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At least 433 records · Page 24

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DOE OSTI2021

Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

Portlandite [Ca(OH) 2 ] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH) 2 ] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO 2 (OH) n ] 2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility.

36 MATERIALS SCIENCE↗

DOE OSTI2022

A Novel Trichothecene Toxin Phenotype Associated with Horizontal Gene Transfer and a Change in Gene Function in Fusarium

Fusarium trichothecenes are among the mycotoxins of most concern to food and feed safety. Production of these mycotoxins and presence of the trichothecene biosynthetic gene (TRI) cluster have been confirmed in only two multispecies lineages of Fusarium: the Fusarium incarnatum-equiseti (Incarnatum) and F. sambucinum (Sambucinum) species complexes. Here, we identified and characterized a TRI cluster in a species that has not been formally described and is represented by Fusarium sp. NRRL 66739. This fungus is reported to be a member of a third Fusarium lineage: the F. buharicum species complex. Cultures of NRRL 66739 accumulated only two trichothecenes, 7-hydroxyisotrichodermin and 7-hydroxyisotrichodermol. Although these are not novel trichothecenes, the production profile of NRRL 66739 is novel, because in previous reports 7-hydroxyisotrichodermin and 7-hydroxyisotrichodermol were components of mixtures of 6–8 trichothecenes produced by several Fusarium species in Sambucinum. Heterologous expression analysis indicated that the TRI13 gene in NRRL 66739 confers trichothecene 7-hydroxylation. This contrasts the trichothecene 4-hydroxylation function of TRI13 in other Fusarium species. Phylogenetic analyses suggest that NRRL 66739 acquired the TRI cluster via horizontal gene transfer from a close relative of Incarnatum and Sambucinum. These findings provide insights into evolutionary processes that have shaped the distribution of trichothecene production among Fusarium species and the structural diversity of the toxins.

Food Science & Technology↗

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 NTRS1972

Hydrocarbon polymeric binder for advanced solid propellant

A series of DEAB initiated isoprene polymerizations were run in the 5-gallon stirred autoclave reactor. Polymerization run parameters such as initiator concentration and feed rate were correlated with the molecular weight to provide a basis for molecular weight control in future runs. Synthetic methods were developed for the preparation of n-1,3-alkadienes. By these methods, 1,3-nonadiene was polymerized using DEAB initiator to give an ester-telechelic polynonadiene. This was subsequently hydrogenated with copper chromite catalyst to give a hydroxyl terminated saturated liquid hydrocarbon prepolymer having greatly improved viscosity characteristics and a Tg 18 degrees lower than that of the hydrogenated polyisoprenes. The hydroxyl-telechelic saturated polymers prepared by the hydrogenolysis of ester-telechelic polyisoprene were reached with diisocyanates under conditions favoring linear chain extension gel permeation chromatography was used to monitor this condensation polymerization. Fractions having molecular weights above one million were produced.

Potts, J. E.↗

NASA NTRS1973

Development of modified poly(perfluoropropyleneoxide) urethane systems for use in liquid oxygen and in enriched 100 percent oxygen atmosphere

This program consisted of two separate though related phases. The initial phase was directed toward improving the mechanical and adhesive properties of the very highly fluorinated-polyurethane resin system derived from the hydroxyl-terminated polyperfluoropropylene oxide and 6-chloro-2,4,5-trifluoro-m-phenylene diisocyanate. Various new curing agents for this system were investigated, with the goal of providing a more thermally stable crosslink (cure) mechanism to provide wider applicability and fuller utilization of the outstanding oxygen resistance of the PFPO system. Complete resistance to liquid- and gaseous-oxygen impact at presures as high as 1035 N/sq cm were attained with the use of the PFPO resin castings. The second corollary phase was directed toward investigating the feasibility and optimization of the allophanate cured, urethane extended polymer derived from hydroxyl-terminated polyperfluoropropyleneoxide and 6-chloro-2,4,5-trifluoro-m-phenylene diisocyanate, as the adhesive system for use in a weld-bond configuration for liquid oxygen tankage. The synthesis and application procedures of the adhesive system to insure liquid oxygen compatibility (under 10 kg-m loading), and the development of procedures and techniques to provide high quality weld-bonded joint configurations were studied.

Harrison, E. S.↗

NASA NTRS1973

Solar wind and terrestrial atmosphere effects on lunar sample surface composition

Samples returned from the Apollo missions have been shown to have undergone a partial surface oxidation with the degree of oxidation being dependent on the intensity and duration of exposure to a terrestrial or other oxidizing atmosphere. Exposure to atomic hydrogen at room temperature, or molecular hydrogen above 100 C results in a surface reduction. The adsorption of water vapor on a test sample was found to be only slightly dependent on the state of surface oxidation, a situation consistent with the formation of hydroxyl groups on the surface when a sample is exposed to hydrogen. That hydroxyl groups are indeed formed is substantiated by the release of water vapor (and by release of heavy water following exposure to deuterium), indicating that water vapor can be synthesized from solar wind hydrogen and sample oxygen. Observations of trace amounts of methane indicate that the reduction process is by no means restricted to the formation of water vapor.

Cadenhead, D. A.↗

NASA NTRS1975

Electrolyte concentration changes during operation of the nickel cadmium cell

The concentration and distribution of aqueous potassium hydroxide (KOH) electrolyte in a sealed nickel cadmium cell is considered. The reactions at both electrodes during charge and discharge involve the production or utilization of hydroxyl ion (OH) or water (H2O) which directly affects concentration. Changes in electrolyte concentration relative to the individual electrode reactions is discussed. Quantitative values are provided for the changes in concentration for 6, 12, and 20 ah cells with accepted quantities of precharge and accepted initial quantity of 31% aqueous KOH. Consideration is given to a more correct equation which includes net changes in hydroxyl concentration in addition to water. Also, expected concentrations of electrolyte in cells in the fully charged, 75% charged, 50% charged, 25% charged and discharged condition are calculated. The expected concentration changes for cells in the accelerated tests are also tabulated and compared with measured values. All calculations are made on the assumption that there are no side reactions. Various properties which depend on KOH concentration are listed. The variables include O2, H2, and Cd(OH)2 solubilities in addition to viscosity and conductivity.

Halpert, G.↗

NASA NTRS1975

Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

Tseng, S.-S.↗

NASA NTRS1976

The response of the ionosphere to the injection of chemically reactive vapors

As a gas released in the ionosphere expands, it is rapidly cooled. When the vapor becomes sufficiently tenuous, it is reheated by collisions with the ambient atmosphere and its flow is then governed by diffusive expansion. As the injected gas becomes well mixed with the plasma, a hole is created by chemical processes. In the case of diatomic hydrogen release, depression of the electron concentrations is governed by the charge exchange reaction between oxygen ions and hydrogen, producing positive hydroxyl ions. Hydroxyl ions rapidly react with the electron gas to produce excited oxygen and hydrogen atoms. Enhanced airglow emissions result from the transition of the excited atoms to lower energy states. The electron temperature in the depleted region rises sharply causing a thermal expansion of the plasma and a further reduction in the local plasma concentration.

Bernhardt, P. A.↗

NASA NTRS1975

Aminoacyl transfer from an adenylate anhydride to polyribonucleotides

Imidazole catalysis of phenylalanyl transfer from phenylalanine adenylate to hydroxyl groups of homopolyribonucleotides is studied as a possible chemical model of biochemical aminoacylation of transfer RNA (tRNA). The effect of pH on imidazole-catalyzed transfer of phenylalanyl residues to poly(U) and poly(A) double helix strands, the number of peptide linkages and their lability to base and neutral hydroxylamine, and the nature of adenylate condensation products are investigated. The chemical model entertained exhibits a constraint by not acylating the hydroxyl groups of polyribonucleotides in a double helix. The constraint is consistent with selective biochemical aminoacylation at the tRNA terminus. Interest in imidazole as a model of histidine residue in protoenzymes participating in prebiotic aminoacyl transfer to polyribonucleotides, and in rendering the tRNA a more efficient adaptor, is indicated.

Weber, A. L.↗

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.↗

NASA NTRS1978

Preparation of linear hydroxy substituted polyphosphazenes

The synthesis of partially hydroxy-substituted phosphazene prepolymers amenable to processing into cellular, flexible polyurethane foams was investigated. Factors determined include (1) the environment of the hydroxyl group; (2) the ease of the hexachlorocyclotriphosphazene polymerization; (3) the nature of the nonreactive substituents; and (4) the mode of introduction of the hydroxyl entity. The specific approaches taken, the rationale of the selections made, and the results are discussed.

Paciorek, K. L.↗

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 NTRS1980

Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413 K

The pressure dependence of the absolute rate constant for the reaction of the hydroxyl radical with acetylene, important in both atmospheric and combustion chemistry, is determined for temperatures between 228 and 413 K. The flash photolysis-resonance fluorescence technique was employed at five temperatures over wide ranges of pressure and acetylene concentrations, with the OH produced by water photolysis and hydroxyl resonance fluorescent photons measured by multiscaling techniques. Results indicate that, except at the lowest temperature, the bimolecular rate constant for the reaction depends strongly on total pressure, with the pressure effect becoming more pronounced with increasing temperature. At limiting high pressures, the rate constant is found to be equal to 6.83 + or - 1.19 x 10 to the -12th exp (-646 + or - 47/T) cu cm/molecule per sec, where T is the temperature. Results thus demonstrate the importance of environmental conditions in theoretical studies of atmospheric and combustion product compositions

Michael, J. V.↗

NASA NTRS1980

The mechanism of growth of quartz crystals into fused silica

It is proposed that the growth of quartz crystals into fused silica is effected by a mechanism involving the breaking of an Si-O bond and its association with an OH group, followed by cooperative motion of the nonbridging oxygen and the hydroxyl group which results in the crystallization of a row of several molecules along a crystalline-amorphous interfacial ledge. This mechanism explains, at least qualitatively, all the results of the earlier experimental study of the dependence of quartz crystal growth upon applied pressure: large negative activation volume; single activation enthalpy below Si-O bond energy; growth velocity constant in time, proportional to the hydroxyl and chlorine content, decreasing with increasing degree of reduction, and enhanced by nonhydrostatic stresses; lower pre-exponential for the synthetic than for the natural silica.

Fratello, V. J.↗

NASA NTRS1980

Temperature dependence of the reaction O/3P/ + OH/2 Pi/ yields O2 + H

Measurements of the absolute rate and temperature dependence of the rate constant for the reaction of ground state atomic oxygen with hydroxyl radicals to yield molecular oxygen and hydrogen atoms over the temperature range 211-499 K are presented. The reaction was monitored in a low-pressure discharge flow resonance fluorescence apparatus under pseudo-first-order conditions in which the oxygen concentration was greater than the hydroxyl concentration. An expression for the temperature dependence of the rate constant is derived from a least-squares fit to the observed bimolecular rate constants, which were found to range from 3.21 to 2.77 x 10 to the -11th cu cm/molecule per sec for temperatures from 211 to 499 K, indicative of a slight negative temperature dependence. Results are compared with those of previous workers, and the significance of the lower value of the rate constant obtained in the present study to models of HO(x) in the upper stratosphere is indicated.

Lewis, R. S.↗

NASA NTRS1982

Methane and nonmethane hydrocarbon concentrations in the Atlantic marine boundary layer

The reactions of reduced tropospheric trace gases with hydroxyl radicals are thought to play a significant role in global tropospheric photochemistry. Since tropospheric methane and nonmethane hydrocarbon (NMHC) concentrations will affect the tropospheric hydroxyl radical concentrations, accurate measurements of tropospheric CH4 and NMHC concentrations are necessary. Such measurements were, therefore, included in the first leg (from Hamburg, West Germany to Montevideo, Uruguay) of the 1980-1981 Antarctic Expedition. On the basis of the obtained data, a pronounced gradient between northern and southern hemispheric methane concentrations was observed in the marine boundary layer in the region of the intertropical convergence zone. Methane concentrations gradually decreased from about 1.70 ppmv at 40 deg N latitude to about 1.68 ppmv at 14 deg N latitude, then dropped sharply between 14 deg N and 10 deg N latitude to about 1.61 ppmv. NMHC data are also discussed.

Cofer, W. R., III↗

NASA NTRS1982

Polyvinyl alcohol cross-linked with two aldehydes

A film forming polyvinyl alcohol resin is admixed, in aqueous solution, with a dialdehyde crosslinking agent which is capable of crosslinking the polyvinyl alcohol resin and a water soluble acid aldehyde containing a reactive aldehyde group capable of reacting with hydroxyl groups in the polyvinyl alcohol resin and an ionizable acid hydrogen atom. The dialdehyde is present in an amount sufficient to react with from 1 to 20% by weight of the theoretical amount required to react with all of the hydroxyl groups of the polyvinyl alcohol. The amount of acid aldehyde is from 1 to 50% by weight, same basis, and is sufficient to reduce the pH of the aqueous admixture to 5 or less. The admixture is then formed into a desired physical shape, such as by casting a sheet or film, and the shaped material is then heated to simultaneously dry and crosslink the article.

Sheibley, D. W.↗