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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Model bias in simulating major chemical components of PM 2.5 in China

High concentrations of PM 2.5 (particulate matter with an aerodynamic diameter less than 2.5 µm) in China have caused severe visibility degradation. Accurate simulations of PM 2.5 and its chemical components are essential for evaluating the effectiveness of pollution control strategies and the health and climate impacts of air pollution. In this study, we compared the GEOS-Chem model simulations with comprehensive datasets for organic aerosol (OA), sulfate, nitrate, and ammonium in China. Model results are evaluated spatially and temporally against observations. The new OA scheme with a simplified secondary organic aerosol (SOA) parameterization significantly improves the OA simulations in polluted urban areas, highlighting the important contributions of anthropogenic SOA from semivolatile and intermediate-volatility organic compounds. The model underestimates sulfate and overestimates nitrate for most of the sites throughout the year. More significant underestimation of sulfate occurs in winter, while the overestimation of nitrate is extremely large in summer. The model is unable to capture some of the main features in the diurnal pattern of the PM 2.5 chemical components, suggesting inaccuracies in the presented processes. Potential model adjustments that may lead to a better representation of the boundary layer height, the precursor emissions, hydroxyl radical concentrations, the heterogeneous formation of sulfate and nitrate, and the wet deposition of nitric acid and nitrate have been tested in the sensitivity analysis. The results show that uncertainties in chemistry perhaps dominate the model biases. The proper implementation of heterogeneous sulfate formation and the good estimates of the concentrations of sulfur dioxide, hydroxyl radical, and aerosol liquid water are essential for the improvement of the sulfate simulation. The update of the heterogeneous uptake coefficient of nitrogen dioxide significantly reduces the modeled concentrations of nitrate. However, the large overestimation of nitrate concentrations remains in summer for all tested cases. The possible bias in the chemical production and the wet deposition of nitrate cannot fully explain the model overestimation of nitrate, suggesting issues related to the atmospheric removal of nitric acid and nitrate. A better understanding of the atmospheric nitrogen budget, in particular, the role of the photolysis of particulate nitrate, is needed for future model developments. Moreover, the results suggest that the remaining underestimation of OA in the model is associated with the underrepresented production of SOA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1992

Relative rate constants for the reactions of OH with methane and methyl chloroform

Atmospheric lifetimes of methane and methyl chloroform are largely determined by the rates of their reactions with hydroxyl radical. The relative lifetimes for this loss path are inversely proportional to the ratio of the corresponding rate coefficients. The relative rate constants were measured in a slow-flow, temperature-controlled photochemical reactor, and were based on rates of disappearance of the parent compounds as measured by FTIR spectroscopy. The temperature range was 277-356 K. Hydroxyl radicals were generated by 254 nm photolysis of O3 in the presence of water vapor. The preferred Arrhenius expression for the results is k(CH3CCl3)/k(CH4) = 0.62 exp (291/T), corresponding to a value of 1.65 at 298 K and 1.77 at 277 K. The respective uncertainties are 5 and 7 percent.

Demore, W. B.↗
NASA NTRS2007

U-937 Toxicity Testing of Lunar Dust Stimulant (JSC-1A-vf)

With NASA planning to extend the human presence to the moon by 2020, the dangers of the lunar environment must be assessed and appropriate countermeasures must be developed. Possible toxic effects of the lunar dust are of particular importance to human health because of the dust's chemical composition, reactivity, and small size. This project focuses on the toxicity of lunar dust stimulant (JSC-1A-vf), in both its active and passive forms, using U-937 human monocyte cells. Simulant was mechanically activated from its passive form by grinding, and its ability to produce hydroxyl radicals was determined. To test for toxicity, active and passivated simulant was diluted in media and applied to the cells for various time periods. Toxicity was then estimated using flow cytometry on the Guava Personal Cell Analysis system. Preliminary results suggest that passivated stimulant is slightly toxic, with an increase in toxicity for activated stimulant. Toxicity results may be affected by cell lysing behavior and quenching of hydroxyl radical production by the cell media.

Bales, Kristyn↗
NASA NTRS2021

Intercomparison of the representations of the atmospheric chemistry of pre-industrial methane and ozone in earth system and other global chemistry-transport models

An intercomparison has been set up to study the representation of the atmospheric chemistry of the pre-industrial troposphere in earth system and other global tropospheric chemistry-transport models. The intercomparison employed a constrained box model and utilised tropospheric trace gas composition data for the pre-industrial times at ninety mid-latitude surface locations. Incremental additions of four organic compounds: methane, ethane, acetone and propane, were used to perturb the constrained box model and generate responses in hydroxyl radicals and tropospheric ozone at each location and with each chemical mechanism. Although the responses agreed well across the chemical mechanisms from the selected earth system and other global tropospheric chemistry-transport models, there were differences in the detailed responses between the chemical mechanisms that could be tracked down by sensitivity analysis to differences in the representation of C1–C3 chemistry. Inter-mechanism ranges in NOx compensation points were about 0.17 ± 0.12 when expressed relative to the inter-mechanism average. Monte Carlo uncertainty analysis carried out with a single chemical mechanism put the intra-mechanism range a factor of three higher at 0.50 ± 0.12. Similar differences between inter-mechanism and intra-mechanism ranges were found for hydroxyl radical depletion but were up to a factor of six wider for ozone formation from incremental additions of organic compounds. The cause of the discrepancies between the inter- and intra-mechanism ranges was found to be the large uncertainties that are present in the laboratory determinations of the rate coefficients and product channel branching ratios of some key chemical reactions involving organic peroxy radicals and hydroperoxides. Whilst these large uncertainties are present in the laboratory determinations, there will be irreducible uncertainties in the predictions from the earth system and other chemistry-transport models of methane and tropospheric ozone trends since pre-industrial times and hence their contributions to the radiative forcing of climate change. Further definitive laboratory studies of the reaction rates and product yields of the reactions of the simple organic peroxy radicals and hydroperoxides are required to resolve and reduce current uncertainties in earth system and chemistry-transport model predictions.

atmospheric chemistry↗
DOE OSTI2022

An automated liquid jet for fluorescence dosimetry and microsecond radiolytic labeling of proteins

X-ray radiolytic labeling uses broadband X-rays for in situ hydroxyl radical labeling to map protein interactions and conformation. High flux density beams are essential to overcome radical scavengers. However, conventional sample delivery environments, such as capillary flow, limit the use of a fully unattenuated focused broadband beam. An alternative is to use a liquid jet, and we have previously demonstrated that use of this form of sample delivery can increase labeling by tenfold at an unfocused X-ray source. Here we report the first use of a liquid jet for automated inline quantitative fluorescence dosage characterization and sample exposure at a high flux density microfocused synchrotron beamline. Our approach enables exposure times in single-digit microseconds while retaining a high level of side-chain labeling. This development significantly boosts the method’s overall effectiveness and efficiency, generates high-quality data, and opens up the arena for high throughput and ultrafast time-resolved in situ hydroxyl radical labeling.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1980

Method of cross-linking polyvinyl alcohol and other water soluble resins

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Phillipp, W. H.↗
NASA NTRS2004

Ionization Cross Sections and Dissociation Channels of DNA Bases by Electron Collisions

Free secondary electrons are the most abundant secondary species in ionizing radiation. Their role in DNA damage, both direct and indirect, is an active area of research. While indirect damage by free radicals, particularly by the hydroxyl radical generated by electron collision with water. is relatively well studied, damage by direct electron collision with DNA is less well understood. Only recently Boudaiffa et al. demonstrated that electrons at energies well below ionization thresholds can induce substantial yields of single- and double-strand breaks in DNA by a resonant, dissociative attachment process. This study attracted renewed interest in electron collisions with DNA, especially in the low energy region. At higher energies ionization becomes important. While Monte Carlo track simulations of radiation damage always include ionization, the probability of dissociative ionization, i.e., simultaneous ionization and dissociation, is ignored. Just like dissociative attachment, dissociative ionization may be an important contributor to double-strand breaks since the radicals and ions produced by dissociative ionization, located in the vicinity of the DNA coil, can readily interact with other parts of the DNA. Using the improved binary-encounter dipole (iBED) formulation, we calculated the ionization cross sections of the four DNA bases, adenine, cytosine, guanine, and thymine, by electrons at energies from threshold to 1 KeV. The present calculation gives cross sections approximately 20% lower than the results by Bemhardt and Paretzke using the Deutsch-Mark and Binary-Encounter-Bethe (BEB) formalisms. The difference is most likely due to the lack of a shielding term in the dipole potential used in the Deutsch-Mark and BEB formalisms. The dissociation channels of ionization for the bases are currently being studied.

Huo, Winifred M.↗
NASA NTRS2021

Impact of Regional Northern Hemisphere Mid-latitude Anthropogenic Sulfur Dioxide Emissions on Local and Remote Tropospheric Oxidants

The unintended consequences of reductions in regional anthropogenic sulfur dioxide (SO2) emissions implemented to protect human health are poorly understood. SO2 decreases began in the 1970s in the US and Europe and are expected to continue into the future, while recent emissions decreases in China are also projected to continue. In addition to the well-documented climate effects (warming) from reducing aerosols, tropospheric oxidation is impacted via aerosol modification of photolysis rates and radical sinks. Impacts on the hydroxyl radical and other trace constituents directly affect climate and air quality metrics such as surface ozone levels. We use the Geophysical Fluid Dynamics Laboratory Atmospheric Model version 3 nudged towards National Centers for Environmental Prediction (NCEP) reanalysis wind velocities to estimate the impact of SO2 emissions from the US, Europe, and China by differencing a control simulation with an otherwise identical simulation in which 2015 anthropogenic SO2 emissions are set to zero over one of the regions. Springtime sulfate aerosol changes occur both locally to the emission region and also throughout the Northern Hemispheric troposphere, including remote oceanic regions and the Arctic. Hydroperoxy (HO2) radicals are directly removed via heterogeneous chemistry on aerosol surfaces, including sulfate, in the model, and we find that sulfate aerosol produced by SO2 emissions from the three individual northern mid-latitude regions strongly reduces both HO2 and hydroxyl (OH) by up to 10 % year-round throughout most of the troposphere north of 30∘ N latitude. Regional SO2 emissions significantly increase nitrogen oxides (NOx) by about 5 %–8 % throughout most of the free troposphere in the Northern Hemisphere by increasing the NOx lifetime as the heterogeneous sink of HO2 on sulfate aerosol declines. Despite the NOx increases, tropospheric ozone decreases at northern mid-latitudes by 1 %–4 % zonally averaged and by up to 5 ppbv in summertime surface air over China, where the decreases in HO2 and OH suppress O3 production. Since 2015 anthropogenic SO2 emissions in China exceed those in the US or Europe, the oxidative response is greatest for the China perturbation simulation. Chemical effects of aerosols on oxidation (reactive uptake) dominate over radiative effects (photolysis rates), the latter of which are only statistically significant locally for the large perturbation over China. We find that the SO2 emissions decrease in China, which has yet to be fully realized, will have the largest impact on oxidants and related species in the Northern Hemisphere free troposphere compared to future decreases in Europe or the US. Our results bolster previous calls for a multipollutant strategy for air pollution mitigation to avoid the unintended consequence of aerosol removal leading to surface ozone increases that offset or mask surface ozone gains achieved by regulation of other pollutants, especially in countries where current usage of high-sulfur emitting fuels may be phased out in the future.

anthropogenic sulfur dioxide emissions↗
NASA NTRS1977

SETI - A preliminary search for narrowband signals at microwave frequencies

In the search for intelligent signals of extraterrestrial origin, certain forms of signals merit immediate and special attention. Extremely narrowband signals of spectral width similar to our own television transmissions are most favored energetically and least likely to be confused with natural celestial emission. A search of selected stars has been initiated using observational and data processing techniques optimized for the detection of such signals. These techniques allow simultaneous observation of 10 to the 5th to 10 to the 6th channels within the observed spectral range. About two hundred nearby (within 80 LY) solar type stars have been observed at frequencies near the main microwave transitions of the hydroxyl radical. In addition, several molecular (hydroxyl) masers and other non-thermal sources have been observed in this way in order to uncover any possible fine spectral structure of natural origin and to investigate the potential of such an instrument for radioastronomy.

Cuzzi, J. N.↗
DOE OSTI2021

The Reactivity of Polyethylene Microplastics in Water under Low Oxygen Conditions Using Radiation Chemistry

Polyethylene (PE) is an intensely utilized polymer, which has consequently led to it becoming a common environmental contaminant. PE and other plastic waste are known to be highly persistent in surface waters; however, chemical and physical changes do take place over time, dependent mostly on highly variable natural conditions, such as oxygen (O2) availability. Gamma radiation was used to generate reactive oxygen species, namely hydroxyl radicals, in initially aerated aqueous solutions to simulate the natural weathering of microplastics in waters where there are fluctuations and often depletions in dissolved O2. The headspace of the irradiated PE-containing solutions was probed for the formation of degradation products using solid-phase microextraction (SPME) fibers in combination with gas chromatography mass spectrometry (GCMS). The major species detected were n-dodecane, with trace levels of tridecane, 2-dodecanone, and hexadecane, which were believed to be predominately adsorbed in the PE microplastics in excess of their aqueous solubility limits. Surface characterization by Raman spectroscopy and light and dark field microscopy indicated no change in the chemical composition of the irradiated PE microplastics under low O2 to anaerobic conditions. However, morphological changes were observed, indicating radical combination reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Kinetics of the Temperature-Dependent e aq - and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

The reactivity of chromium(III) species with the major oxidizing and reducing radiolysis products of water was investigated in aqueous solutions at temperatures up to 150 °C. The reaction between the hydrated electron (e aq - ) and Cr(III) species showed a positive temperature dependence over this temperature range. The reaction was also studied in pH 2.5 and 3.5 solutions for the first time. This work also studied the reaction between acidic Cr(III) species and the hydroxyl radical (·OH). It was found that Cr 3+ did not react significantly with the ·OH radical, but the first hydrolysis species, Cr(OH) 2+ , did with a rate coefficient of k= (7.2±0.3)×10 8 M -1 s -1 at 25 °C. The oxidation of Cr(OH) 2+ by the ·OH radical formed an absorbing product species that ultimately oxidized to give Cr(VI). In conclusion, these newly measured reaction rates allow for the development of improved models of aqueous chromium speciation for the effective remediation of liquid high-level nuclear waste via vitrification processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Effects of Halides on Organic Compound Degradation during Plasma Treatment of Brines

Plasma has been proposed as an alternative strategy to treat organic contaminants in brines. Chemical degradation in these systems is expected to be partially driven by halogen oxidants, which have been detected in halide-containing solutions exposed to plasma. In this study, we characterized specific mechanisms involving the formation and reactions of halogen oxidants during plasma treatment. Here, we first demonstrated that addition of halides accelerated the degradation of a probe compound known to react quickly with halogen oxidants (i.e., para -hydroxybenzoate) but did not affect the degradation of a less reactive probe compound (i.e., benzoate). This effect was attributed to the degradation of para-hydroxybenzoate by hypohalous acids, which were produced via a mechanism involving halogen radicals as intermediates. We applied this mechanistic insight to investigate the impact of constituents in brines on reactions driven by halogen oxidants during plasma treatment. Bromide, which is expected to occur alongside chloride in brines, was required to enable halogen oxidant formation, consistent with the generation of halogen radicals from the oxidation of halides by hydroxyl radical. Other constituents typically present in brines (i.e., carbonates, organic matter) slowed the degradation of organic compounds, consistent with their ability to scavenge species involved during plasma treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Molecularly Functionalized Electrodes for Efficient Electrochemical Water Remediation

Here, the development and investigation of materials that leverage unique interfacial effects on electronic structure and redox chemistry are likely to play an outstanding role in advanced technologies for wastewater treatment. Here, the use of surface functionalization of metal oxides with a Ru(II)poly(pyridyl) complex was reported as a way to create hybrid assemblies with optimized electrochemical performance for water remediation, superior to those that could be achieved with the molecular catalyst or metal-oxide electrodes used individually. Mechanistic analysis demonstrated that the molecularly functionalized electrodes could suppress the formation of hydroxyl radicals (i. e., the dominant remediation pathway for bare metal-oxide electrodes), allowing the water remediation to proceed through the highly oxidizing Ru 3+ ions in the surface-bound complexes. Furthermore, the underlying metal-oxide substrates played a crucial role in altering the electronic structure and electrochemical properties of the surface-bound catalyst, such that the competing side reaction (i. e., water splitting) was largely inhibited.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Examination of OH and H 2 O 2 production by uniform and non-uniform modes of dielectric barrier discharge in He/air mixture

In this work we have carried out a parametrical study of hydroxyl radical (OH) generation in nanosecond dielectric barrier discharge (DBD) in He/air mixture using a laser-induced fluorescence approach. Specifically, the foci of the study are the investigation of differences between uniform and non-uniform modes of the discharges and the difference in production of OH and H 2 O 2 Nanosecond-time scale imaging of the discharge shows transition from streamer to diffuse mode when applied electric field to the discharge gap approaches ~90 kV cm –1 . The results show that both OH production in the gas phase and downstream H 2 O 2 delivery rates to liquid depend on the discharge mode operation and are respectively 30% and 3 times higher for the non-uniform DBD compared to the diffuse discharge.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2014

Changes in Global Tropospheric OH Expected as a Result of Climate Change Over the Last Several Decades

The oxidizing capacity of the troposphere is controlled primarily by the abundance of hydroxyl radical (OH). The global mean concentration of OH, [OH]_GLOBAL, inferred from measurements of methyl chloroform, has remained relatively constant during the past several decades, despite rising levels of CH4 that should have led to a steady decline. Here we examine other factors that may have affected [OH]_GLOBAL, such as the changing overhead burden of stratospheric O3 using observations from OMI, TOMS and SBUV; rising tropospheric H2O using observations from AIRS and reanalysis fields from MERRA; and widening of the climatological tropics using widening rate estimates from the literature and global OH fields from the GEOS Chemistry-Climate Model. Our analysis suggests these factors may have contributed a positive trend to [OH]_GLOBAL large enough to counter the decrease due to CH4.

Climate Change↗
DOE OSTI2021

Membrane-Confined Iron Oxychloride Nanocatalysts for Highly Efficient Heterogeneous Fenton Water Treatment

Heterogeneous advanced oxidation processes (AOPs) allow for the destruction of aqueous organic pollutants via oxidation by hydroxyl radicals ( • OH). However, practical treatment scenarios suffer from the low availability of short-lived • OH in aqueous bulk, due to both mass transfer limitations and quenching by water constituents, such as natural organic matter (NOM). In this work, we overcome these challenges by loading iron oxychloride catalysts within the pores of a ceramic ultrafiltration membrane, resulting in an internal heterogeneous Fenton reaction that can degrade organics in complex water matrices with pH up to 6.2. With • OH confined inside the nanopores (~ 20 nm), this membrane reactor completely removed various organic pollutants with water fluxes of up to 100 L m –2 h –1 (equivalent to a retention time of 10 s). This membrane, with a pore size that excludes NOM (>300 kDa), selectively exposed smaller organics to •OH within the pores under confinement and showed excellent resiliency to representative water matrices (simulated surface water and sand filtration effluent samples). Moreover, the membrane exhibited sustained AOPs (>24 h) and could be regenerated for multiple cycles. Our results suggest the feasibility of exploiting ultrafiltration membrane-based AOP platforms for organic pollutant degradation in complex water scenarios.

36 MATERIALS SCIENCE↗