar radiation and increases the planetary albedo, thereby cooling the surface and possibly altering the climate. Major volcanic eruptions, which increase the sulfate aerosol burden by a factor of 100 or more, may cause significant global climate anomalies. Sulfate aerosols might also be capable of activating stratospheric chlorine reservoirs on a global scale (unlike PCSs, which represent a localized polar winter phenomenon), although existing evidence suggests relatively minor perturbations in chlorine chemistry. Nevertheless, if atmospheric concentrations of chlorine (associated with anthropogenic use of chlorofluorocarbons) continue to increase by a factor of two or more in future decades, aircraft emissions of sulfur dioxide and water vapor may take on greater significance.

Turco, Richard P.↗
DOE OSTI2023

Influence of residual chlorine on Ru/TiO 2 active sites during CO 2 methanation

Titania-supported ruthenium (Ru/TiO 2 ) is an established catalyst for the hydrogenation of carbon dioxide to methane (Sabatier reaction). Chlorine contamination, owed to the RuCl 3 precursor, is demonstrated to have a detrimental impact on methanation activity. After calcination and reduction the catalyst contains residual chlorine, shown by XPS. An aqueous ammonia wash removes Cl without leaching Ru. The washed catalysts exhibit improvements in CH 4 site-time yields. Low Ru loading catalysts encounter the greatest activity enhancements after washing (~4.5-fold). DFT calculations indicate that chlorine and CO 2 directly compete for adsorption on Ru step sites, with Cl impeding the adsorption of CO 2 at under-coordinated sites and at higher Cl coverages. H 2 -chemisorption/TPR show that Cl removal lowers the onset of low temperature H 2 dissociation on Ru. Finally, DRIFTS provide evidence that the removal of Cl facilitates low temperature dissociative binding of CO 2 , indicated by the formation of surface bound linear CO species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

The use of multiple indices of physiological activity to access viability in chlorine disinfected Escherichia coli O157:H7

A suite of fluorescent intracellular stains and probes was used, in conjunction with viable plate counts, to assess the effect of chlorine disinfection on membrane potential (rhodamine 123; Rh123 and bis-(1,3-dibutylbarbituric acid) trimethine oxonol; DiBAC4(3)), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-ditolyl tetrazolium chloride; CTC) and substrate responsiveness (direct viable counts; DVC) in the commensal pathogen Escherichia coli O157:H7. After a 5 min exposure to the disinfectant, physiological indices were affected in the following order: viable plate counts > substrate responsiveness > membrane potential > respiratory activity > membrane integrity. In situ assessment of physiological activity by examining multiple targets, as demonstrated in this study, permits a more comprehensive determination of the site and extent of injury in bacterial cells following sublethal disinfection with chlorine. This approach to assessing altered bacterial physiology has application in various fields where detection of stressed bacteria is of interest.

NASA Discipline Environmental Health↗
DOE OSTI2024

First-Principles Study on the Role of Cu and Cl-Based Dopants in NiO

Utilization of wide band gap oxide-based materials in thin-film solar energy technologies has increased in recent years. Among the numerous candidate oxide materials, NiO has shown many desirable optoelectronic properties that are applicable to thin-film PV technologies such as cadmium telluride PV. However, one critical factor requiring further investigation is the p-type doping behavior of NiO, specifically when the cadmium telluride solar cell undergoes conventional processes such as copper doping and chlorine-based activation treatment. The previous literature has shown a large degree of variability in hole concentrations in NiO when copper is used as the primary dopant. This study uses first-principles computational modeling based on density functional theory coupled with defect equilibria calculations to quantitatively explore the role of copper and chlorine-based extrinsic dopants in the p-type doping activity of NiO. The study reveals the importance of extrinsic dopants and their binding interactions with nickel vacancies to effectively p-dope NiO. It is suggested that both the formation of V Ni + Cu Ni and V Ni + Cl O defect pairs under a supersaturated state of NiO are potential mechanisms for increasing hole densities. On the other hand, the production of 2Cu Ni severely limits the effectiveness of p-doping in NiO, even in the presence of the aforementioned defect pairs. Furthermore, the study provides a guideline for experimentalists interested in using copper or chlorine species to understand how to controllably p-dope NiO during thin-film synthesis.

chlorine↗
DOE OSTI2021

Effect of chlorine and chromium on sulfur solubility in low-activity waste glass

According to an empirical sulfur solubility model developed from over 200 simulated low-activity waste (LAW) glasses, chlorine and chromium show strong effects on lowering sulfur solubility in glass. This work was aimed at understanding the mechanism behind the negative effect of chlorine and chromium on sulfur solubility. A simplified LAW glass was prepared and saturated by sodium sulfate, sodium chloride, and sodium chromate salts as single components and as mixtures with different ratios at 25 mol%, 50 mol%, and 75 mol% of sulfate mixed with chloride or chromate. A crucible-scale salt-saturation was performed by mixing the crushed glass powder with an excess amount of salts, melting at 1150 °C for one hour, and quenching. Three mixing-melting-quenching cycles were applied to determine saturation concentrations of sulfur, chromium, and chlorine incorporated into the simplified LAW glass. The glass compositions were analyzed by inductively coupled plasma–atomic emission spectroscopy, ion chromatography, and X-ray emission spectroscopy. It is proposed that the negative effect of chlorine and chromium on sulfur solubility can be explained based on the simple hypothesis that sulfur, chlorine, and chromium are present in the glass as anions competing for the voids or interstitial sites of the glass matrix, and that their solubility strongly depends on the effective size of corresponding anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Nighttime OClO in the Winter Arctic Vortex

We show that a nighttime profile of OClO in the Arctic vortex during the winter of 2000 is overestimated, by nearly a factor of 2, using an isentropic trajectory model constrained by observed profiles of ClOx (ClO + 2 X ClOOCl) and BrO. Calculated abundances of nighttime OClO are shown to be sensitive to the abundance of BrOx (BrO + BrCl), details of the air parcel history during the most recent sunrise/sunset transitions, and the BrCl yield from the reaction BrO + ClO. Many uncertainties are considered, and the discrepancy between measured and modeled nighttime OClO appears to be robust. This discrepancy suggests that production of OClO occurs more slowly than implied by standard photochemistry. If the yield of BrCl from the reaction of BrO + ClO is increased from 7% (JPL 2002 value) to 11% (near the upper limit of the uncertainty), good agreement is found between measured and modeled nighttime OClO. This study highlights the importance of accurate knowledge of BrO + ClO reaction kinetics as well as air parcel trajectories for proper interpretation of nighttime OClO. These factors have a considerably smaller impact on the interpretation of OClO observations obtained during twilight (90(deg) <=SZA <= 92(deg)), when photolytic processes are still active.

chlorine activation↗
NASA NTRS1992

Composition measurements of the 1989 Arctic winter stratosphere by airborne infrared solar absorption spectroscopy

The paper reports simultaneous measurements of the stratospheric burdens of H2O, HDO, OCS, CO2, O3, N2O, CO, CH4, CF2Cl2, CFCl3, CHF2Cl, C2H6, HCN, NO, NO2, HNO3, ClNO3, HOCl, HCl, and HF made by the JPL MkIV interferometer on board the NASA DC-8 aircraft during January and early February 1989 as part of the Airborne Arctic Stratosphere Experiment. Data were obtained on 11 flights at altitudes of up to 12 km over a geographic region covering the NE Atlantic Ocean, Iceland, and Greenland. Analyses of the chemically active gases reveal highly perturbed conditions within the vortex. The ClNO3 abundance was chemically enhanced near the edge of the vortex but was then depleted inside. NO2 was severely depleted inside the vortex. In contrast to Antarctica, H2O and HNO3 were both more abundant inside the vortex than outside. It is suggested that although the Arctic vortex did not get cold enough to produce any dehydration, or as vertically extensive denitrification as occurred in Antarctica, nevertheless, enough heterogeneous chemistry occurred to convert over 90 percent of the inorganic chlorine to active forms in the 14- to 27-km altitude range by early February 1989.

Toon, G. C.↗
DOE OSTI2026

Direct Measurement of Cl − Activity in Metal Chloride Molten Salts using a Cl 2 /Cl − Electrode

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. The activity of the chloride ion in the salt has a large influence on the redox characteristics of the corresponding molten salt. There exists a knowledge gap for the direct measurement of chlorobasicity (Lewis basicity) in molten-salt mixtures. Here, the focus of this work was to develop a Cl 2 /Cl − electrode for the direct measurement of chloride activity in molten metal-chloride salt mixtures. The LiCl–KCl eutectic system was utilized as the reference melt to determine the change in chloride ion activity as increasing concentrations of MgCl 2 are added to the LiCl–KCl eutectic working electrode. The results of the measurements indicated a reduction in chloride ion activity as the concentration of magnesium chloride increased, consistent with the complexation of free chlorides by Lewis acidic magnesium cationic species. The Temkin model was used to estimate the thermodynamic properties of MgCl 4 2− complex.

Chloride↗
NASA NTRS1972

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Holleck, G. L.↗
NASA NTRS1990

Calculations of ozone destruction during the 1988/89 Arctic winter

Calculations of ozone depletion during the 1988/89 Arctic winter using a Lagrangian coupled photochemical-microphysical model are presented. Abundances of ClO in excess of 1 ppbv were observed at the end of the Airborne Arctic Stratospheric Expedition on February 10, 1989. These are shown to be consistent with the removal of more than 90 percent of the reactive nitrogen and the conversion of more than 80 percent of reservoir chlorine to active forms. This chemical state implies that ozone losses of more than 20 ppbv/day can be sustained in heavily denitrified air throughout much of February according to current photochemistry. As much as 74 percent of the loss is calculated to be due to ClO dimer photolysis. Following the warming of the vortex in mid-February 1989, ozone loss through ClO dimer photolysis becomes less effective as the rate of thermal decomposition of the ClO dimer increases. Thus, model results suggest that thermal decomposition of the dimer plays an important role in limiting ozone loss in the Arctic spring.

Mckenna, D. S.↗
NASA NTRS1995

Heterogeneous Chemistry Related to Stratospheric Aircraft

Emissions from stratospheric aircraft that may directly or indirectly affect ozone include NO(y), H2O, soot and sulfuric acid. To fully assess the impact of such emissions, it is necessary to have a full understanding of both the homogeneous and heterogeneous transformations that may occur in the stratosphere. Heterogeneous reactions on stratospheric particles play a key role in partitioning ozone-destroying species between their active and reservoir forms. In particular, heterogeneous reactions tend to activate odd chlorine while deactivating odd nitrogen. Accurate modeling of the net atmospheric effects of stratospheric aircraft requires a thorough understanding of the competing effects of this activation/deactivation. In addition, a full understanding of the potential aircraft impacts requires that the abundance, composition and formation mechanisms of the particles themselves be established. Over the last three years with support from the High Speed Research Program, we have performed laboratory experiments to determine the chemical composition, formation mechanism, and reactivity of stratospheric aerosols.

Tolbert, Margaret A.↗