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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Quantifying the Causes of Differences in Tropospheric OH Within Global Models

The hydroxyl radical (OH) is the primary daytime oxidant in the troposphere and provides the main loss mechanism for many pollutants and greenhouse gases, including methane (CH4). Global mean tropospheric OH differs by as much as 80% among various global models, for reasons that are not well understood. We use neural networks (NNs), trained using archived output from eight chemical transport models (CTMs) that participated in the Polar Study using Aircraft, Remote Sensing, Surface Measurements and Models, of Climate, Chemistry, Aerosols and Transport Model Intercomparison Project (POLMIP), to quantify the factors responsible for differences in tropospheric OH and resulting CH4 lifetime (Tau CH4) between these models. Annual average Tau CH4, for loss by OH only, ranges from 8.0 to 11.6 years for the eight POLMIP CTMs. The factors driving these differences were quantified by inputting 3-D chemical fields from one CTM into the trained NN of another CTM. Across all CTMs, the largest mean differences in Tau CH4 (Delta Tau CH4) result from variations in chemical mechanisms (Delta Tau CH4 = 0.46 years), the photolysis frequency (J) of O3 yields O(D-1) (0.31 years), local O3 (0.30 years), and CO (0.23 years). The Delta Tau CH4 due to CTM differences in NO(x) (NO + NO2) is relatively low (0.17 years), although large regional variation in OH between the CTMs is attributed to NO(x). Differences in isoprene and J(NO2) have negligible overall effect on globally averaged tropospheric OH, although the extent of OH variations due to each factor depends on the model being examined. This study demonstrates that NNs can serve as a useful tool for quantifying why tropospheric OH varies between global models, provided that essential chemical fields are archived.

Surface Measurements and Models↗
DOE OSTI2025

Two-dimensional mapping of absolute OH densities in an atmospheric pressure plasma effluent via planar laser-induced fluorescence: effects of He/H 2 O and He/O 2 mixtures in N 2 and air, with and without solid targets

Planar laser-induced fluorescence (LIF) was employed to measure the absolute density of hydroxyl radicals (OH) in the effluent of the COST Reference Microplasma Jet for two feed gas mixtures: He/H 2 O and He/O 2 . Experiments were conducted with the effluent propagating into air and N 2 environments. For the He/H 2 O case, measurements were also performed with the effluent impinging on a solid target at varying distances from the jet nozzle. Calibration of the OH-LIF signal from the COST-Jet was achieved by comparing it to a reference signal generated by the photofragmentation of H 2 O 2 . Results demonstrated that OH densities were sustained longer when the effluent propagates in a nitrogen environment compared to air, particularly with water added to the feed gas. The broader OH distribution in N 2 suggests slower consumption due to the absence of oxygen, which accelerates OH depletion in air via reactions involving O 2 and HO 2 . Even when water was not added to the feed, as in the He/O 2 case, appreciable OH densities were observed, due to gas impurities and reactive species interactions with atmospheric humidity, forming reaction fronts that delineate the gas flow. Two-dimensional fluid dynamics simulations elucidated the influence of atmospheric gas entrainment and solid targets on the OH distribution. Experimental trends were further compared with a zero-dimensional chemistry model to explore OH production and consumption mechanisms in air and nitrogen environments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2016

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January-February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO +NO2) by a factor of 2, resulting in OHCOL approx.30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January-February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP.

Hydroxyl radical↗
NASA NTRS1982

Atmospheric methyl iodide /CH3I/

It is found that atmospheric concentrations of CH3I are not greater than about 3 pptv over most of the earth's surface and drop to less than half this value above the boundary layer, suggesting that the compound is not likely to play such important roles, on a global scale, as the destruction of tropospheric O3 and free radicals and the increasing of the NO2/NO ratio and hydroxyl radical densities. It is hypothesized that a large portion of the global CH3I comes from oceanic regions of high biomass productivity, where the compound may play a key role in local atmospheric chemistry. Attention is given to CH3I measurement uncertainties with regard to global distribution, sources, and sinks.

Rasmussen, R. A.↗
NASA NTRS1994

Aircraft-borne, laser-induced fluorescence instrument for the in situ detection of hydroxyl and hydroperoxyl radicals

The odd-hydrogen radicals OH and HO2 are central to most of the gas-phase chemical transformations that occur in the atmosphere. Of particular interest is the role that these species play in controlling the concentration of stratospheric ozone. This paper describes an instrument that measures both of these species at volume mixing ratios below one part in 10(exp 14) in the upper troposphere and lower stratosphere. The hydroxyl radical (OH) is measured by laser induced fluorescence at 309 nm. Tunable UV light is used to pump OH to the first electric state near 282 nm. the laser light is produced by a high-repetition rate pulsed dye-laser powered with all solid-state pump lasers. HO2 is measured as OH after gas-phase titration with nitric oxide. Measurements aboard a NASA ER-2 aircraft demonstrate the capability of this instrument to perform reliably with very high signal-to-noise ratios (greater than 30) achieved in short integration times (less than 20 sec).

Wennberg, P. O.↗
NASA NTRS1973

Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone.

Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 300 K for OH + O3 yielding HO2 + O2 is eight times ten to the -14th power cubic centimeters per second. The rate constant for HO2 + O3 yielding OH + 2O2 is three times ten to the -15th power cubic centimeters per second. These results have implications concerning stratospheric ozone.

Demore, W. B.↗
DOE OSTI2020

A comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene

In this work, a comparative reactivity study of 1-alkene fuels from ethylene to 1-heptene has been performed using ignition delay time (IDT) measurements from both a high-pressure shock tube and a rapid compression machine, at an equivalence ratio of 1.0 in ‘air’, at a pressure of 30 atm in the temperature range of 600–1300 K. At low temperatures (< 950 K), the results show that 1-alkenes with longer carbon chains show higher fuel reactivity, with 1-pentene being the first fuel to show negative temperature coefficient (NTC) behavior followed by 1-hexene and 1-heptene. At high temperatures (> 950 K), the experimental results show that all of the fuels except propene show very similar fuel reactivity, with the IDTs of propene being approximately four times longer than for all of the other 1-alkenes. To analyze the experimental results, a chemistry mechanism has been developed using consistent rate constants for these alkenes. At 650 K, flux analyses show that hydroxyl radicals add to the double bond, followed by addition to molecular oxygen producing hydroxy-alkylperoxy radicals, which can proceed via the Waddington mechanism or alternate internal H-atom isomerizations in chain branching similar to those for alkanes. We have found that the major chain propagation reaction pathways that compete with chain branching pathyways mainly produce hydroxyl rather than hydroperoxyl radicals, which explains the less pronounced NTC behavior for larger 1-alkenes compared to their corresponding alkanes. At 1200 K, flux analyses show that the accumulation of hydroperoxyl radicals is important for the auto-ignition of 1-alkenes from propene to 1-heptene. The rate of production of hydroperoxyl radicals for 1-alkenes from 1-butene to 1-heptene is higher than that for propene, which is due to the longer carbon chain facilitating hydroperoxyl radical formation via more efficient reaction pathways. This is the major reason that propene presents lower fuel reactivity than the other 1-alkenes at high temperatures.

1-Alkene↗
NASA NTRS1984

Saturated laser fluorescence in turbulent sooting flames at high pressure

The primary objective was to develop a quantitative, single pulse, laser-saturated fluorescence (LSF) technique for measurement of radical species concentrations in practical flames. The species of immediate interest was the hydroxyl radical. Measurements were made in both turbulent premixed diffusion flames at pressures between 1 and 20 atm. Interferences from Mie scattering were assessed by doping with particles or by controlling soot loading through variation of equivalence ratio and fuel type. The efficacy of the LSF method at high pressure was addressed by comparing fluorescence and adsorption measurements in a premixed, laminar flat flame at 1-20 atm. Signal-averaging over many laser shots is sufficient to determine the local concentration of radical species in laminar flames. However, for turbulent flames, single pulse measurements are more appropriate since a statistically significant number of laser pulses is needed to determine the probability function (PDF). PDFs can be analyzed to give true average properties and true local kinetics in turbulent, chemically reactive flows.

King, G. B.↗
NASA NTRS2009

Luna: What Did We Learn and What Should We Expect?

This presentation presents a look at the space program's background prior to lunar exploration and highlights the Apollo program and lessons learned from lunar exploration. The possibilities of exposures and difficulties attributed to lunar dust are described, including obscured vision, clogged equipment, coated surfaces, and inhalation, among others. A lunar dust simulant is proposed to support preliminary studies. Lunar dust is constantly activated by meteorite lunar dust, UV radiation and elements of solar wind - this active dust could produce reactive species. Methods of deactivation must be determined before new lunar missions, but first we must understand how to reactivate dust on Earth. Activation methods tested and described here include crushing/grinding or UV activation. Grinding time has a direct effect on amount of hydroxyl radicals produced upon addition of ground quartz to a solution. An increase in hydroxyl production was also seen for a lunar simulant with increased grinding.

Wallace, William T.↗
NASA NTRS1990

Measurement of trace stratospheric constituents with a balloon borne laser radar

The objective of this research was to measure the concentration of the stratospheric hydroxyl radical and related chemical species as a function of altitude, season, and time of day. Although hydroxyl plays a very important role in the chemistry controlling stratospheric ozone, little is known about its behavior because it has been a difficult species to measure. The instrument employed in this program was a laser radar, employing the technique of remote laser induced fluorescence. This instrument offers a number of attractive features including extreme specificity and sensitivity, a straightforward relationship between observed quantity and the desired concentration, and immunity to self-contamination.

Heaps, William S.↗
NASA NTRS1982

Is cell aging caused by respiration-dependent injury to the mitochondrial genome

Though intrinsic mitochondrial aging has been considered before as a possible cause of cellular senescence, the mechanisms of such mitochondrial aging have remained obscure. In this article, the hypothesis of free-radical-induced inhibition of mitochondrial replenishment in fixed postmitotic cells is expanded. It is maintained that the respiration-dependent production of superoxide and hydroxyl radicals may not be fully counteracted, leading to a continuous production of lipoperoxides and malonaldehyde in actively respiring mitochondria. These compounds, in turn, can easily react with the mitochondrial DNA which is in close spatial relationship with the inner mitochondrial membrane, producing an injury that the mitochondria may be unable to counteract because of their apparent lack of adequate repair mechanisms. Mitochondrial division may thus be inhibited leading to age-related reduction of mitochondrial numbers, a deficit in energy production with a concomitant decrease in protein synthesis, deterioration of physiological performance, and, therefore, of organismic performance.

Fleming, J. E.↗
DOE OSTI2021

Watching a hydroperoxyalkyl radical (•QOOH) dissociate

A prototypical hydroperoxyalkyl radical (•QOOH) intermediate, transiently formed in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay to hydroxyl radical and cyclic ether products. Direct time-domain measurements of •QOOH unimolecular dissociation rates over a wide range of energies were found to be in accord with those predicted theoretically using state-of-the-art electronic structure characterizations of the transition state barrier region. Unimolecular decay was enhanced by substantial heavy-atom tunneling involving O-O elongation and C-C-O angle contraction along the reaction pathway. Master equation modeling yielded a fully a priori prediction of the pressure-dependent thermal unimolecular dissociation rates for the •QOOH intermediate—again increased by heavy-atom tunneling—which are required for global models of atmospheric and combustion chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Improvements in the Goddard balloon-borne lidar

The Goddard balloon-borne lidar system for the measurement of stratospheric ozone and the hydroxyl radical has made three additional flights since the last laser radar conference. On September 27, 1984, a flight was made from Palestine, Texas obtaining a measurement of hydroxyl diurnal variation at 36 km. These data are presented on the plot which shows hydroxyl concentration as a function of GMT for the range cell closest to the instrument. Local noon corresponds to 18 hours on the plot. The rapid drop in concentration after noon is not predicted by models of stratospheric chemistry. It may represent the effects of contamination of the sample volume by hydrocarbons outgassed from the balloon. The more recent flights on June 30, 1985, and December 6, 1985, focussed on measurements of concentration in the lower stratosphere (less than 30 km). The June flight succeeded in obtaining an average concentration measurement (1.8 + or - 0.0000018 molecules/cubic cm) over the altitude range 21 to 26 km. The December flight obtained measurements down to 24 km with a better signal-to-noise ratio than that obtained in June. Prospects for further improvement in sensitivity and absolute calibration will be discussed.

Heaps, W. S.↗
NASA NTRS2004

High Temperature Decomposition of Hydrogen Peroxide

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydropemxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Clyde F. Parrish↗
NASA NTRS2005

High temperature decomposition of hydrogen peroxide

Nitric oxide (NO) is oxidized into nitrogen dioxide (NO2) by the high temperature decomposition of a hydrogen peroxide solution to produce the oxidative free radicals, hydroxyl and hydroperoxyl. The hydrogen peroxide solution is impinged upon a heated surface in a stream of nitric oxide where it decomposes to produce the oxidative free radicals. Because the decomposition of the hydrogen peroxide solution occurs within the stream of the nitric oxide, rapid gas-phase oxidation of nitric oxide into nitrogen dioxide occurs.

Clyde F Parrish↗