Science.gov

Sample records for aqueous chemical conditions

  1. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1) Adsorption of dilute PFOS(aq) and PFOA(aq) to acoustically cavitating bubble interfaces was greater than equilibrium expectations due to high-velocity bubble radial oscillations; 2) Relative ozone oxidation kinetics of aqueous iodide, sulfite, and thiosulfate were at variance with previously reported bulk aqueous kinetics; 3) Organics that directly chelated with the anode surface were oxidized by direct electron transfer, resulting in immediate carbon dioxide production but slower overall oxidation kinetics. Chemical reactions at aqueous interfaces can be the rate-limiting step of a reaction network and often display novel mechanisms and kinetics as compared to homogeneous chemistry.

  2. Chemical behavior of iodine in aqueous solutions up to 150/sup 0/C. I. An experimental study of nonredox conditions

    SciTech Connect

    Toth, L.M.; Pannell, K.D.; Kirkland, O.L.

    1984-04-01

    The chemical behavior of iodine, I/sub 2/, in (pH = 6 to 10) aqueous solutions containing 2500 ppM boron as H/sub 3/BO/sub 3/ (0.231 M) was studied at temperatures up to 150/sup 0/C. Absorption spectrophotometry was used to identify and monitor the iodine species present. The I/sub 2/ hydrolysis chemistry was found to be consistent with the two-stage mechanism: I/sub 2/ + H/sub 2/O reversible HOI + H/sup +/ + I/sup -/, 3 HOI reversible IO/sub 3//sup -/ + 2I/sup -/ + 3H/sup +/, where the intermediate species is designated as HOI to emphasize that its exact structure and composition are not defined. Three objectives were considered: (1) species identification, with special attention given to HOI; (2) the kinetics of reaction between iodine and water to produce iodide and iodate ions; and (3) partition coefficients between liquid and vapor phases for individual iodine species. Kinetic rate constants for the disproportionation of the HOI intermediate were measured. A typical activation energy for this reaction was found to be 28.4 kJ/mol (6.8 kcal/mol). Although some initial results had suggested an ionic strength dependency, a more detailed examination of the ionic strength effect on this disproportionation reaction suggests that the intermediate in solution throughout the pH 7 to 10 range is primarily an uncharged species such as the triatomic HOI. No absorption bands can be assigned to the HOI intermediate even though it has been shown, in some cases, to be present at concentrations of greater than or equal to 1 x 10/sup -3/ M. A very low molar absorptivity (< 10 M/sup -1/ cm/sup -1/) is probably responsible for its undetectability. A partition coefficient of > 1 x 10/sup 4/ has been estimated for HOI.

  3. Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2002-01-01

    The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG < -3.5 kcal/mol), reversible (deltaG between +/-3.5 kcal/mol), or unfavorable (deltaG > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

  4. Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations under Mild Aqueous Conditions

    NASA Astrophysics Data System (ADS)

    Weber, Arthur L.

    2002-08-01

    The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (ΔG) were estimated for four types of reactions of biochemical importance - carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (ΔG < -3.5 kcal/mol), reversible (ΔG between +/-3.5 kcal/mol), or unfavorable (ΔG > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

  5. Chemical Reactions of Portland Cement with Aqueous CO2 and Their Impacts on Cement's Mechanical Properties under Geologic CO2 Sequestration Conditions.

    PubMed

    Li, Qingyun; Lim, Yun Mook; Flores, Katharine M; Kranjc, Kelly; Jun, Young-Shin

    2015-05-19

    To provide information on wellbore cement integrity in the application of geologic CO2 sequestration (GCS), chemical and mechanical alterations were analyzed for cement paste samples reacted for 10 days under GCS conditions. The reactions were at 95 °C and had 100 bar of either N2 (control condition) or CO2 contacting the reaction brine solution with an ionic strength of 0.5 M adjusted by NaCl. Chemical analyses showed that the 3.0 cm × 1.1 cm × 0.3 cm samples were significantly attacked by aqueous CO2 and developed layer structures with a total attacked depth of 1220 μm. Microscale mechanical property analyses showed that the hardness and indentation modulus of the carbonated layer were 2-3 times greater than for the intact cement, but those in the portlandite-dissolved region decreased by ∼50%. The strength and elastic modulus of the bulk cement samples were reduced by 93% and 84%, respectively. The properties of the microscale regions, layer structure, microcracks, and swelling of the outer layers combined to affect the overall mechanical properties. These findings improve understanding of wellbore integrity from both chemical and mechanical viewpoints and can be utilized to improve the safety and efficiency of CO2 storage. PMID:25893278

  6. Plasmon-driven sequential chemical reactions in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-01

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  7. Plasmon-driven sequential chemical reactions in an aqueous environment

    PubMed Central

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-01-01

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight. PMID:24958029

  8. Uranium dioxide dissolution under acidic aqueous conditions

    SciTech Connect

    Steward, S.A.; Mones, E.T.

    1995-11-20

    Understanding of the long-term dissolution of waste forms in groundwater is required for the safe disposal of high level nuclear waste in a geologic repository, because waste-form radionuclides could be released by dissolution and transported in groundwater. The dissolution of the uranium dioxide (UO{sub 2}) matrix in spent nuclear fuel is considered the rate-limiting step for release of radioactive fission products. The intrinsic UO{sub 2} dissolution rate sets an upper limit on the aqueous radionuclide release rate. Unsaturated spent fuel tests have shown that pH`s of leachates have decreased to a range of 4 to 6, presumably due to air radiolysis that oxidizes nitrogen, producing nitric acid. Dissolution rates under such acidic conditions may be different than those previously reported for alkaline groundwater conditions. No dissolution rate measurements of UO{sub 2} or spent fuel have been reported for acidic conditions possibly relevant to a geologic repository. The purpose of our work has been to measure the intrinsic dissolution rates of uranium dioxide under acidic conditions that are relevant to a repository and allow for modeling. Experiments have been completed at room-temperature and 75 C, pH`s of 4 and 6, and air and oxygen saturated aqueous solutions. These are compared with earlier work on spent fuel and UO{sub 2} using alkaline solutions.

  9. Chemical Equilibrium Composition of Aqueous Systems

    Energy Science and Technology Software Center (ESTSC)

    1996-12-30

    MINEQL is a subroutine package to calculate equilibrium composition of an aqueous system, accounting for mass transfer. MINEQL-EIR contains an additional base on enthalpy and heat capacity data and has the option to do calculations at temperatures different from 25 degrees C.

  10. Aqueous Alteration and Martian Bulk Chemical Composition

    NASA Astrophysics Data System (ADS)

    Taylor, J.; Boynton, W. V.; McLennan, S. M.

    2009-12-01

    The bulk compositions of the terrestrial planets are fundamentally important in testing models for planetary accretion. This is particularly true for the abundances of volatile elements. In the absence of direct samples of the mantle, we must rely on samples of surface materials obtained from orbit (specifically from the Mars Odyssey Gamma-Ray Spectrometer, GRS), Martian meteorites, and in situ analyses. Use of these databases requires understanding the processes that formed and modified the igneous rocks composing the crust; aqueous processes are particularly important. Halogens are useful elements for understanding Martian bulk composition and surface aqueous alteration. Here, we focus on Cl, which is an incompatible element during partial melting. Cosmochemically, Cl is a moderately volatile element with a condensation temperature of 948 Kelvin, only slightly below that of K (1006 Kelvin), another incompatible lithophile element. Cl is substantially lost during magma degassing at or near the surface, making it difficult to determine its abundances in the interior through analyses of rocks, leading to an underestimate of Cl abundance in bulk silicate Mars. GRS data for Mars between approximately 52 degrees north and south show that K and Cl are uncorrelated. This is not surprising as they fractionate easily by release of Cl-bearing gases from magmas near the surface and during eruptions, by aqueous alteration of surface materials, and by the large solubility of Cl salts in water. A positive correlation of Cl with H supports the role of water in Cl redistribution. In spite of the lack of correlation between K and Cl, the mean Cl/K ratio is roughly chondritic: 1.5 ±0.1 compared to 1.28 in CI chondrites. However, Cl appears to be enriched at least in the uppermost few tens of cm analyzed by the GRS: Cl correlates with both H and S, but a linear fit to the data shows a positive Cl intercept of about 0.3, which suggests a decoupling of Cl from S and H. Adjusting the mean Cl abundance at the surface by subtracting 0.3 yields a global near-surface Cl/K of 0.6, about half the chondritic value. These data provide one framework for understanding the details of aqueous alteration on Mars. A reasonable interpretation of the Cl/K ratio at the surface is that the moderately-volatile elements K and Cl are present in chondritic proportions in bulk Mars, but are redistributed by volcanic and aqueous processes. Considering their similar incompatible igneous behavior, any deviations in Cl/K are likely caused in part by aqueous processes on or near the surface. Thus, Cl/K might be a useful index for identifying regions enriched or depleted in deposits modified or formed by aqueous alteration. Enhancement of Cl/K above chondritic could also be caused by additions from volcanic outgassing and variations in the K concentration of igneous rocks, so additional parameters are clearly necessary (e.g., H and S concentrations). Although complicated, these compositional relationships emphasize the need to understand aqueous processing on Mars quantitatively.

  11. Physical-chemical conditions of ore deposition

    USGS Publications Warehouse

    Barton, P.B., Jr.

    1981-01-01

    Ore deposits form under a wide range of physical and chemical conditions, but those precipitating from hot, aqueous fluids-i.e. the hydrothermal deposits-form generally below 700??C and at pressures of only 1 or 2 kbar or less. Natural aqueous fluids in rocks may extract metal and sulfur from a variety of rock types or may acquire them as a residual heritage from a crystallizing silicate magma. Ore-forming hydrothermal fluids never appear as hot springs (except in deep, submarine situations) because they boil, mix with surface waters, and cool, thereby losing their ore-bearing ability before reaching the surface. Mineral systems function as chemical buffers and indicators just as buffers and indicators function in a chemical laboratory. By reading the record written in the buffer/indicator assemblages of minerals one can reconstruct many aspects of the former chemical environment. By studying the record of changing conditions one may deduce information regarding the processes functioning to create the succession of chemical environments and the ore deposits they represent. The example of the OH vein at Creede, Colorado, shows a pH buffered by the K-feldspar + muscovite + quartz assemblage and the covariation of S2 and O2 buffered by the assemblage chlorite + pyrite + quartz. Boiling of the ore fluid led to its oxidation to hematite-bearing assemblages and simultaneously produced an intensely altered, sericitic capping over the vein in response to the condensation of vapors bearing acidic components. The solubility of metals as calculated from experimental and theoretical studies of mineral solubility appears too low by at least one or two powers of ten to explain the mineralization at Creede. In contrast to Creede where the mineral stabilities all point to a relatively consistent chemistry, the Mississippi Valley type deposits present a puzzle of conflicting chemical clues that are impossible to reconcile with any single equilibrium situation. Thus we must seriously consider metastable equilibria; those most likely involve redox disequilibrium among the sulfur species in solution and perhaps also involve organic compounds. ?? 1981.

  12. Thermodynamics of Water and Aqueous Solutions under Mantle Conditions

    NASA Astrophysics Data System (ADS)

    Brown, J. M.; Vance, S.; Bollengier, O.; Shaw, G. H.; Abramson, E.

    2014-12-01

    Interactions between aqueous solutions and rocks extending from the surface and through the deep mantle control the state and evolution of Earth. The accurate representation of the fluid chemical energy as a function of pressure, temperature and composition over a wide range of conditions is prerequisite in understanding phase equilibria and solubilities in multicomponent systems. End-member thermodynamic properties of water (densities, specific heats, sound speeds, and more) have been extensively explored in a regime below about 100 MPa and an available complex formulation for the Helmholtz free energy (IAPWS-95) accurately represents these data and a smaller number of measurements extending to 1 GPa. However, this parameterization systematically misfits higher pressure data and is not easily adjusted to provide a better description. To address these points, we developed a flexible framework for the acquisition and description of Gibbs' free energy of water and aqueous solutions. Through use of local basis functions, the thermodynamic state surface can be adjusted to account for improved experimental constraints or for results in new regimes of pressure and temperature. Based on our experimental work on pure water, MgSO4(aq), Na2SO4(aq), and ammonia-water mixtures, new insights are provided on the volumetric behavior of fluids at high pressure. For the ionic solutions, where the partial molar volume at infinite dilution, Vo, is dominated by electrostriction at low pressure, the initial pressure derivative of Vo is large. At high pressure, where Vo is more related to the "size" of the ions, it is only weakly pressure dependent. The non-ideal behavior of these ionic solutions over an extended range of pressures and temperatures is successfully described using a standard three-term parameterization representing solvent (Debye-Hckel), solvent-ion, and ion-ion interactions. The solvent-ion and ion-ion interaction parameters show less dependence on pressure and temperature than Vo or the Debye-Hckel term and non-ideal behavior is generally suppressed at higher pressures.

  13. Molecular simulation of aqueous electrolytes: Water chemical potential results and Gibbs-Duhem equation consistency tests

    NASA Astrophysics Data System (ADS)

    Moučka, Filip; Nezbeda, Ivo; Smith, William R.

    2013-09-01

    This paper deals with molecular simulation of the chemical potentials in aqueous electrolyte solutions for the water solvent and its relationship to chemical potential simulation results for the electrolyte solute. We use the Gibbs-Duhem equation linking the concentration dependence of these quantities to test the thermodynamic consistency of separate calculations of each quantity. We consider aqueous NaCl solutions at ambient conditions, using the standard SPC/E force field for water and the Joung-Cheatham force field for the electrolyte. We calculate the water chemical potential using the osmotic ensemble Monte Carlo algorithm by varying the number of water molecules at a constant amount of solute. We demonstrate numerical consistency of these results in terms of the Gibbs-Duhem equation in conjunction with our previous calculations of the electrolyte chemical potential. We present the chemical potential vs molality curves for both solvent and solute in the form of appropriately chosen analytical equations fitted to the simulation data. As a byproduct, in the context of the force fields considered, we also obtain values for the Henry convention standard molar chemical potential for aqueous NaCl using molality as the concentration variable and for the chemical potential of pure SPC/E water. These values are in reasonable agreement with the experimental values.

  14. FBX aqueous chemical dosimeter for measurement of dosimetric parameters.

    PubMed

    Moussous, O; Medjadj, T; Benguerba, M

    2011-02-01

    We investigated the ferrous sulphate-benzoic acid-xylenol orange (FBX) aqueous chemical dosimeter for measurement of dosimetric parameters such as the output factor, backscatter factor and lateral beam profiles for different square fields sizes for (60)Co γ-rays. A water phantom was employed to measure these parameters. An ionization chamber (IC) was used for calibration and comparison. A comparison of the resulting measurements with an ionization chamber's measured parameters showed good agreement. We thus believe that the tissue equivalent FBX dosimetry system can measure the dosimetric parameters for (60)Co with reasonable accuracy. PMID:21036054

  15. Biocatalysis in semi-aqueous and nearly anhydrous conditions.

    PubMed

    Hudson, Elton P; Eppler, Ross K; Clark, Douglas S

    2005-12-01

    In the past few years there have been prolific advances in activating enzymes for nonaqueous biocatalysis. Molecular dynamics simulations complement recent experimental results and offer new insights into the deleterious effects of organic solvents, such as water stripping and active-site penetration. Methods for activating enzymes in semi-aqueous or nonaqueous media include protein engineering, chemical modification, and co-lyophilization with non-buffer salts. Enzyme immobilization on novel polymeric supports and the use of zeolite molecular sieves can also increase solvent tolerance, enhance activity, and improve enantioselectivity. The recent implementation of enzymes in ionic liquids has also led to better long-term stability relative to traditional organic solvents and the simultaneous solubilization of enzymes, cofactors and substrates. PMID:16256329

  16. DERMAL ABSORPTION OF CHEMICALS: EFFECT OF APPLICATION OF CHEMICAL AS A SOLID, AQUEOUS PASTE, SUSPENSION OR IN VOLATILE VEHICLE

    EPA Science Inventory

    The purpose of this study was to investigate the dermal absorption of chemicals applied to female F344 rats in different physical forms. hese forms included chemical as a solid, aqueous paste, suspension or dissolved in the volatile vehicle ethanol. he chemicals investigated were...

  17. 'GREENER' CHEMICAL SYNTHESES USING ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Microwave (MW) irradiation in conjunction with water as reaction media has proven to be a greener chemical approach for expeditious N-alkylation reactions of amines and hydrazines wherein the reactions under mildly basic conditions afford tertiary amines and double N-alkylation t...

  18. Influence of aqueous chemistry on the chemical composition of fog water and interstitial aerosol in Fresno

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Ge, Xinlei; Collier, Sonya; Xu, Jianzhong; Sun, Yele; Wang, Youliang; Herckes, Pierre; Zhang, Qi

    2015-04-01

    A measurement study was conducted in the Central Valley (Fresno) of California in January 2010, during which radiation fog events were frequently observed. Fog plays important roles in atmospheric chemistry by scavenging aerosol particles and trace gases and serving as a medium for various aqueous-phase reactions. Understanding the effects of fog on the microphysical and chemical processing of aerosol particles requires detailed information on their chemical composition. In this study, we characterized the chemical composition of fog water and interstitial aerosol particles to study the effects of fog processing on aerosol properties. Fog water samples were collected during the 2010 Fresno campaigns with a Caltech Active Strand Cloud water Collector (CASCC) while interstitial submicron aerosols were characterized in real time with an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a scanning Mobility Particle Sizer (SMPS). The fog water samples were later analyzed using the HR-ToF-AMS, ion chromatography, and a total carbon analyzer. The chemical composition and characteristics of interstitial particles during the fog events were compared to those of dissolved inorganic and organic matter in fog waters. Compared to interstitial aerosols, fog water is composed of a higher fraction of ammonium nitrate and oxygenated organics, due to aqueous formation of secondary aerosol species as well as enhanced gas-to-particle partitioning of water soluble species under water rich conditions. Sulfate is formed most efficiently in fog water although its contribution to total dissolved mass is relatively low. The HR-ToF-AMS mass spectra of organic matter in fog water (FOM) are very similar to that of oxygenated organic aerosols (OOA) derived from positive matrix factorization (PMF) of the HR-ToF-AMS spectra of ambient aerosol (r2 = 0.96), but FOM appears to contain a large fraction of acidic functional groups than OOA. FOM is also enriched of organic nitrogen compounds, with an average N/C ratio ~3.8 times that of OOA. Most strikingly is the enhancement of the CxHyN2+ family ions in FOM spectra, indicating the presence of imidazole compounds, which commonly result from the aqueous phase reactions of tropospheric aldehyde such as glyoxal, formaldehyde or acetaldehyde with amino compounds. The results of this study demonstrate that aqueous phase reactions in fog water lead to the formation of some oxidized and nitrogen-containing compounds. Details and the environmental implications of results will be discussed.

  19. Chemical characterization and anaerobic biodegradability of hydrothermal liquefaction aqueous products from mixed-culture wastewater algae.

    PubMed

    Tommaso, Giovana; Chen, Wan-Ting; Li, Peng; Schideman, Lance; Zhang, Yuanhui

    2015-02-01

    This study examined the chemical characteristics and the anaerobic degradability of the aqueous product from hydrothermal liquefaction (HTL-ap) from the conversion of mixed-culture algal biomass grown in a wastewater treatment system. The effects of the HTL reaction times from 0 to 1.5 h, and reaction temperatures from 260 °C to 320 °C on the anaerobic degradability of the HTL-ap were quantified using biomethane potential assays. Comparing chemical oxygen demand data for HTL-ap from different operating conditions, indicated that organic matter may partition from organic phase to aqueous phase at 320 °C. Moderate lag phase and the highest cumulative methane production were observed when HTL-ap was obtained at 320 °C. The longest lag phase and the smallest production rate were observed in the process fed with HTL-ap obtained at 300 °C. Nevertheless, after overcoming adaptation issues, this HTL-ap led to the second highest accumulated specific methane production. Acetogenesis was identified as a possible rate-limiting pathway. PMID:25455086

  20. Cementation and Aqueous Alteration of a Sandstone Unit Under Acidic Conditions in Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Blake, D. F.; Ming, D. W.; Morris, R. V.; Gellert, R.; Clark, B.; Vaniman, D. T.; Chipera, S. J.; Thompson, L. M.; Bristow, T. F.; Rampe, E. B.; Crisp, J. A.

    2016-01-01

    The Curiosity rover landed on Mars in August 2012 to explore the sedimentary history and to assess the habitability of Gale Crater. After 1200 sols of surface operations and over 12 km of traverse distance, the mineralogy of 10 samples has been determined by the CheMin X-ray diffractometer (XRD) and the chemical composition of nearly 300 targets has been established by the Alpha Particle X-ray Spectrometer (APXS). Light-toned fracture zones containing elevated concentrations of silica have been studied by Curiosity's instruments to determine the nature of the fluids that resulted in the enrichment of SiO2. Multiple fluid exposures are evident, and the chemistry and mineralogy data indicate at least two aqueous episodes may have occurred under acidic conditions.

  1. Pulse radiolysis of tetrazolium violet in aqueous and aqueous-alcoholic solutions under oxidative and reductive conditions

    NASA Astrophysics Data System (ADS)

    Kovács, A.; Wojnárovits, L.; Pálfi, T.; Emi-Reynolds, G.; Fletcher, J.

    2008-09-01

    The radiolytic reduction of colourless tetrazolium salts to coloured formazans in liquid and solid state is suggested for dosimetry purposes. In order to clarify the reaction mechanism, a pulse radiolysis study was conducted in aqueous and aqueous-alcoholic solutions under oxidative and reductive conditions. Under reducing conditions, fast formation of the electron adduct tetrazolinyl radical was observed: coloured formazan final product formed during the decay of electron adduct. Both the decay of the tetrazolinyl radical and the formation of the formazan were found to be second order. The spectra of the formazan were similar in neutral and alkaline solutions, but with higher absorbance in the latter solutions due to the higher molar absorption coefficient. Under oxidative conditions formazan did not form; hydroxylated products through OH-adducts were observed in the pH range studied.

  2. SORPTION AND TRANSPORT OF HYDROPHOBIC ORGANIC CHEMICALS IN AQUEOUS AND MIXED SOLVENT SYSTEMS: MODEL DEVELOPMENT AND PRELIMINARY EVALUATION

    EPA Science Inventory

    A theoretical approach, based upon the assumption of predominance of solvophobic interactions, was formulated to quantitatively describe the sorption and transport of hydrophobic organic chemicals (HOC) from aqueous and aqueous-organic-solvent mixtures. In the theoretical approac...

  3. Conditions of aqueous alteration of 9 CM chondrites estimated from mineralogy and compositional variations of matrix

    NASA Astrophysics Data System (ADS)

    Yoshioka, K.; Nakamura, T.; Fujimaki, H.

    2011-12-01

    CM chondrites have undergone prevailed aqueous alteration in the parent asteroids and the alteration changed mineralogical and isotope signatures of water-bearing C-type asteroids.[1,2] In the previous studies, classification schemes of CM chondrites by the alteration degree were proposed by )[3,4] In the present study, we have performed a mineralogical study of 9 CM chondrites found in Antarctica in order to estimatie the nature and extents of aqueous alteration reactions. At first, small pieces (200 microns in size) of matrix were picked up and analyzed by synchroton radiation X-ray diffraction to identify minerals and relative abundances. The results of the X-ray diffraction analysis and SEM observations indicate that serpentine is present in the matrix of all samples as a major phase, suggesting that all samples have undergone aqueous alteration and have not been heated to temperature enough to dehydrate serpentine. Two out of 9 samples (LEW85311 and LAP03178 hereafter GroupA) contain Fe-Ni metal grains in both chondrule and matrix and anhydrous silicates (olivine and pyroxene) in matrix. Five of 9 samples (GRA06172, MET01072, LEW87022, LAP02269 and GRO95566 hereafter GroupB) contain fine-grained PCPs and anhydrous silicates but no metallic phases in matrix. In addition their chondrules are altered only in glassy parts and in limited parts of anhydrous silicates. The rest two of 9 samples (LAP031166 and MAC88100 hereafter GroupC) don't contain Fe-Ni metal and PCPs and contain little anhydrous silicates in matrix. In addition chondrules are almost completely altered. Since metallic phases are more susceptible to aqueous alteration than anhydrous silicates, the results suggest that the alteration degree is in the order of GroupA< GrouB< GroupC. The EPMA analysis indicates that most data of matrix composition fall within the triangle area defined by [1]: the area is enclosed by the composition of PCPs and two serpentines (the serpentin compositions are defined by those from Murry and Nogoya meteorites) in a Mg-Fe-Si ternary diagram. Nine samples have different compositional trends and PCP/(PCP+serpentine) ratios, suggesting that these 9 samples have suffered various extents of aqueous alteration. The matrix compositions reflect the conditions of aqueous alteration, because of its fine-grained nature. Therefore, it is expected that, for instance, GroupA samples show compositional trends similar within the Group, but different from other Groups. However, GroupA sample (LAP03178) has the same trend as GroupB sample (GRO95566), and GroupB sample (MET01072) has the same trend as GroupC sample (MAC88100).This suggests that aqueous alteration process is very complex: the starting matrix compositions are variable, and the resultant matrix compositions are also different. This indicates that matrix chemical composition alone is not enough to define the alteration degree. [1]McSween (1986), GCA 51, 2469-2477 [2]Clayton and Mayeda (1984) Earth and Planetary Science Letters 67, 151-161 [3]Zolensky et.al (1997) GCA 61, 5099-5115 [4]Rubin et al. (2007) GCA 71, 2361-2382

  4. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    PubMed

    McNeill, V Faye

    2015-02-01

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed. PMID:25609552

  5. Effect of adsorbents and chemical treatments on the removal of strontium from aqueous solutions.

    PubMed

    Ahmadpour, A; Zabihi, M; Tahmasbi, M; Bastami, T Rohani

    2010-10-15

    In the present investigation, three different solid wastes namely almond green hull, eggplant hull, and moss were initially treated and used as adsorbents for the adsorption of strontium ion from aqueous solutions. Adsorbent types and chemical treatments are proved to have effective roles on the adsorption of Sr(II) ion. Among the three adsorbents, almond green hull demonstrated strong affinity toward strontium ion in different solutions. The effectiveness of this new adsorbent was studied in batch adsorption mode under a variety of experimental conditions such as: different chemical treatments, various amounts of adsorbent, and initial metal-ion concentration. The optimum doses of adsorbent for the maximum Sr(II) adsorption were found to be 0.2 and 0.3 g for 45 and 102 mg L(-1) solutions, respectively. High Sr(II) adsorption efficiencies were achieved only in the first 3 min of adsorbent's contact time. The kinetics of Sr(II) adsorption on almond green hull was also examined and it was observed that it follows the pseudo second-order behavior. Both Langmuir and Freundlich models well predicted the experimental adsorption isotherm data. The maximum adsorption capacity on almond green hull was found to be 116.3 mg g(-1). The present study also confirmed that these low cost agriculture byproducts could be used as efficient adsorbents for the removal of strontium from wastewater streams. PMID:20633988

  6. Chemical-equilibrium calculations for aqueous geothermal brines

    SciTech Connect

    Kerrisk, J.F.

    1981-05-01

    Results from four chemical-equilibrium computer programs, REDEQL.EPAK, GEOCHEM, WATEQF, and SENECA2, have been compared with experimental solubility data for some simple systems of interest with geothermal brines. Seven test cases involving solubilities of CaCO/sub 3/, amorphous SiO/sub 2/, CaSO/sub 4/, and BaSO/sub 4/ at various temperatures from 25 to 300/sup 0/C and in NaCl or HCl solutions of 0 to 4 molal have been examined. Significant differences between calculated results and experimental data occurred in some cases. These differences were traced to inaccuracies in free-energy or equilibrium-constant data and in activity coefficients used by the programs. Although currently available chemical-equilibrium programs can give reasonable results for these calculations, considerable care must be taken in the selection of free-energy data and methods of calculating activity coefficients.

  7. Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.

    PubMed

    Deshpande, Sagar; Jaiswal, Rakesh; Matei, Marius Febi; Kuhnert, Nikolai

    2014-09-17

    Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product. PMID:25116442

  8. Aqueous phase oligomerization of methyl vinyl ketone through photooxidation - Part 2: Development of the chemical mechanism and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Ravier, S.; Clément, J.-L.; Monod, A.

    2014-08-01

    We developed a chemical mechanism based on laboratory experiments that have shown efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. The mechanism is then implemented into a multiphase box model that simulates (i) oligomer formation upon uptake of MVK from the gas phase, and (ii) SOA formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. Model results show that under atmospheric conditions, the oligomer formation rate strongly depends on the availability of dissolved oxygen. If oxygen is consumed too quickly or its solubility is kinetically or thermodynamically limited, oligomerization is accelerated, in agreement with the laboratory studies. The comparison of predicted oligomer formation shows that for most model assumptions (e.g. depending on the assumed partitioning of MVK and MACR), SOA formation from isoprene in the gas phase exceeds aqueous SOA formation by a factor 3-4. However, at high aerosol liquid water content and potentially high partitioning of oligomer precursors into the aqueous phase, SOA formation in both phases might be equally efficient.

  9. Aqueous alteration of VHTR fuels particles under simulated geological conditions

    NASA Astrophysics Data System (ADS)

    Ait Chaou, Abdelouahed; Abdelouas, Abdesselam; Karakurt, Gökhan; Grambow, Bernd

    2014-05-01

    Very High Temperature Reactor (VHTR) fuels consist of the bistructural-isotropic (BISO) or tristructural-isotropic (TRISO)-coated particles embedded in a graphite matrix. Management of the spent fuel generated during VHTR operation would most likely be through deep geological disposal. In this framework we investigated the alteration of BISO (with pyrolytic carbon) and TRISO (with SiC) particles under geological conditions simulated by temperatures of 50 and 90 °C and in the presence of synthetic groundwater. Solid state (scanning electron microscopy (SEM), micro-Raman spectroscopy, electron probe microanalyses (EPMA) and X-ray photoelectron spectroscopy (XPS)) and solution analyses (ICP-MS, ionique chromatography (IC)) showed oxidation of both pyrolytic carbon and SiC at 90 °C. Under air this led to the formation of SiO2 and a clay-like Mg-silicate, while under reducing conditions (H2/N2 atmosphere) SiC and pyrolytic carbon were highly stable after a few months of alteration. At 50 °C, in the presence and absence of air, the alteration of the coatings was minor. In conclusion, due to their high stability in reducing conditions, HTR fuel disposal in reducing deep geological environments may constitute a viable solution for their long-term management.

  10. Iron oxide functionalized graphene nano-composite for dispersive solid phase extraction of chemical warfare agents from aqueous samples.

    PubMed

    Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Goud, D Raghavender; Dubey, D K; Pardasani, Deepak

    2015-05-15

    Present study deals with the preparation and evaluation of graphene based magnetic nano-composite for dispersive solid phase extraction of Chemical Weapons Convention (CWC) relevant chemicals from aqueous samples. Nano-composite, Fe3O4@SiO2-G was synthesized by covalently bonding silica coated Fe3O4 onto the graphene sheets. Nerve agents (NA), Sulfur mustard (SM) and their non-toxic environmental markers were the target analytes. Extraction parameters like amount of sorbent, extraction time and desorption conditions were optimized. Dispersion of 20 milligram of sorbent in 200mL of water sample for 20min. followed by methanol/chloroform extraction produced average to good recoveries (27-94%) of targeted analytes. Recoveries of real agents exhibited great dependency upon sample pH and ionic strength. Sarin produced maximum recovery under mild acidic conditions (56% at pH 5) while VX demanded alkaline media (83% at pH 9). Salts presence in the aqueous samples was found to be advantageous, raising the recoveries to as high as 94% for SM. Excellent limits of detection (LOD) for sulphur mustard and VX (0.11ngmL(-1) and 0.19ngmL(-1) respectively) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals. PMID:25828545

  11. FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    The chemical research in the late 1990's witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into the atmo...

  12. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have effective vapor pressures that are orders of magnitude lower when ammonium hydroxide is present (pH 7) than without (at lower pH). In Po Valley experiments, nitrogen-containing organics were prominent precursors and intermediates. Pyruvate and oxalate were among the products. Importantly, formation of aqSOA helps to explain the high O/C ratios found in atmospheric aerosols. While uncertainties remain large, global modeling suggests that aqSOA is comparable in magnitude to SOA formed through gas phase chemistry and vapor pressure driven partitioning (gasSOA).

  13. Mechanisms of chemical vapor generation by aqueous tetrahydridoborate. Recent developments toward the definition of a more general reaction model

    NASA Astrophysics Data System (ADS)

    D'Ulivo, Alessandro

    2016-05-01

    A reaction model describing the reactivity of metal and semimetal species with aqueous tetrahydridoborate (THB) has been drawn taking into account the mechanism of chemical vapor generation (CVG) of hydrides, recent evidences on the mechanism of interference and formation of byproducts in arsane generation, and other evidences in the field of the synthesis of nanoparticles and catalytic hydrolysis of THB by metal nanoparticles. The new "non-analytical" reaction model is of more general validity than the previously described "analytical" reaction model for CVG. The non-analytical model is valid for reaction of a single analyte with THB and for conditions approaching those typically encountered in the synthesis of nanoparticles and macroprecipitates. It reduces to the previously proposed analytical model under conditions typically employed in CVG for trace analysis (analyte below the μM level, borane/analyte ≫ 103 mol/mol, no interference). The non-analytical reaction model is not able to explain all the interference effects observed in CVG, which can be achieved only by assuming the interaction among the species of reaction pathways of different analytical substrates. The reunification of CVG, the synthesis of nanoparticles by aqueous THB and the catalytic hydrolysis of THB inside a common frame contribute to rationalization of the complex reactivity of aqueous THB with metal and semimetal species.

  14. Phytotoxic activity and chemical composition of aqueous volatile fractions from Eucalyptus species.

    PubMed

    Zhang, Jinbiao; An, Min; Wu, Hanwen; Liu, De Li; Stanton, Rex

    2014-01-01

    The essential oils from four Eucalyptus species (E. spathulata, E. salubris, E. brockwayii and E. dundasii) have been previously confirmed to have stronger inhibitory effects on germination and seedling growth of silverleaf nightshade (Solanum elaeagnifolium Cav.). The aqueous volatile fractions (AVFs) were the water soluble volatile fractions produced together with the essential oils (water insoluble fractions) during the steam distillation process. The aim of this study was to further assess the phytotoxicity of AVFs from the four Eucalyptus species and their chemical composition. The fresh leaves of the four Eucalyptus species were used for the extraction of AVFs. The AVFs were tested for their phytotoxic effects on the perennial weed, silverleaf nightshade under laboratory conditions. The chemical compositions of the AVFs were determined by gas chromatograph-mass spectrometry (GC-MS). Our results showed that the AVFs had strong inhibition on the germination and seedling growth of silverleaf nightshade. The inhibition index increased with the increasing concentrations of AVFs. The inhibitory effects of the AVFs varied between different Eucalyptus species. The AVF from E. salubris demonstrated the highest inhibitory activity on the weed tested, with complete inhibition on germination and seedling growth at a concentration of 75%. The GC-MS analysis revealed that 1,8-cineole, isopentyl isovalerate, isomenthol, pinocarvone, trans-pinocarveol, alpha-terpineol and globulol were the main compounds in the AVFs. These results indicated that all AVFs tested had differential inhibition on the germination and seedling growth of silverleaf nightshade, which could be due to the joint effects of compounds present in the AVFs as these compounds were present in different quantities and ratio between Eucalyptus species. PMID:24681490

  15. Phytotoxic Activity and Chemical Composition of Aqueous Volatile Fractions from Eucalyptus Species

    PubMed Central

    Zhang, Jinbiao; An, Min; Wu, Hanwen; Liu, De Li; Stanton, Rex

    2014-01-01

    The essential oils from four Eucalyptus species (E. spathulata, E. salubris, E. brockwayii and E. dundasii) have been previously confirmed to have stronger inhibitory effects on germination and seedling growth of silverleaf nightshade (Solanum elaeagnifolium Cav.). The aqueous volatile fractions (AVFs) were the water soluble volatile fractions produced together with the essential oils (water insoluble fractions) during the steam distillation process. The aim of this study was to further assess the phytotoxicity of AVFs from the four Eucalyptus species and their chemical composition. The fresh leaves of the four Eucalyptus species were used for the extraction of AVFs. The AVFs were tested for their phytotoxic effects on the perennial weed, silverleaf nightshade under laboratory conditions. The chemical compositions of the AVFs were determined by gas chromatograph–mass spectrometry (GC-MS). Our results showed that the AVFs had strong inhibition on the germination and seedling growth of silverleaf nightshade. The inhibition index increased with the increasing concentrations of AVFs. The inhibitory effects of the AVFs varied between different Eucalyptus species. The AVF from E. salubris demonstrated the highest inhibitory activity on the weed tested, with complete inhibition on germination and seedling growth at a concentration of 75%. The GC-MS analysis revealed that 1,8-cineole, isopentyl isovalerate, isomenthol, pinocarvone, trans-pinocarveol, alpha-terpineol and globulol were the main compounds in the AVFs. These results indicated that all AVFs tested had differential inhibition on the germination and seedling growth of silverleaf nightshade, which could be due to the joint effects of compounds present in the AVFs as these compounds were present in different quantities and ratio between Eucalyptus species. PMID:24681490

  16. GREEN CHEMICAL SYNTHESIS THROUGH CATALYSIS AND ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

    Green chemical synthesis through catalysis and alternate reaction conditions

    Encompassing green chemistry techniques and methodologies, we have initiated several projects at the National Risk Management Research laboratory that focus on the design and development of chemic...

  17. Single step signal group-imidazole labeling of organic phosphate groups under aqueous conditions

    DOEpatents

    Giese, R.W.; Wang, P.

    1996-04-30

    Compounds and methods for single step, covalent labeling of the phosphate group of an organic substance under aqueous conditions are described. The labeling compound includes any kind of detectable signal group covalently bound to an imidazole moiety, which can be imidazole or a substituted imidazole. A preferred labeling compound has the formula shown in the accompanying diagram. 4 figs.

  18. Single step signal group-imidazole labeling of organic phosphate groups under aqueous conditions

    DOEpatents

    Giese, Roger W.; Wang, Poguang

    1996-01-01

    Compounds and methods for single step, covalent labeling of the phosphate group of an organic substance under aqueous conditions are described. The labeling compound includes any kind of detectable signal group covalently bound to an imidazole moiety, which can be imidazole or a substituted imidazole. A preferred labeling compound has the formula ##STR1##

  19. Chemical modification of amino acids by atmospheric-pressure cold plasma in aqueous solution

    NASA Astrophysics Data System (ADS)

    Takai, Eisuke; Kitamura, Tsuyoshi; Kuwabara, Junpei; Ikawa, Satoshi; Yoshizawa, Shunsuke; Shiraki, Kentaro; Kawasaki, Hideya; Arakawa, Ryuichi; Kitano, Katsuhisa

    2014-07-01

    Plasma medicine is an attractive new research area, but the principles of plasma modification of biomolecules in aqueous solution remain elusive. In this study, we investigated the chemical effects of atmospheric-pressure cold plasma on 20 naturally occurring amino acids in aqueous solution. High-resolution mass spectrometry revealed that chemical modifications of 14 amino acids were observed after plasma treatment: (i) hydroxylation and nitration of aromatic rings in tyrosine, phenylalanine and tryptophan; (ii) sulfonation and disulfide linkage formation of thiol groups in cysteine; (iii) sulfoxidation of methionine and (iv) amidation and ring-opening of five-membered rings in histidine and proline. A competitive reaction experiment using 20 amino acids demonstrated that sulfur-containing and aromatic amino acids were preferentially decreased by the plasma treatment. These data provide fundamental information for elucidating the mechanism of protein inactivation for biomedical plasma applications.

  20. Chemical Potentials, Activity Coefficients, and Solubility in Aqueous NaCl Solutions: Prediction by Polarizable Force Fields.

    PubMed

    Moučka, Filip; Nezbeda, Ivo; Smith, William R

    2015-04-14

    We describe a computationally efficient molecular simulation methodology for calculating the concentration dependence of the chemical potentials of both solute and solvent in aqueous electrolyte solutions, based on simulations of the salt chemical potential alone. We use our approach to study the predictions for aqueous NaCl solutions at ambient conditions of these properties by the recently developed polarizable force fields (FFs) AH/BK3 of Kiss and Baranyai (J. Chem. Phys. 2013, 138, 204507) and AH/SWM4-DP of Lamoureux and Roux (J. Phys. Chem. B 2006, 110, 3308 - 3322) and by the nonpolarizable JC FF of Joung and Cheatham tailored to SPC/E water (J. Phys. Chem. B 2008, 112, 9020 - 9041). We also consider their predictions of the concentration dependence of the electrolyte activity coefficient, the crystalline solid chemical potential, the electrolyte solubility, and the solution specific volume. We first highlight the disagreement in the literature concerning calculations of solubility by means of molecular simulation in the case of the JC FF and provide strong evidence of the correctness of our methodology based on recent independently obtained results for this important test case. We then compare the predictions of the three FFs with each other and with experiment and draw conclusions concerning their relative merits, with particular emphasis on the salt chemical potential and activity coefficient vs concentration curves and their derivatives. The latter curves have only previously been available from Kirkwood-Buff integrals, which require approximate numerical integrations over system pair correlation functions at each concentration. Unlike the case of the other FFs, the AH/BK3 curves are nearly parallel to the corresponding experimental curves at moderate and higher concentrations. This leads to an excellent prediction of the water chemical potential via the Gibbs-Duhem equation and enables the activity coefficient curve to be brought into excellent agreement with experiment by incorporating an appropriate value of the standard state chemical potential in the Henry Law convention. PMID:26574385

  1. Chemical characterization of some aqueous leachates from crop residues in 'CELSS'

    NASA Technical Reports Server (NTRS)

    Madsen, Brooks C.

    1992-01-01

    Aqueous leachate samples prepared from crop residues that are produced as a component of the Controlled Ecological Life Support System program designed to support long duration space missions have been compared and general chemical characterization has been accomplished. Solid phase extraction and high performance liquid chromatography were used to accomplish comparisons based on chromatographic and ultraviolet absorption properties of the components that are present. Specific compounds were not identified, however, general composition related to the presence of phenol-like compounds was explored.

  2. Surface plasmon differential ellipsometry of aqueous solutions for bio-chemical sensing

    NASA Astrophysics Data System (ADS)

    Stewart, C. E.; Hooper, I. R.; Sambles, J. R.

    2008-05-01

    A differential surface plasmon ellipsometry technique is presented which allows the sensing of refractive index changes in aqueous solutions at the level of better than 5 10-7 refractive index units. This level of sensitivity is comparable to the best currently available surface plasmon based sensing systems and can be implemented as a bio-chemical sensor. The technique has the additional advantage of being ideally suited to the development of a multi-channel array sensor.

  3. Changes in the color, chemical stability and antioxidant capacity of thermally treated anthocyanin aqueous solution over storage.

    PubMed

    Sui, Xiaonan; Bary, Solène; Zhou, Weibiao

    2016-02-01

    Many anthocyanin-containing foods are thermally processed to ensure their safety, and stored for some time before being consumed. However, the combination of thermal processing and subsequent storage has a significant impact on anthocyanins. This study aimed to investigate the color, chemical stability, and antioxidant capacity of thermally treated anthocyanin aqueous solutions during storage at 4, 25, 45, and 65 °C, respectively. Anthocyanin aqueous solutions were thermally treated before storage. Results showed that the degradation rate of anthocyanins in aqueous solutions was much faster than those in real food. The color of the anthocyanin aqueous solutions changed dramatically during storage. The anthocyanin aqueous solutions stored at 4 °C showed the best chemical stability. Interestingly, the antioxidant capacity of the anthocyanin aqueous solutions stored at lower temperatures remained the same; however, the antioxidant capacity of those thermally treated at 120 or 140 °C and stored at 45 or 65 °C significantly decreased. PMID:26304379

  4. Chemically tuned anode with tailored aqueous hydrocarbon binder for direct methanol fuel cells.

    PubMed

    Lee, Chang Hyun; Lee, So Young; Lee, Young Moo; McGrath, James E

    2009-07-21

    An anode for direct methanol fuel cells was chemically tuned by tailoring an aqueous hydrocarbon catalyst (SPI-BT) binder instead of using a conventional perfluorinated sulfonic acid ionomer (PFSI). SPI-BT designed in triethylamine salt form showed lower proton conductivity than PFSI, but it was stable in the catalyst ink forming the aqueous colloids. The aqueous colloidal particle size of SPI-BT was much smaller than that of PFSI. The small SPI-BT colloidal particles contributed to forming small catalyst agglomerates and simultaneously reducing their pore volume. Consequently, the high filling level of binders in the pores, where Pt-Ru catalysts are mainly located on the wall and physically interconnected, resulted in increased electrochemical active surface area of the anode, leading to high catalyst utilization. In addition, the chemical affinity between the SPI-BT binder and the membrane material derived from their similar chemical structure induced a stable interface on the membrane-electrode assembly (MEA) and showed low electric resistance. Upon adding SPI-BT, the synergistic effect of high catalyst utilization, improved mass transfer behavior to Pt-Ru catalyst, and low interfacial resistance of MEA became greater than the influence of reduced proton conductivity in the electrochemical performance of single cells. The electrochemical performance of MEAs with SPI-BT anode was enhanced to almost the same degree or somewhat higher than that with PFSI at 90 degrees C. PMID:19485372

  5. Methods and additives for delaying the release of chemicals in aqueous fluids

    SciTech Connect

    Burnham, J.W.; Briscoe, J.E.; Elphingstone, E.A.

    1980-05-13

    Additives are provided for bringing about the delayed release of a chemical such as a gel breaker or demulsifier in an aqueous fluid such as a gelled oil well hydraulic fracturing or fracture-acidizing fluid. The additives are pelletized solids consisting of the chemical to be released such as sodium laryl sulfate. A gelling agent capable of being hydrated such as a polysaccharide, and a breaker for the gel produced by the gelling agent when hydrated such as a persulfate or an enzyme. 33 claims.

  6. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    SciTech Connect

    Yeh, G.T.; Iskra, G.A.; Szecsody, J.E.; Zachara, J.M.; Streile, G.P.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength.

  7. Modelling the multiphase chemical processing of Monoethanolamine from industrial CCS processes in tropospheric aqueous particles and clouds

    NASA Astrophysics Data System (ADS)

    Tilgner, Andreas; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2013-04-01

    Using amine based solvent technology is an option to realise CO2 capture from the exhaust of power plants. Amines such as Monoethanolamine (MEA) may potentially be released in trace amounts during the carbon capture and storage (CCS) process. In order to investigate the tropospheric chemical fate of MEA from CO2 capturing processes and their oxidation products, multiphase modelling was performed and a reduced mechanism for future 3D model applications was developed in the present study. Based on former laboratory investigations and mechanism developments, an up-to-date multiphase mechanism describing the gas and aqueous phase chemistry of MEA has been developed in the present study. The developed multiphase phase oxidation scheme of MEA and its oxidation products, incl. nitrosamines, nitramines and amides, was coupled to the existing multiphase chemistry mechanism (RACM-MIM2ext-CAPRAM3.0i-red, Deguillaume et al. 2010) and the CAPRAM Halogen Module 2.0. Overall, the multiphase mechanism comprises 1276 chemical processes including 668 gas and 518 aqueous phase reactions as well as 90 phase transfers. The multiphase amine module contains in total 138 processes. The final mechanism was used in the Lagrangian parcel model SPACCIM (Wolke et al., 2005) to investigate e.g. the main oxidation pathways, the formation of hazardous oxidation products and seasonal differences. Simulations were performed using a meteorological scenario with non-permanent clouds, different environmental trajectories and seasonal conditions. The simulations revealed the importance of both cloud droplets and deliquescent particles to be an important compartment for the multiphase processing of MEA and its products. Due to the shifted partitioning of MEA towards the aqueous phase, the model investigations implicated that aqueous phase oxidation by OH radicals represents the main sink for MEA under daytime cloud summer conditions. Reaction flux analyses have shown that under deliquescent particle conditions, the Cl radical represents an important oxidant. Moreover, the simulations showed that MEA oxidations are quite restricted under low photochemical winter conditions leading to much longer tropospheric residence times. Additionally, the model simulations implicated that the aqueous phase reduces substantially the formation of harmful compounds such as MEA-nitramine in the gas phase. Furthermore, simulations revealed that the aqueous formation of N-nitrosoamines is not a relevant process under tropospheric conditions. In order to provide a condensed mechanism applicable for regional scale dispersion modelling, a mechanism reduction was performed based on comprehensive reaction flux investigations. The developed reduced mechanism contains just 303 gas and 112 aqueous phase reactions and 32 phase transfers. The reduced mechanism describes adequately the multiphase chemistry of MEA and its key oxidation products. The required computational costs are reduced by about 45 % compared to the full MEA mechanism. Thus, the reduced mechanism provides the basis for further regional dispersion model studies. References Deguillaume L., Tilgner A., Schrödner R., Wolke R., Chaumerliac N., Herrmann H.: Journal of Atmospheric Chemistry 64 (1), pp 1-35 (2010). Wolke R., Sehili A. M., Simmel M., Knoth O., Tilgner A., Herrmann H.: Atmospheric Environment 39, 4375-4388 (2005).

  8. Tannin (Polyphenol) Stability in Aqueous Solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Understanding the chemical stability of tannins (polyphenolics) in soils is critical to understanding their biological activities and fate. We examined the stability of chemically defined tannins in aqueous solutions under conditions simulating natural and laboratory conditions. We evaluated tanni...

  9. Asian dust particles converted into aqueous droplets under remote marine atmospheric conditions

    PubMed Central

    Tobo, Yutaka; Zhang, Daizhou; Matsuki, Atsushi; Iwasaka, Yasunobu

    2010-01-01

    The chemical history of dust particles in the atmosphere is crucial for assessing their impact on both the Earths climate and ecosystem. So far, a number of studies have shown that, in the vicinity of strong anthropogenic emission sources, Ca-rich dust particles can be converted into aqueous droplets mainly by the reaction with gaseous HNO3 to form Ca(NO3)2. Here we show that other similar processes have the potential to be activated under typical remote marine atmospheric conditions. Based on field measurements at several sites in East Asia and thermodynamic predictions, we examined the possibility for the formation of two highly soluble calcium salts, Ca(NO3)2 and CaCl2, which can deliquesce at low relative humidity. According to the results, the conversion of insoluble CaCO3 to Ca(NO3)2 tends to be dominated over urban and industrialized areas of the Asian continent, where the concentrations of HNO3 exceed those of HCl ([HNO3/HCl]>?1). In this regime, CaCl2 is hardly detected from dust particles. However, the generation of CaCl2 becomes detectable around the Japan Islands, where the concentrations of HCl are much higher than those of HNO3 ([HNO3/HCl]

  10. Formation of sulfur and nitrogen cross-linked macromolecules under aqueous conditions

    NASA Astrophysics Data System (ADS)

    Amrani, Alon; Turner, Jeffrey W.; Ma, Qisheng; Tang, Yongchun; Hatcher, Patrick G.

    2007-09-01

    Polysulfides and ammonia are abundant in young depositional environments and play an important role in the formation of macromolecular structures such as protokerogen and humics. In this work, we study the co-incorporation of polysulfides and ammonia into simple carbonyl model compounds, octanal and trans 2-octenal, in order to study their effect on the formation of a cross-linked macromolecule and suggest a feasible mechanism. The reactions, performed in aqueous solutions at ambient temperature and pH ˜6 to 9, simulate formation of S and N cross-linked polymers in the natural environment. The complex S and N containing polymer was studied by 15N enrichment coupled to 2D NMR ( 1H, 13C, 15N) techniques and chemical degradation of S-S bonds followed by deuterium labeling and GC-MS analyses. In addition, molecular modeling techniques were used to provide theoretical interpretations and important insights at the molecular level. The results indicate that polysulfide out competes ammonia in the formation of Michael adducts while ammonia is equally competitive with polysulfides when the reaction is addition to the carbonyl position. The co-incorporation of ammonia and polysulfides into carbonyls rapidly forms N and S cross-linked polymers. The effects of ammonia and amines on the polymerization processes are by two means: (i) reaction with carbonyls through an imine functionality to form oligomers and polymers and (ii) catalysis of sulfur nucleophiles onto carbonyls by transfer of a proton which enhances the rate of polymerization. A similar catalytic effect is observed when glycine is used instead of ammonia. This mechanism is especially important under basic to neutral conditions like those that prevail in marine environments. The results show that ammonia and glycine or possibly other amino acids and/or peptides are intimately involved with sulfur nucleophiles throughout the polymerization processes that occur at low temperatures and thus are suggested as key reactants in diagenetic formation of protokerogen and humics.

  11. Quantum chemical ab initio modeling of molecular structure of K, Mg aspartate salts in aqueous media

    NASA Astrophysics Data System (ADS)

    Soldatov, Vladimir S.; Pushkarchuk, Alexander L.; Kuvaeva, Zoya I.

    2008-07-01

    The results of systematic theoretical studies of molecular structure, charge distribution and bond characteristics (bond lengths and bond orders) of potassium - magnesium aspartates ((Aspbar)3 K+ Mg2+) in aqueous solution obtained by ab initio quantum-chemical method are presented. The supermolecules including (Aspbar)3 K+ Mg2+ + nH2O + (n = 20, 40, 60, 100;) were considered. In all the cases supermolecule structure were optimized by using the total energy minimization of the system. The features of a structure of associates formed as a result of interaction of potassium and magnesium aspartates with molecules of water are studied. Is was shown, that in the aqueous solution K and Mg aspartates form stable complexes, the structural elements in which are joined by electrostatic interaction.

  12. Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

    PubMed

    Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

    2014-04-15

    Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs. PMID:24552655

  13. Dynamic sodium chemical shift imaging for the study of aqueous humor flow.

    PubMed

    Weinberg, D V; Kolodny, N H; Kohler, S J; Burr, T A; Celi, A; D'Amico, D J; Gragoudas, E S

    1991-07-01

    Ocular images were obtained using sodium chemical shift imaging (CSI) and 1,4,7,10-tetraazacyclododecane-N,N'N",N"'-tetramethylenephospho nate thulium (III) [Tm(DOTP)5-], a paramagnetic chemical shift reagent. After injecting the shift reagent into the anterior chamber of rabbits, serial imaging was done, monitoring the change in chemical shift with time. Sodium CSI produced images of the eye in three dimensions, quantitatively depicting the spatial and temporal changes in the concentration of a paramagnetic tracer substance. The Tm(DOTP)5- is eliminated from the anterior chamber by first-order kinetics with a half-life of 49 min. These data suggest that this substance is eliminated from the anterior chamber at the same rate as aqueous humor is replaced. Sodium CSI shows promise as a valuable technique for monitoring fluid dynamics in the living eye. PMID:2071335

  14. General method allowing the use of 100% aqueous loading conditions in reversed-phase liquid chromatography.

    PubMed

    Pettersson, Sylvia Winkel; Persson, Börje S; Nyström, Mats

    2004-04-15

    Reversed-phase HPLC purification of peptides, using n-alkyl modified spherical silica, has become a widely used technique within the pharmaceutical industry. One drawback of these materials is the necessity of having at least 5% organic modifier in the mobile phase, in order to avoid de-wetting of the porous stationary phase. For some preparative reversed-phase separations, it is an advantage if the feed solution can be loaded onto the column under 100% aqueous conditions. This study describes the use of post-column pressure control to avoid de-wetting of regular reversed-phase stationary phases when operated under 100% aqueous conditions. The applicability of post-column pressure control as a means of maintaining the column fully wetted is demonstrated with various buffers and with packing materials having different alkyl-chain lengths. Two peptides, insulin and oxytocin, in overloaded quantities, were loaded under 100% aqueous conditions onto a regular C8 column, and then eluted by a acetonitrile gradient following standard procedures. The retention volume and the peak shape showed that the separation was satisfactory, and proved that post-column pressure control can be used to overcome wettability problems, which are otherwise often observed for reversed-phase packing materials with high ligand density. PMID:15026009

  15. Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

    NASA Astrophysics Data System (ADS)

    Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

    2014-05-01

    In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

  16. Unblocked statistical-coil tetrapeptides in aqueous solution: quantum-chemical computation of the carbon-13 NMR chemical shifts.

    PubMed

    Vila, Jorge A; Baldoni, Hctor A; Ripoll, Daniel R; Scheraga, Harold A

    2003-06-01

    We recently reported a theoretical characterization of representative ensembles of statistical-coil conformations for tetrapeptides with unblocked termini in aqueous solution, at pH 7. The results showed good agreement between the computed Boltzmann-averaged and experimentally-determined values for both the vicinal coupling constants (3)J(NHalpha) and the alpha-proton chemical shifts. Here, we carry out a cluster analysis of the ensembles of conformations generated in that study, and use them to compute the Boltzmann-averaged values of the quantum-chemical (13)C chemical shifts for different amino acids in the unblocked tetrapeptides GGXA (where X stands for Phe, Arg, His, Glu, Ile, Lys, Gln, Tyr, Leu, Thr, Ala, Gly and Val). The values of the (13)C chemical shifts in these thirteen amino acids (for which experimental data are available) were computed by using Density Functional Theory with a 6-311+G(2d,p) basis set. Good agreement is found in terms of both the correlation coefficient (R) and standard deviations of the difference between the computed Bolztmann-averaged and the NMR-determined values for the (13)C chemical shifts. These results suggest that it may be possible to build a reliable theoretically-derived database of chemical shifts for statistical-coil residues. The results of the current study contribute to our understanding of the relations between chemical shifts, dihedral angles and vicinal coupling constants, (3)J(NHalpha). In addition, they can shed light as to how the statistical-coil conformation is related to the conformational preference of more structured states, such as the alpha-helical conformation. PMID:12766407

  17. Process for preparing chemically modified micas for removal of cesium salts from aqueous solution

    DOEpatents

    Yates, Stephen Frederic; DeFilippi, Irene; Gaita, Romulus; Clearfield, Abraham; Bortun, Lyudmila; Bortun, Anatoly

    2000-09-05

    A chemically modified mica composite formed by heating a trioctahedral mica in an aqueous solution of sodium chloride having a concentration of at least 1 mole/liter at a temperature greater than 180 degrees Centigrade for at least 20 hours, thereby replacing exchangeable ions in the mica with sodium. Formation is accomplished at temperatures and pressures which are easily accessed by industrial equipment. The reagent employed is inexpensive and non-hazardous, and generates a precipitate which is readily separated from the modified mica.

  18. Intrinsic formation of nanocrystalline neptunium dioxide under neutral aqueous conditions relevant to deep geological repositories.

    PubMed

    Husar, Richard; Hübner, René; Hennig, Christoph; Martin, Philippe M; Chollet, Mélanie; Weiss, Stephan; Stumpf, Thorsten; Zänker, Harald; Ikeda-Ohno, Atsushi

    2015-01-25

    The dilution of aqueous neptunium carbonate complexes induces the intrinsic formation of nanocrystalline neptunium dioxide (NpO2) particles, which are characterised by UV/Vis and X-ray absorption spectroscopies and transmission electron microscopy. This new route of nanocrystalline NpO2 formation could be a potential scenario for the environmental transport of radionuclides from the waste repository (i.e. under near-field alkaline conditions) to the geological environment (i.e. under far-field neutral conditions). PMID:25479067

  19. Aqueous Chemical Modeling of Sedimentation on Early Mars with Application to Surface-Atmosphere Evolution

    NASA Technical Reports Server (NTRS)

    Catling, David C.

    2004-01-01

    This project was to investigate models for aqueous sedimentation on early Mars from fluid evaporation. Results focused on three specific areas: (1) First, a fluid evaporation model incorporating iron minerals was developed to compute the evaporation of a likely solution on early Mars derived from the weathering of mafic rock. (2) Second, the fluid evaporation model was applied to salts within Martian meteorites, specifically salts in the nakhlites and ALH84001. Evaporation models were found to be consistent with the mineralogy of salt assemblages-anhydrite, gypsum, Fe-Mg-Ca carbonates, halite, clays-- and the concentric chemical fractionation of Ca-to Mg-rich carbonate rosettes in ALH84001. We made progress in further developing our models of fluid concentration by contributing to updating the FREZCHEM model. (3) Third, theoretical investigation was done to determine the thermodynamics and kinetics involved in the formation of gray, crystalline hematite. This mineral, of probable ancient aqueous origin, has been observed in several areas on the surface of Mars by the Thermal Emission Spectrometer on Mars Global Surveyor. The "Opportunity" Mars Exploration Rover has also detected gray hematite at its landing site in Meridiani Planum. We investigated how gray hematite can be formed via atmospheric oxidation, aqueous precipitation and subsequent diagenesis, or hydrothermal processes. We also studied the geomorphology of the Aram Chaos hematite region using Mars Orbiter Camera (MOC) images.

  20. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 false General conditions for chemical tests. 219.11... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to have...), evidence consent to taking of specimens, their release for toxicological analysis under...

  1. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 false General conditions for chemical tests. 219.11... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to have...), evidence consent to taking of specimens, their release for toxicological analysis under...

  2. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 false General conditions for chemical tests. 219.11... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to have...), evidence consent to taking of specimens, their release for toxicological analysis under...

  3. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 4 2010-10-01 2010-10-01 false General conditions for chemical tests. 219.11 Section 219.11 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to...

  4. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 4 2011-10-01 2011-10-01 false General conditions for chemical tests. 219.11 Section 219.11 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to...

  5. Chemically modified biochar produced from conocarpus waste increases NO3 removal from aqueous solutions.

    PubMed

    Usman, Adel R A; Ahmad, Mahtab; El-Mahrouky, Mohamed; Al-Omran, Abdulrasoul; Ok, Yong Sik; Sallam, Abdelazeem Sh; El-Naggar, Ahmed H; Al-Wabel, Mohammad I

    2016-04-01

    Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO3 removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO3 sorption capacity of 45.36 mmol kg(-1) predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO3 sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m(2) g(-1)) and formation of strong ionic complexes with NO3. At an initial pH of 2, more than 89 % NO3 removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar. PMID:26100325

  6. Detailed investigation of the radical-induced destruction of chemical warfare agent simulants in aqueous solution.

    PubMed

    Abbott, Amberashley; Sierakowski, Tim; Kiddle, James J; Clark, Kristin K; Mezyk, Stephen P

    2010-06-10

    The persistence of delivered chemical warfare agents (CWAs) in a variety of environmental matrices is of serious concern to both the military and civilian populations. Ultimately understanding all of the degradation pathways of the various CWAs in different environmental matrices is essential for determining whether native processes would offer sufficient decontamination of a particular material or if active chemical decontamination is required. Whereas much work on base-promoted chemical degradation has been reported, additional remediation strategies such as the use of advanced oxidation or reduction process free radical treatments may also be a viable option. We have examined here the primary kinetics and reaction mechanisms for an extensive library of chemical warfare agent simulants with the oxidizing hydroxyl radical and reducing hydrated electrons in water. From these values, it is seen that the reductive destruction occurs primarily through a single mechanism, consisting of hydrated electron capture at the phosphorus group with subsequent elimination, whereas hydroxyl radical oxidation shows two separate reaction mechanisms, dependent on the aqueous pK(a) of the leaving group. PMID:20469938

  7. EVALUATION OF CHEMICAL AMENDMENTS FOR PH AND REDOX STABILIZTION IN AQUEOUS SUSPENSIONS OF THREE CALIFORNIA SOILS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many chemically and biologically important trace element, heavy metal, and organic contaminant reactions in soils are constrained by pH and redox conditions and changes in these conditions can significantly affect reaction rates. Although closed-system, batch methods have been used for many years to...

  8. Sulfur removal from Gediz lignite using aqueous sodium hydroxide solutions under mild oxidative conditions

    SciTech Connect

    Yaman, S.; Kuecuekbayrak, S.

    1999-11-01

    Sulfur removal from a high-sulfur Turkish lignite (Gediz) using aqueous sodium hydroxide solutions having dissolved oxygen was investigated under mild oxidative conditions. Effects of the parameters such as sodium hydroxide/lignite weight ratio, temperature, and partial pressure of oxygen were investigated within the ranges of 0.05--0.8, 423--498 K, and 1--2 MPa, respectively. Optimum values of these parameters were determined regarding sulfur removal and coal recovery. Influences of dry oxidation of the lignite sample as a pretreatment at 573 K and subsequent washing of some treated lignite samples with 1 N HCl were investigated.

  9. CO₂ carbonation under aqueous conditions using petroleum coke combustion fly ash.

    PubMed

    González, A; Moreno, N; Navia, R

    2014-12-01

    Fly ash from petroleum coke combustion was evaluated for CO2 capture in aqueous medium. Moreover the carbonation efficiency based on different methodologies and the kinetic parameters of the process were determined. The results show that petroleum coke fly ash achieved a CO2 capture yield of 21% at the experimental conditions of 12 g L(-1), 363°K without stirring. The carbonation efficiency by petroleum coke fly ash based on reactive calcium species was within carbonation efficiencies reported by several authors. In addition, carbonation by petroleum coke fly ash follows a pseudo-second order kinetic model. PMID:25000300

  10. Possible interrelations among chemical freeze-out conditions

    NASA Astrophysics Data System (ADS)

    Tawfik, A.; El-Bakry, M. Y.; Habashy, D. M.; Mohamed, M. T.; Abbas, E.

    2016-03-01

    At thermal equilibrium, different chemical freeze-out conditions have been proposed so far. They have an ultimate aim of proposing a universal description for the chemical freeze-out parameters (Tch and μb), which are to be extracted from the statistical fitting of different particle ratios measured at various collision energies with calculations from thermal models. A systematic comparison between these conditions is presented. The physical meaning of each of them and their sensitivity to the hadron mass cuts are discussed. Based on availability, some of them are compared with recent lattice calculations. We found that most of these conditions are thermodynamically equivalent, especially at small baryon chemical potential. We propose that further crucial consistency tests should be performed at low energies. The fireball thermodynamics is another way of guessing conditions describing the chemical freeze-out parameters extracted from high-energy experiments. We endorse the possibility that the various chemical freeze-out conditions should be interpreted as different aspects of one universal condition.

  11. Chemical and Isotopic Study of Lab-formed Carbonates Under Cryogenic and Hydrothermal Conditions

    NASA Technical Reports Server (NTRS)

    Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Golden, D. C.; Ming, D. W.; Gibson, E. K.

    2004-01-01

    Aqueous environments on early Mars were probably relatively short-lived and localized, as evidenced by the lack of abundant secondary minerals detected by the TES instrument. In order to better understand the aqueous history of early Mars we need to be able to interpret the evidence preserved in secondary minerals formed during these aqueous events. Carbonate minerals, in particular, are important secondary minerals for interpreting past aqueous environments as illustrated by the carbonates preserved in ALH84001. Carbonates formed in short-lived, dynamic aqueous events often preserve kinetic rather than equilibrium chemical and isotopic processes, and predicting the behavior of such systems is facilitated by empirical data.

  12. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  13. Chemical characterization of the main products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; Čusak, A.; Grgić, I.; Claeys, M.

    2014-08-01

    Guaiacol (2-methoxyphenol) and its derivatives can be emitted into the atmosphere by thermal degradation (i.e., burning) of wood lignins. Due to its volatility, guaiacol is predominantly distributed atmospherically in the gaseous phase. Recent studies have shown the importance of aqueous-phase reactions in addition to the dominant gas-phase and heterogeneous reactions of guaiacol, in the formation of secondary organic aerosol (SOA) in the atmosphere. The main objectives of the present study were to chemically characterize the main products of the aqueous-phase photonitration of guaiacol and examine their possible presence in urban atmospheric aerosols. The aqueous-phase reactions were carried out under simulated sunlight and in the presence of hydrogen peroxide and nitrite. The formed guaiacol reaction products were concentrated by solid-phase extraction and then purified with semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state proton, carbon-13 and two-dimensional nuclear magnetic resonance (NMR) spectroscopy, and direct infusion negative ion electrospray ionization tandem mass spectrometry ((-)ESI-MS/MS). The NMR and product ion (MS2) spectra were used for unambiguous product structure elucidation. The main products of guaiacol photonitration are 4-nitroguaiacol (4NG), 6-nitroguaiacol (6NG), and 4,6-dinitroguaiacol (4,6DNG). Using the isolated compounds as standards, 4NG and 4,6DNG were unambiguously identified in winter PM10 aerosols from the city of Ljubljana (Slovenia) by means of HPLC/(-)ESI-MS/MS. Owing to the strong absorption of ultraviolet and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  14. Photoluminescence of ZnO nanostructures grown by the aqueous chemical growth technique

    NASA Astrophysics Data System (ADS)

    Kenanakis, G.; Androulidaki, M.; Koudoumas, E.; Savvakis, C.; Katsarakis, N.

    2007-07-01

    Zinc oxide nanostructured films were grown by the aqueous chemical growth technique using equimolar aqueous solutions of zinc nitrate and hexamethylenetetramine as precursors. Silicon(100) and glass substrates were placed in Pyrex glass bottles with polypropylene autoclavable screw caps containing the precursors described above, and heated at 95 ∘C for several hours. X-ray diffraction 2θ/θ scans showed that the only crystallographic phase present was the hexagonal wurtzite structure. Scanning electron microscopy showed the formation of flowerlike ZnO nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred nanometers. The photoluminescence spectra of the ZnO nanostructures were recorded at 18-295 K using a cw He-Cd laser (325 nm) and a pulsed laser (266 nm). The ZnO nanostructures exhibit an ultraviolet emission band centered at ˜3.192 eV in the vicinity of the band edge, which is attributed to the well-known excitonic transition in ZnO.

  15. Use of silica-immobilized humin for heavy metal removal from aqueous solution under flow conditions.

    PubMed

    de la Rosa, G; Gardea-Torresdey, J L; Peralta-Videa, J R; Herrera, I; Contreras, C

    2003-10-01

    Humin extracted from Sphagnum peat moss was immobilized in a silica matrix and column experiments were performed in order to evaluate the removal and recovery of metal ions from aqueous solution under flow conditions. These experiments also allowed testing the recycling capacity of the column. Single-element solutions of Cu(II) and Pb(II), and a multi-metal solution containing Cd(II), Cu(II), Pb(II), Ni(II), and Cr(III) were passed through the columns at a flow rate of 2 ml/min. A 0.5 M sodium citrate solution was used as the stripping agent in the metal-ion recovery process. Humin immobilized in the silica matrix exhibited a similar, and in some cases, even a higher capacity than other biosorbents for the removal of metal ions from aqueous solutions under flow conditions. The sodium citrate was effective in removing Cu(II), Pb(II), Cd(II), and Ni(II) from the metal saturated column. The selectivity of the immobilized biomass was as follows: Cr(III)>Pb(II)>Cu(II)>Cd(II)>Ni(II). This investigation provides a new, environmentally friendly and cost-effective possibility to clean up heavy-metal contaminated wastewaters by using the new silica-immobilized humin material. PMID:12835051

  16. Inhibition of methemoglobin formation in aqueous solutions under aerobic conditions by the addition of amino acids.

    PubMed

    Wei, Yuping; Li, Chunlong; Zhang, Liang; Su, Zhiguo; Xu, Xia

    2014-03-01

    Hemoglobin (Hb) as an important iron-containing oxygen-transport protein is easily oxidized to the ferric met-form, methemoglobin (metHb), and loses the capacity of binding oxygen during storage. In this study, the experimental data indicate that the presence of Tyr and Glu significantly suppress the metHb formation in the Hb solutions in aqueous environment under aerobic conditions at the temperature of 25 and 37 °C, respectively. At pO2 of 144Torr the metHb percentage in the Hb solutions was the lowest with less than 10% at day 7 after incubation with Tyr at the ratio of 24 at pH 9.5 at 25 °C. At 37 °C, the metHb percentage did not reach 5% after 12h of incubation with Glu at the ratio of 24 at pH 9. Molecular simulation analysis suggest that the presence of Tyr or Glu may contribute to the formation of the breakwater network, the stabilization of distal histidine, the changes in the size of heme pocket, and eventually result in the inhibition of metHb formation. This study provides insight into a new design for Hb-oxygen based carriers with strongly inhibition of metHb formation in aqueous environment under aerobic conditions, even at physiological temperature in vitro. PMID:24342540

  17. Promoted oxidation of phenol in aqueous solution using molecular oxygen at mild conditions

    SciTech Connect

    Vogel, F.; Harf, J.; Hug, A.; Rohr, P.R. von

    1999-05-01

    Wet oxidation with molecular oxygen at mild conditions (temperature < 200 C, pressure {le} 2 MPa) is an economically attractive pretreatment step for non-biodegradable aqueous waste streams. In order to overcome the low reactivity of molecular oxygen towards organic molecules at these mild process conditions, an initiator was used in combination with ferrous ions in the acidic range. The promoted oxidation of phenol in aqueous solution was investigated in a 4 liters stirred autoclave. It was possible to degrade the phenol at temperatures as low as 100 C without observing an induction time. The remaining solution contained mainly acetic and formic acid and was well biodegradable. The oxidative behavior of the oxygen/phenol system could be explained using the well-known autoxidation mechanism for aliphatic molecules. 4-hydroperoxy-phenol is suggested as a key intermediate. Measured products are p-benzoquinone, hydroquinone, catechol, maleic, oxalic, pyruvic, formic, and acetic acid. Dimers could also be identified in sample extracts. A global pathway including all identified products is presented.

  18. Evaluation of chemical and diastereoisomeric stability of S-adenosylmethionine in aqueous solution by capillary electrophoresis.

    PubMed

    Desiderio, Claudia; Cavallaro, Rosaria A; De Rossi, Antonella; D'Anselmi, Fabrizio; Fuso, Andrea; Scarpa, Sigfrido

    2005-07-01

    Capillary electrophoresis was used for monitoring the stability of S-adenosylmethionine in aqueous solution under different conditions of storage and incubation used for "in vitro" and "in vivo" experiments, by evaluating both the entity of degradation and the possibility of epimerization at the sulfonium group. The determination of S,S-S-adenosylmethionine in presence of its R,S-epimer and degradation products was performed in uncoated capillary of 50 microm ID using 150 mM sodium phosphate buffer at pH 2.5. The analyses were performed in short or long-end injection modes depending if a fast monitoring of the degradation products or the evaluation of the diastereoisomeric ratio were carried out, respectively. In the long-end injection mode the baseline separation of S-adenosylmethionine diastereoisomeric forms and degradation products was obtained in less than 10 min with efficiency values in the range of 172,520-311,439 number of theoretical plates per meter. The results showed that freezing was the optimum storage mode for S-adenosylmethionine aqueous solutions preserving from degradation and diastereoisomeric ratio alterations. Under incubation conditions at 38 degrees C during 14 days period S-adenosylmethionine showed a strong degradation and the formation of three main increasing degradation products. After 7 and 14 days only the 52% and 32% of the initial drug concentration were available and the active S,S-S-adenosylmethionine form was the most affected. PMID:15925246

  19. Resistance to chemical disinfection under conditions of microgravity

    NASA Astrophysics Data System (ADS)

    Marchin, George L.

    1998-01-01

    In unit gravity, bacteria and disinfecting resin beads co-sediment to the septum in a fluid processing apparatus (FPA) resulting in effective chemical disinfection. In microgravity bacteria in suspension have access to a larger volume of the FPA because of a lack of sedimentation. Further, when disinfecting resin beads are added to the FPA they also remain in suspension reducing their effective concentration. Typically, therefore, disinfection experiments in microgravity return larger numbers of viable bacteria than ground-based controls. Preliminary experiments aboard the MIR Space Station with Pseudomonas aeruginosa additionally suggest that the longer bacteria are retained in microgravity the more resistant they become to chemical disinfection. This phenomenon is probably due to additional time to develop resistant biofilms on the interior of the FPA. To partially solve these problems we have developed additional disinfecting materials to use in conjunction with polyiodide containing resin beads. One of these materials carbon beads coated with 3-trimethoxy silylpropyl dimethyloctadecyl ammonium chloride (Dow-Corning 5700®), acts synergistically with polyiodide resin disinfectants. Carbon beads so treated are still able to remove aqueous iodine from the water stream while providing an additional level of chemical disinfection. This additional capability prevents contamination of the carbon beads with heterotrophic bacteria and insures that bacteria surviving iodine disinfection are efficiently devitalized.

  20. Prediction of aqueous solubility, vapor pressure and critical micelle concentration for aquatic partitioning of perfluorinated chemicals.

    PubMed

    Bhhatarai, Barun; Gramatica, Paola

    2011-10-01

    The majority of perfluorinated chemicals (PFCs) are of increasing risk to biota and environment due to their physicochemical stability, wide transport in the environment and difficulty in biodegradation. It is necessary to identify and prioritize these harmful PFCs and to characterize their physicochemical properties that govern the solubility, distribution and fate of these chemicals in an aquatic ecosystem. Therefore, available experimental data (10-35 compounds) of three important properties: aqueous solubility (AqS), vapor pressure (VP) and critical micelle concentration (CMC) on per- and polyfluorinated compounds were collected for quantitative structure-property relationship (QSPR) modeling. Simple and robust models based on theoretical molecular descriptors were developed and externally validated for predictivity. Model predictions on selected PFCs were compared with available experimental data and other published in silico predictions. The structural applicability domains (AD) of the models were verified on a bigger data set of 221 compounds. The predicted properties of the chemicals that are within the AD, are reliable, and they help to reduce the wide data gap that exists. Moreover, the predictions of AqS, VP, and CMC of most common PFCs were evaluated to understand the aquatic partitioning and to derive a relation with the available experimental data of bioconcentration factor (BCF). PMID:20958003

  1. Blue-shifted and picosecond amplified UV emission from aqueous chemical grown ZnO microrods

    NASA Astrophysics Data System (ADS)

    Empizo, Melvin John F.; Yamanoi, Kohei; Santos-Putungan, Alexandra B.; Arita, Ren; Minami, Yuki; Luong, Mui Viet; Shimizu, Toshihiko; Estacio, Elmer S.; Somintac, Armando S.; Salvador, Arnel A.; Sarmago, Roland V.; Sarukura, Nobuhiko

    2015-10-01

    Room-temperature amplified spontaneous emission (ASE) has been observed from aqueous chemical grown zinc oxide (ZnO) microrods. The well-faceted microrods have only a single narrow ultraviolet (UV) emission at 390 nm (3.2 eV) with average lifetimes as fast as 85-100 ps. The characteristic ASE also exhibits blue-shifted peaks and shortened lifetimes. At present, the peak shifting and the lifetime shortening are attributed to the band filling and photo-induced screening effects and to the nonradiative relaxation process, respectively. Results indicate that the ZnO microrods have good structural and optical quality which leads to their suitable use for optoelectronic applications.

  2. Validity conditions for moment closure approximations in stochastic chemical kinetics

    SciTech Connect

    Schnoerr, David; Sanguinetti, Guido; Grima, Ramon

    2014-08-28

    Approximations based on moment-closure (MA) are commonly used to obtain estimates of the mean molecule numbers and of the variance of fluctuations in the number of molecules of chemical systems. The advantage of this approach is that it can be far less computationally expensive than exact stochastic simulations of the chemical master equation. Here, we numerically study the conditions under which the MA equations yield results reflecting the true stochastic dynamics of the system. We show that for bistable and oscillatory chemical systems with deterministic initial conditions, the solution of the MA equations can be interpreted as a valid approximation to the true moments of the chemical master equation, only when the steady-state mean molecule numbers obtained from the chemical master equation fall within a certain finite range. The same validity criterion for monostable systems implies that the steady-state mean molecule numbers obtained from the chemical master equation must be above a certain threshold. For mean molecule numbers outside of this range of validity, the MA equations lead to either qualitatively wrong oscillatory dynamics or to unphysical predictions such as negative variances in the molecule numbers or multiple steady-state moments of the stationary distribution as the initial conditions are varied. Our results clarify the range of validity of the MA approach and show that pitfalls in the interpretation of the results can only be overcome through the systematic comparison of the solutions of the MA equations of a certain order with those of higher orders.

  3. Influences of solution chemical conditions on mobilization of TNT from contaminated soil

    SciTech Connect

    Dante, D.A.; Tiller, C.L.; Pennell, K.D.

    1996-12-31

    2,4,6-trinitrotoluene (TNT) and its byproducts are common contaminants on US military installations. Many potential remediation processes are in part limited by the transfer of TNT from the contaminated soil into the aqueous phase. The purpose of this research is to assess the release of TNT from contaminated soil under varying solution chemical conditions. In particular, influences of pH, aquatic natural organic matter, and addition of two surfactants is investigated. Uncontaminated soil was collected from a near-surface site at the Alabama Army Ammunition Plant and was artificially contaminated with TNT prior to the mobilization experiments. Results for the pH experiments show that more TNT is mobilized at neutral pH conditions than at low pH conditions. The presence of dissolved organic matter enhances the release of TNT from soil, but not by a large amount. Surfactant addition has the most significant effect on TNT mobilization.

  4. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: chemical characterization of the products

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Kitanovski, Zoran; Kroflič, Ana; Čusak, Alen

    2014-05-01

    One of the largest primary sources of organic aerosol in the atmosphere is biomass burning (BB) (Laskin et al. 2009); in Europe its contribution to annual mean of PM10 is between 3 and 14 % (Maenhaut et al. 2012). During the process of wood burning many different products are formed via thermal degradation of wood lignin. Hardwood burning produces mainly syringol (2,6-dimetoxyphenol) derivatives, while softwood burning exclusively guaiacol (2-methoxyphenol) and its derivatives. Taking into account physical properties of methoxyphenols only, their concentrations in atmospheric waters might be underestimated. So, their aqueous phase reactions can be an additional source of SOA, especially in regions under significant influence of wood combustion. An important class of compounds formed during physical and chemical aging of the primary BBA in the atmosphere is nitrocatechols, known as strong absorbers of UV and Vis light (Claeys et al. 2012). Very recently, methyl-nitrocatechols were proposed as suitable markers for highly oxidized secondary BBA (Iinuma et al. 2010, Kitanovski et al. 2012). In the present work, the formation of SOA through aqueous phase photooxidation and nitration of guaiacol was examined. The key objective was to chemically characterize the main low-volatility products and further to check their possible presence in the urban atmospheric aerosols. The aqueous phase reactions were performed in a thermostated reactor under simulated sunlight in the presence of H2O2 and nitrite. Guaiacol reaction products were first concentrated by solid-phase extraction (SPE) and then subjected to semi-preparative liquid chromatography.The main product compounds were fractionated and isolated as pure solids and their structure was further elucidated by using nuclear magnetic resonance spectroscopy (1H, 13C and 2D NMR) and direct infusion negative ion electro-spray ionization tandem mass spectrometry (( )ESI-MS/MS). The main photonitration products of guaiacol (4-nitroguaiacol, 6-nitroguaiacol and 4,6-dinitroguaiacol) were examined for their presence in winter aerosol samples by using an optimized HPLC-(-)ESI-MS/MS. 4-nitroguaiacol and 4,6-dinitroguaiacol were unambiguously identified in winter PM10 from Ljubljana, Slovenia, whereas the absence of 6-nitroguaiacol was further explained with the help of long-term reaction monitoring. To our knowledge, our study represents the first report on the identification of 4,6-dinitroguaiacol in ambient aerosols. Laskin, A. et al. (2009) Environ. Sci. Technol. 43, 3764-3771. Maenhaut, W. et al. (2012) Sci. Tot. Environ. 437, 226-236. Claeys, M. et al. (2012) Environ. Chem. 9, 273-284. Iinuma, Y. et al. (2010) Environ. Sci. Technol. 44, 8453-8459. Kitanovski, Z. et al. (2012)J. Chromatogr. A 1268, 35-43.

  5. Identification of the chemical constituents in aqueous extract of Zhi-Qiao and evaluation of its antidepressant effect.

    PubMed

    Wu, Ming; Zhang, Hongwu; Zhou, Chao; Jia, Hongmei; Ma, Zhuo; Zou, Zhongmei

    2015-01-01

    The immature fruit of Citrus aurantium L. (Zhi-Qiao, ZQ) has been used as a traditional medicine in China. Our previous study has shown that ZQ decoction may contribute to the antidepressant-like action of Chaihu-Shu-Gan-San. However, there are no reports on the chemical constituents of ZQ aqueous extract or its anti-depression effects. Firstly, this research reported the on-line identification of the chemical constituents in the aqueous extract of ZQ by coupling ultra-performance liquid chromatography/time-of-flight mass spectrometry (UPLC-Q-TOF/MS). A total of 31 chemical constituents were identified in ZQ aqueous extract, including one tannic acid, five flavones, 13 flavanones, one limonoid, three coumarins, three cyclic peptides, and five polymethoxylated flavonoids. The antidepressant effect of ZQ aqueous extract was evaluated in vivo and the results indicated that the mice immobility time during the forced swimming test and the tail suspension test were significantly reduced with ZQ treatment. MTT assays showed both ZQ aqueous extract and its major constituents (naringin, hesperidin, neohesperidin, and nobiletin) had neuroprotective effect on corticosterone-induced neurotoxicity in PC12 cells. The in vivo and in vitro results suggest that ZQ has an antidepressant effect. PMID:25913931

  6. Structure of a Novel Enzyme That Catalyzes Acyl Transfer to Alcohols in Aqueous Conditions

    SciTech Connect

    Mathews, I.; Soltis, M.; Saldajeno, M.; Ganshaw, G.; Sala, R.; Weyler, W.; Cervin, M.A.; Whited, G.; Bott, R.

    2009-06-03

    The unusual architecture of the enzyme (MsAcT) isolated from Mycobacterium smegmatis forms the mechanistic basis for favoring alcoholysis over hydrolysis in water. Unlike hydrolases that perform alcoholysis only under anhydrous conditions, MsAcT demonstrates alcoholysis in substantially aqueous media and, in the presence of hydrogen peroxide, has a perhydrolysis:hydrolysis ratio 50-fold greater than that of the best lipase tested. The crystal structures of the apoenzyme and an inhibitor-bound form have been determined to 1.5 {angstrom} resolution. MsAcT is an octamer in the asymmetric unit and forms a tightly associated aggregate in solution. Relative to other structurally similar monomers, MsAcT contains several insertions that contribute to the oligomerization and greatly restrict the shape of the active site, thereby limiting its accessibility. These properties create an environment by which MsAcT can catalyze transesterification reactions in an aqueous medium and suggests how a serine hydrolase can be engineered to be an efficient acyltransferase.

  7. IMPROVED DECONTAMINATION: INTERFACIAL, TRANSPORT, AND CHEMICAL PROPERTIES OF AQUEOUS SURFACTANT CLEANERS

    EPA Science Inventory

    This investigation is focused on decontamination using environmentally benign aqueous solutions, specifically the removal of organics and associated radionuclide and heavy metal contaminants by synthetic surfactants. Aqueous-based solutions promise several advantages for deconta...

  8. Nanoscale carbon materials from hydrocarbons pyrolysis: Structure, chemical behavior, utilisation for non-aqueous supercapacitors

    SciTech Connect

    Savilov, Serguei V.; Strokova, Natalia E.; Ivanov, Anton S.; Arkhipova, Ekaterina A.; Desyatov, Andrey V.; Hui, Xia; Aldoshin, Serguei M.; Lunin, Valery V.

    2015-09-15

    Highlights: • N-doped and regular carbon nanomaterials were obtained by pyrolitic technique. • Dynamic vapor sorption of different solvents reveals smaller S{sub BET} values. • Steric hindrance and specific chemical interactions are the reasons for this. • Nitrogen doping leads to raise of capacitance and coulombic efficiency with non-aqueous N-containing electrolyte. - Abstract: This work systematically studies adsorption properties of carbon nanomaterials that are synthesized through hydrocarbons that is a powerful technique to fabricate different kinds of carbon materials, e.g., nanotubes, nanoshells, onions, including nitrogen substituted. The adsorption properties of the as-synthesized carbons are achieved by low temperature nitrogen adsorption and organic vapors sorption. Heptane, acetonitrile, water, ethanol, benzene and 1-methylimidazole, which are of great importance for development of supercapacitors, are used as substrates. It is discovered that while nitrogen adsorption reveals a high specific surface area, this parameter for most of organic compounds is rather small depending not only on the size of its molecule but also on chemical interactions for a pair adsorbent–adsorbate. The experimental values of heat of adsorption for carbon and N-substituted structures, when Coulomb cross-coupling of nitrogen atoms in adsorbent and adsorbate takes place, confirms this supposition.

  9. Aqueous dispersions of few-layer-thick chemically modified magnesium diboride nanosheets by ultrasonication assisted exfoliation

    PubMed Central

    Das, Saroj Kumar; Bedar, Amita; Kannan, Aadithya; Jasuja, Kabeer

    2015-01-01

    The discovery of graphene has led to a rising interest in seeking quasi two-dimensional allotropes of several elements and inorganic compounds. Boron, carbon’s neighbour in the periodic table, presents a curious case in its ability to be structured as graphene. Although it cannot independently constitute a honeycomb planar structure, it forms a graphenic arrangement in association with electron-donor elements. This is exemplified in magnesium diboride (MgB2): an inorganic layered compound comprising boron honeycomb planes alternated by Mg atoms. Till date, MgB2 has been primarily researched for its superconducting properties; it hasn’t been explored for the possibility of its exfoliation. Here we show that ultrasonication of MgB2 in water results in its exfoliation to yield few-layer-thick Mg-deficient hydroxyl-functionalized nanosheets. The hydroxyl groups enable an electrostatically stabilized aqueous dispersion and create a heterogeneity leading to an excitation wavelength dependent photoluminescence. These chemically modified MgB2 nanosheets exhibit an extremely small absorption coefficient of 2.9 ml mg−1 cm−1 compared to graphene and its analogs. This ability to exfoliate MgB2 to yield nanosheets with a chemically modified lattice and properties distinct from the parent material presents a fundamentally new perspective to the science of MgB2 and forms a first foundational step towards exfoliating metal borides. PMID:26041686

  10. Sorption of lead from aqueous solution by chemically modified carbon adsorbents.

    PubMed

    Nadeem, Muhammad; Mahmood, A; Shahid, S A; Shah, S S; Khalid, A M; McKay, G

    2006-12-01

    An indigenously prepared, steam activated and chemically modified carbon from husk and pods of Moringa oleifera (M. oleifera), an agricultural waste, was comparatively examined as an adsorbent for the removal of lead from aqueous solutions. Studies were conducted as a function of contact time, initial metal concentration, dose of adsorbent, agitation speed, particle size and pH. Maximum uptake capacities were found to be, 98.89, 96.58, 91.8, 88.63, 79.43% for cetyltrimethyl ammonium bromide (CTAB), phosphoric, sulfuric, hydrochloric acid treated and untreated carbon adsorbents, respectively. Bangham, pseudo-first- and second-order, intra-particle diffusion equations were implemented to express the sorption mechanism by utilized adsorbents. Adsorption rate of lead ions was found to be considerably faster for chemically modified adsorbents than unmodified. The results of adsorption were fitted to both the Langmuir and Freundlich models. Satisfactory agreement between the metal uptake capacities by the adsorbents at different time intervals was expressed by the correlation coefficient (R(2)). The Langmuir model represented the sorption process better than the Freundlich one, with R(2) values ranging from 0.994 to 0.998. PMID:16839677

  11. Chemical Treatment Effects on Si(111) Surfaces in Aqueous NaF Solution

    NASA Astrophysics Data System (ADS)

    Tomita, Noriko; Adachi, Sadao

    2001-12-01

    Chemically treated Si(111) surfaces in aqueous NaF solution have been investigated using spectroscopic ellipsometry (SE), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and wettability measurements. The SE data indicate that the solution causes the removal of the native oxide upon immersing the sample in the solution. After the native oxide is etched away completely, the SE data yield the spectrum of a slightly roughened surface. The SE-estimated roughness is ˜ 0.64 nm, which is considerably larger than the AFM determined rms value (˜ 0.26 nm); the difference is considered to be due to the SE technique being sensitive not only to the surface microroughness but also to the adsorbed chemical species. The XPS data support the fact that the native oxide is removed upon immersing the sample in the solution. It is also shown that the Si LMM signal at ˜ 1160 eV can provide direct information regarding the relative quality of surface regions prepared by different methods. The wettability measurements show that the as-degreased surface is hydrophilic (θ˜ 35\\circ), while the NaF-etched surface is hydrophobic (θ˜ 70\\circ).

  12. Aqueous dispersions of few-layer-thick chemically modified magnesium diboride nanosheets by ultrasonication assisted exfoliation.

    PubMed

    Das, Saroj Kumar; Bedar, Amita; Kannan, Aadithya; Jasuja, Kabeer

    2015-01-01

    The discovery of graphene has led to a rising interest in seeking quasi two-dimensional allotropes of several elements and inorganic compounds. Boron, carbon's neighbour in the periodic table, presents a curious case in its ability to be structured as graphene. Although it cannot independently constitute a honeycomb planar structure, it forms a graphenic arrangement in association with electron-donor elements. This is exemplified in magnesium diboride (MgB2): an inorganic layered compound comprising boron honeycomb planes alternated by Mg atoms. Till date, MgB2 has been primarily researched for its superconducting properties; it hasn't been explored for the possibility of its exfoliation. Here we show that ultrasonication of MgB2 in water results in its exfoliation to yield few-layer-thick Mg-deficient hydroxyl-functionalized nanosheets. The hydroxyl groups enable an electrostatically stabilized aqueous dispersion and create a heterogeneity leading to an excitation wavelength dependent photoluminescence. These chemically modified MgB2 nanosheets exhibit an extremely small absorption coefficient of 2.9 ml mg(-1) cm(-1) compared to graphene and its analogs. This ability to exfoliate MgB2 to yield nanosheets with a chemically modified lattice and properties distinct from the parent material presents a fundamentally new perspective to the science of MgB2 and forms a first foundational step towards exfoliating metal borides. PMID:26041686

  13. Temporal Changes in Aqu/C60 Physical-Chemical, Deposition, and Transport Characteristics in Aqueous Systems

    EPA Science Inventory

    Little is known about how temporal changes in the physicalchemical properties of C60 aggregates formed in aqueous systems (termed aqu/C60) can impact transport pathways contributing to ecological exposures. In this study three aqu/C60 suspensions of short-term (100 days), interm...

  14. Temporal Changes in Aqu/C60 Physical-Chemical, Deposition, and Transport Characteristics in Aqueous Systems

    EPA Science Inventory

    Little is known about how temporal changes in the physical–chemical properties of C60 aggregates formed in aqueous systems (termed aqu/C60) can impact transport pathways contributing to ecological exposures. In this study three aqu/C60 suspensions of short-term (100 days), interm...

  15. Optimization of nickel adsorption from aqueous solution by using activated carbon prepared from waste apricot by chemical activation

    NASA Astrophysics Data System (ADS)

    Erdoğan, S.; Önal, Y.; Akmil-Başar, C.; Bilmez-Erdemoğlu, S.; Sarıcı-Özdemir, Ç.; Köseoğlu, E.; İçduygu, G.

    2005-12-01

    Waste apricot supplied by Malatya apricot plant (Turkey) was activated by using chemical activation method and K 2CO 3 was chosen for this purpose. Activation temperature was varied over the temperature range of 400-900 °C and N 2 atmosphere was used with 10 °C/min heat rate. The maximum surface area (1214 m 2/g) and micropore volume (0.355 cm 3/g) were obtained at 900 °C, but activated carbon was predominantly microporous at 700 °C. The resulting activated carbons were used for removal of Ni(II) ions from aqueous solution and adsorption properties have been investigated under various conditions such as pH, activation temperature, adsorbent dosage and nickel concentration. Adsorption parameters were determined by using Langmuir model. Optimal condition was determined as; pH 5, 0.7 g/10 ml adsorbent dosage, 10 mg/l Ni(II) concentration and 60 min contact time. The results indicate that the effective uptake of Ni(II) ions was obtained by activating the carbon at 900 °C.

  16. Aqueous Dissolution of Silver Iodide and Associated Iodine Release Under Reducing Conditions with Sulfide

    SciTech Connect

    Yaohiro Inagaki; Toshitaka Imamura; Kazuya Idemitsu; Tatsumi Arima; Osamu Kato; Hidekazu Asano; Tsutomu Nishimura

    2007-07-01

    Aqueous dissolution tests of silver iodide (AgI) were performed in Na{sub 2}S solutions in order to evaluate, empirically, dissolution of AgI to release iodine under reducing conditions with sulfide. The results indicated that AgI dissolves to release iodine being controlled by mainly precipitation of Ag{sub 2}S. However, the dissolution of AgI can be depressed to proceed, and the thermodynamic equilibrium cannot be attained easily. Solid phase analysis for the reacted AgI suggested that a thin layer of solid silver forming at AgI surface may evolve to be protective against transportation of reactant species, which can lead to the depression in the dissolution of AgI. (authors)

  17. Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

    USGS Publications Warehouse

    Marion, G.M.; Kargel, J.S.; Catling, D.C.; Jakubowski, S.D.

    2005-01-01

    Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice. The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (??) > activity of water (aw). The errors (%) in our model associated with these properties, however, fall in the order: ?? > K > aw. The transposition between K and ?? is due to a more accurate model for estimating K than for estimating ??. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements. To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO4. 12H2O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic. Copyright ?? 2005 Elsevier Ltd.

  18. Hydrogen from ethanol reforming with aqueous fraction of pine pyrolysis oil with and without chemical looping.

    PubMed

    Zin, R Md; Ross, A B; Jones, J M; Dupont, V

    2015-01-01

    Reforming ethanol ('EtOH') into hydrogen rich syngas using the aqueous fraction from pine bio-oil ('AQ') as a combined source of steam and supplementary organic feed was tested in packed bed with Ni-catalysts 'A' (18wt%/α-Al2O3) and 'B' (25wt%/γ-Al2O3). The catalysts were initially pre-reduced by H2, but this was followed by a few cycles of chemical looping steam reforming, where the catalysts were in turn oxidised in air and auto-reduced by the EtOH/AQ mixture. At 600°C, EtOH/AQ reformed similarly to ethanol for molar steam to carbon ratios (S/C) between 2 and 5 on the H2-reduced catalysts. At S/C of 3.3, 90% of the carbon feed converted on catalyst A to CO2 (58%), CO (30%) and CH4 (2.7%), with 17wt% H2 yield based on dry organic feedstock, equivalent to 78% of the equilibrium value. Catalyst A maintained these outputs for four cycles while B underperformed due to partial reduction. PMID:25461011

  19. Chemical vapor deposited carbon nanotubes for aqueous H2-Cl2 fuel cells.

    PubMed

    Suryavanshi, U B; Bhosale, C H

    2010-06-01

    Carbon nanotubes having large surface area is an interesting material to develop H2-Cl2 fuel cell electrodes. The attempts were made to deposit carbon nanotubes on porous substrates by chemical vapour deposition. Turpentine oil (C10H16) was used as a precursor, decomposed at 1100 degrees C reactor temperature. Nickel, platinum, tin, Ni-Pt, Ni-Sn, Pt-Sn, Ni-Pt-Sn catalysts were used to grow carbon nanotubes. Nickel was deposited with electrodeposition, platinum with sputter coater and tin with vacuum deposition technique. The developed electrodes were characterized by XRD, SEM, TEM, FTIR, and resistivity by van-der Pauw method. Carbon nanotubes have been formed for 0.25 N nickel deposited for 45 and 60 min; 0.5 N, 0.75 N and 1 N nickel deposited for 15 to 60 min, at the interval of 15. Ni-Pt, Ni-Sn, Pt-Sn and Ni-Pt-Sn activated carbon also shows the well grown CNTs. Aqueous H2-Cl2 fuel cell performance was tested with these grown carbon nanotubes. 40% KCl with 1067 mohm(-1) cm(-1) conductivity was used as electrolyte. Linear sweep voltametry shows reduction potential for hydrogen gas. Chronoamperometry results show better half cell performance for nickel, deposited with 1 N, 45 min deposition time period; and combination of Ni-Pt-Sn with 140, and 110-100 mA/cm2 stable current density respectively. PMID:20355406

  20. Contact Antimicrobial Surface Obtained by Chemical Grafting of Microfibrillated Cellulose in Aqueous Solution Limiting Antibiotic Release.

    PubMed

    Saini, Seema; Belgacem, Naceur; Mendes, Joana; Elegir, Graziano; Bras, Julien

    2015-08-19

    Contact active surfaces are an innovative tool for developing antibacterial products. Here, the microfibrillated cellulose (MFC) surface was modified with the β-lactam antibiotic benzyl penicillin in aqueous medium to prepare antimicrobial films. Penicillin was grafted on the MFC surface using a suspension of these nanofilaments or directly on films. Films prepared from the penicillin-modified MFC were characterized by Fourier transform infrared spectroscopy, contact angle measurements, elemental analysis, and X-ray photoelectron spectroscopy and tested for antibacterial activity against the Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. Penicillin-grafted MFC films exhibited successful killing effect on Gram-positive bacteria with 3.5-log reduction whereas bacteriostatic efficiency was found in penicillin-grafted MFC suspension. The zone of inhibition test and leaching dynamic assay demonstrated that penicillin was not diffused into the surrounding media, thus proving that the films were indeed contact active. Thus, penicillin can be chemically bound to the modified substrate surface to produce promising nonleaching antimicrobial systems. PMID:26218855

  1. Neutron Diffraction of Aqueous Tetramethylammonium Chloride (TMA) Solutions and TMA Intercalated Swelling Clays Under Burial Conditions

    NASA Astrophysics Data System (ADS)

    Patel, R.; Howard, C. A.; Greenwell, C.; Youngs, T.; Soper, A. K.; Skipper, N. T.

    2014-12-01

    There is a need for the improvement and optimisation of clay swelling inhibitors for the enhancement of oil and gas exploration. The hydration region of both ions and the possibility of ion pairing in 1 molar aqueous solution of clay swelling inhibitor, tetramethylammonium chloride (TMACl), in D2O, under elevated hydrostatic-pressures and temperatures has been determined with unprecedented detail using a combination of neutron diffraction and small-angle scattering in conjunction with hydrogen/deuterium isotopic labeling. The O-H correlation function (H-bonds) for the water in the 1.0M solution is measured and compared with that for pure D2O. Also investigated is the effect of burial conditions on the d-spacing of TMA-intercalated vermiculite. Contrary to expectations, no aggregation of TMA ions due to hydrophobic interactions is observed, nor are any ionic pairs of TMA+ and Cl- at these burial conditions. The data revealed a more ordered water-water structure with the addition of TMACl from bulk D2O. There is no change in the hydration structure measured at the applied elevated conditions. This is in remarkable contrast to pure water at the same conditions which is well known to be compressible. The dry d-spacing of the TMA-exchanged Eucatex vermiculite is measured at 13.66 Å which increases to 14.03 Å with the addition of D2O. Beyond this, there is no change in d-spacing with increasing pressure and temperature indicating the strength of the TMA ions binding to the clay interlayers and therefore its performance as a clay-swelling inhibitor.

  2. Fate of hydraulic fracturing chemicals under down-hole conditions

    NASA Astrophysics Data System (ADS)

    Blotevogel, J.; Kahrilas, G.; Corrin, E. R.; Borch, T.

    2013-12-01

    Hydraulic fracturing is a method to increase the yield of oil and natural gas extraction from unconventional rock formations. The process of hydrofracturing occurs via injecting water, sand, and chemicals into the production well and subjecting this mixture to high pressures to crack the rock shale, allowing increased amounts of gas and oil to seep out of the target formation. Typical constituents of the chemical mixtures are biocides, which are applied to inhibit growth of sulfate reducing bacteria in order to prevent pipe corrosion and production of hazardous gases. However, very little is known about the persistence, fate, and activity of biocides when subjected to the high temperatures and pressures of down-hole conditions. Thus, the objective of this talk is to present data from ongoing experiments focused on determining the fate of biocides commonly used for hydraulic fracturing under conditions simulating down-hole environments. Using stainless steel reactors, the high pressures and temperatures of down-hole conditions in the Marcellus shale are simulated, while concentration, speciation, and degradation of priority biocides are observed as a function of time, using primarily LC/MS techniques. The impact of water quality, shale, temperature, and pressure on the transformation kinetics and pathways of biocides will be discussed. Finally, field samples (both sediments and flowback brine) from the Marcellus shale are analyzed to verify that our lab simulations mirror real-life conditions and results.

  3. Improved Decontamination: Interfacial Transport, and Chemical Properties of Aqueous Surfactant Cleaners

    SciTech Connect

    Robert M. Counce

    2003-05-30

    The aqueous cleaning parameter of interest in this series of studies was the pH of the aqueous cleaning solution. A sessile droplet of industrial quench oil was analyzed to determine the effect of varied solution pH its removal from a stainless steel surface.

  4. Technical Note: Quantification of interferences of wet chemical HONO measurements under simulated polar conditions

    NASA Astrophysics Data System (ADS)

    Kleffmann, J.; Wiesen, P.

    2008-02-01

    In the present pilot study, an optimized LOPAP instrument for the detection of nitrous acid (HONO) in the atmosphere (DL 0.2 pptV) was tested at the high alpine research station "Jungfraujoch" at 3580 m altitude in the Swiss Alps under conditions comparable to polar regions. HONO concentrations in the range <0.5-50 pptV with an average of 7.5 pptV were observed at the "Jungfraujoch". The diurnal profiles obtained exhibited clear maxima at noon and minima with very low concentration during the night supporting the proposed photochemical production of HONO. In good agreement with recent measurements at the South Pole, it was demonstrated, that interferences of chemical HONO instruments can significantly influence the measurements and lead to considerable overestimations, especially for low pollution level. Accordingly, the correction of interferences is of paramount importance for those instruments, which sample HONO on aqueous or humid surfaces.

  5. Biological and chemical phosphorus solubilization from pyrolytical biochar in aqueous solution.

    PubMed

    He, Hui; Qian, Ting-Ting; Liu, Wu-Jun; Jiang, Hong; Yu, Han-Qing

    2014-10-01

    Biochar, a massive byproduct of biomass pyrolysis during biofuel generation, is a potential P source for the mitigation of P depletion. However, the chemical and biological effect of the release of P from biochar is still unclear. In this study, two types of Lysinibacillus strains (Lysinibacillussphaericus D-8 and Lysinibacillus fusiformis A-5) were separated from a sediment and their P-solubilizing characteristics to biochar was first reported. Compared with the bacterial mixture W-1 obtained from a bioreactor, the introduction of A-5 and D-8 significantly improved P solubilization. The release of P from biochar by A-5 and D-8 reached 54% and 47%, respectively, which is comparable to that under rigorous chemical conditions. SEM images and XPS spectra demonstrated that the physicochemical properties of the biochar surface have changed in the process which may be caused by the activities of the microbes. PMID:25065807

  6. Human Serum Albumin Increases the Stability of Green Tea Catechins in Aqueous Physiological Conditions

    PubMed Central

    Zinellu, Angelo; Sotgia, Salvatore; Scanu, Bastianina; Forteschi, Mauro; Giordo, Roberta; Cossu, Annalisa; Posadino, Anna Maria; Carru, Ciriaco; Pintus, Gianfranco

    2015-01-01

    Epicatechin (EC), epigallocatechin (EGC), epicatechingallate (ECG) and epigallocatechingallate (EGCG) are antioxidants present in the green tea, a widely used beverage whose health benefits are largely recognized. Nevertheless, major physicochemical limitations, such as the high instability of catechins, pose important questions concerning their potential pharmacological use. Recent studies indicate that binding of catechins with plasmatic proteins may modulate their plasma concentration, tissue delivery and biological activity. After 5 minutes of incubation with HSA both ECG and EGCG were fully bound to HSA, while after 48h incubation only 41% of EC and 70% of EGC resulted linked. HSA had a strong stabilizing effect on all catechins, which could be found in solution between 29 and 85% even after 48h of incubation. In the absence of HSA, EGC and EGCG disappeared in less than 24h, while ECG and EC were found after 48h at 5 and 50%, respectively. The stabilizing effect of HSA toward EGCG, obtained in aqueous physiological conditions, resulted stronger in comparison to cysteine and HCl, previously reported to stabilize this polyphenol. Because of the multitude of contradictory data concerning in vivo and in vitro antioxidant-based experimentations, we believe our work may shed some light on this debated field of research. PMID:26230943

  7. Radiolysis of pyridoxine (vitamin B 6) in aqueous solution under different conditions

    NASA Astrophysics Data System (ADS)

    Albarrán, Guadalupe; Ramírez-Cahero, Fernando; Aliev, Roustam

    2008-05-01

    Aqueous solutions of pyridoxine (1 mM) without or with additive of K 3[Fe(CN) 6] (2.5 mM) were gamma-irradiated at different doses and dose rate of 2.16 kGy/h in the absence of air, in the presence of air or by their saturation with N 2O. The radiolytic products were analyzed with HPLC, mass spectrometry and UV spectroscopy. 2,4,5-Trihydroxymethyl-3-pyridinol, pyridoxal, isopyridoxal and 6-hydroxypyridoxine were formed by radiolysis in the absence of K 3[Fe(CN) 6], and their concentrations were much higher in samples saturated with N 2O. Pyridoxi-3,6-quinone was found by radiolysis under all the above-mentioned conditions but only in the presence of K 3[Fe(CN) 6]. Besides, the pyridoxal formation increased in the presence of this oxidizing agent. G values of pyridoxal formation and pyridoxine degradation were quantified. Some details of the radiolytic product formation were discussed.

  8. Optimization for the removal of orthophosphate from aqueous solution by chemical precipitation using ferrous chloride.

    PubMed

    An, Ju-Suk; Back, Ye-Ji; Kim, Ki-Chul; Cha, Ran; Jeong, Tae-Young; Chung, Hyung-Keun

    2014-08-01

    The precipitation reaction between the orthophosphate and Fe2+ ions was studied to describe the optimum condition for the removal of orthophosphate from the aqueous solution. The effects of pH, Fe:P molar ratio, and alkalinity were evaluated for the initial orthophosphate concentrations in the range from 1.55 to 31.00 mg/L - PO4(3-) -P. The optimum pH was found to be 8.0 in all orthophosphate concentration ranges. When the stoichiometric moles of Fe2+ were added, the removal efficiencies were significantly less than the theoretical values. It is likely that the precipitation of Fe(OH)2(s) is partially formed. For the initial orthophosphate concentration of 3.10 mg/L PO4(3-) -P or greater, the removal efficiencies with the Fe:P molar ratio of 3.0:1.0 approached to the theoretical values, yielding greater than 98.5%. If the molar ratio of Fe:P was great enough, the precipitation reaction was completed within 1 h. As the alkalinity increases, the experimental removal efficiencies were significantly greater than the theoretical values. This is because the formation of vivianite is favoured over FeCO3(s). Finally, it was demonstrated that the orthophosphate (1.40-6.80 mg/L PO4(3-) -P) in the secondary effluents from wastewater treatment plants was effectively removed by dosing sufficient amount of Fe2+ ions. PMID:24956757

  9. Diverse Aqueous Conditions on Mars from New Orbital Detections of Carbonate and Sulfate

    NASA Astrophysics Data System (ADS)

    Wray, James J.; Squyres, S. W.

    2010-10-01

    Diverse aqueous environments on ancient Mars have been a key inference from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on NASA's Mars Reconnaissance Orbiter, which has identified many alteration minerals in a range of settings [e.g., 1-4]. Here we report two new minerals detected using CRISM. In the southern highlands northwest of the Hellas basin, a mid-sized crater exposes carbonate in its central uplift. Spectral absorptions at 1, 2.33, and 2.53 microns are most consistent with Fe-carbonate, distinct from the Mg-carbonates identified from orbit by [5]. Fe-carbonate is associated with Mg-phyllosilicate in fractured materials formerly buried kilometers beneath the surface, and--like the Mg/Fe-carbonate found by the Spirit rover [6]--suggests a reducing, neutral-to-alkaline alteration environment. One of the largest phyllosilicate exposures on Mars occurs in the Mawrth Vallis region [e.g., 7]. We identify bassanite (Ca-sulfate hemihydrate) in layers underlying the phyllosilicate-bearing beds [8], a stratigraphy distinct from that predicted by global models of martian aqueous history [9]. Bassanite could have formed via acid-sulfate alteration of Ca-carbonate, through dehydration of gypsum, or under hydrothermal conditions [10]. These detections expand the known mineralogic diversity of Mars and the range of environments to explore for past habitability. [1] Mustard, J. F. et al. (2008) Nature 454, 305-309. [2] Murchie, S. L. et al. (2009) J. Geophys. Res. 114, E00D06. [3] Ehlmann, B. L. et al. (2009) J. Geophys. Res. 114, E00D08. [4] Wray, J. J. et al. (2009) Geology 37, 1043-1046. [5] Ehlmann, B. L. et al. (2008) Science 322, 1828-1832. [6] Morris, R. V. et al. Science, in press, doi:10.1126/science.1189667. [7] Poulet, F. et al. (2005) Nature 438, 623-627. [8] Wray, J. J. et al. Icarus, in press, doi:10.1016/j.icarus.2010.06.001. [9] Bibring, J.-P. et al. (2006) Science 312, 400-404. [10] Vaniman, D. T. et al. (2009) LPSC 40, 1654.

  10. Influences of solution chemical conditions on mobilization of TNT from contaminated soil

    SciTech Connect

    Dante, D.A.; Tiller, C.L.; Pennell, K.D.

    1996-12-31

    Residual explosives and their byproducts are common contaminants at several US military installations. One of the major explosive contaminants is 2,4,6-Trinitrotoluene (TNT) (a hydrophobic organic compound). Contamination from TNT has resulted from manufacturing and handling processes which occurred at military installations, especially Army Ammunition Plants (AAP), over many decades until environmental regulations were implemented. TNT causes adverse effects to the environment, including growth inhibition to plants, toxicity to aquatic life, and possible mutagenicity, and also is toxic to humans. As a result of the effects of TNT on the environment and current environmental regulations, substantial research effort has been focused on determining the fate of TNT in natural systems and the development of remediation processes. Many potential remediation processes, such as those involving plants or microorganisms, are in part limited by the transfer of TNT from solid phases (e.g., sorbed to soil or present as TNT granules) to the aqueous phase. The purpose of this research is to assess the release of TNT from a soil phase to a mobile aqueous phase under varying solution chemical conditions. In particular, influences of pH, aquatic natural organic matter, and surfactants are investigated.

  11. Chemical reactions in viscous liquids under space conditions

    NASA Astrophysics Data System (ADS)

    Kondyurin, A.; Lauke, B.; Richter, E.

    A long-term human flight needs a large-size space ships with artificial self-regulating ecological life-support system. The best way for creation of large-size space ship is a synthesis of light construction on Earth orbit, that does not need a high energy transportation carriers from Earth surface. The construction can be created by the way of chemical polymerisation reaction under space environment. But the space conditions are very specific for chemical reactions. A high vacuum, high energy particles, X-rays, UV- and VUV-irradiations, atomic oxygen, microgravity have a significant influence on chemical reactions. Polymerisation reactions in liquid active mixture were studied in simulated space environment. The epoxy resins based on Bisphenol A and amine curing agents were investigated under vacuum, microwave plasma discharge and ion beam. An acceleration of polymerisation reaction with free radicals formation was observed. The polymerisation reaction can be carried out under space environment. The study was supported by Alexander von Humboldt Foundation (A. Kondyurin) and European Space Agency, ESTEC (contract 17083/03/NL/Sfe "Space Environmental Effects on the Polymerisation of Composite Structures").

  12. Experimental study of the influence of chemical reactions on convective dissolution of CO2 in aqueous solutions.

    NASA Astrophysics Data System (ADS)

    Thomas, Carelle; Lemaigre, Lorena; Haudin, Florence; Zalts, Anita; D'Onofrio, Alejandro; De Wit, Anne

    2014-05-01

    Within the global context of climate change, carbon dioxide (CO2) sequestration into deep saline aquifers is one of the technologies being considered in order to tackle the accumulation of anthropogenic CO2 in the atmosphere. Upon injection of CO2 into these porous geological formations, the less dense CO2 rises above the aqueous phase, spreads laterally under the upper impermeable cap rock and starts to dissolve into the underlying brine. This leads to a buoyantly unstable stratification of denser CO2-enriched brine on top of less dense brine, which can give rise to density-driven convective fingering in the fluid. This hydrodynamic instability is a favorable process for CO2 sequestration as it accelerates the mixing of CO2 into the aqueous phase and therefore enhances the safety of the storage in the saline aquifer (by reducing the risks of leaks of CO2 to the atmosphere). The influence of chemical reactions and of the physico-chemical characteristics of the geological reservoir on the development of this instability is, however, still not completely understood. In this context, we study experimentally in a laboratory-scale reactor the influence of chemical reactions on convective fingering occurring during dissolution of CO2 in reactive aqueous solutions. Experiments are performed in Hele-Shaw cells (constructed of two vertical transparent plates separated by a thin gap) in which gaseous CO2 at atmospheric pressure flows above aqueous solutions containing chemical reactants. Dynamics occurring within the transparent fluids are visualized by Schlieren techniques, which track dynamical changes in refractive index related to density gradients in the solutions. We show that in some cases the convection can be enhanced by chemical reactions as they accelerate the development of the fingers, shorten their onset time and increase the number of fingers. In particular, we show that the presence of a color indicator (for instance bromocresol green) in the aqueous solution can affect the fingering dynamics. Color indicators should therefore be used with caution in this kind of study.

  13. Induced Sporicidal Activity of Chlorhexidine against Clostridium difficile Spores under Altered Physical and Chemical Conditions

    PubMed Central

    Nerandzic, Michelle M.; Donskey, Curtis J.

    2015-01-01

    Background Chlorhexidine is a broad-spectrum antimicrobial commonly used to disinfect the skin of patients to reduce the risk of healthcare-associated infections. Because chlorhexidine is not sporicidal, it is not anticipated that it would have an impact on skin contamination with Clostridium difficile, the most important cause of healthcare-associated diarrhea. However, although chlorhexidine is not sporicidal as it is used in healthcare settings, it has been reported to kill spores of Bacillus species under altered physical and chemical conditions that disrupt the spore’s protective barriers (e.g., heat, ultrasonication, alcohol, or elevated pH). Here, we tested the hypothesis that similarly altered physical and chemical conditions result in enhanced sporicidal activity of chlorhexidine against C. difficile spores. Principal Findings C. difficile spores became susceptible to heat killing at 80°C within 15 minutes in the presence of chlorhexidine, as opposed to spores suspended in water which remained viable. The extent to which the spores were reduced was directly proportional to the concentration of chlorhexidine in solution, with no viable spores recovered after 15 minutes of incubation in 0.04%–0.0004% w/v chlorhexidine solutions at 80°C. Reduction of spores exposed to 4% w/v chlorhexidine solutions at moderate temperatures (37°C and 55°C) was enhanced by the presence of 70% ethanol. However, complete elimination of spores was not achieved until 3 hours of incubation at 55°C. Elevating the pH to ≥9.5 significantly enhanced the killing of spores in either aqueous or alcoholic chlorhexidine solutions. Conclusions Physical and chemical conditions that alter the protective barriers of C. difficile spores convey sporicidal activity to chlorhexidine. Further studies are necessary to identify additional agents that may allow chlorhexidine to reach its target within the spore. PMID:25861057

  14. Kinetics of Organic Transformations Under Mild Aqueous Conditions: Implications for the Origin of Life and Its Metabolism

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2003-01-01

    The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction half-life at 50 C, and to reveal the effect of functional groups on reactivity. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable (i. e. acetate decarboxylation half-life was l0(exp 18) years at 50 C); whereas, organic substances containing two oxygenated groups in which one group was a beta-positioned carbonyl group were the most reactive (i. e. acetoacetate decarboxylation half-life was l0(exp-2) years at 50 C). Of all functional groups the beta-positioned carbonyl group (aldehyde or ketone) was the strongest activating group, giving rates of reaction that were up to 10(exp 24)-times faster than rates of similar molecules lacking the beta-carbonyl group. From this knowledge of organic reactivity and the inherent constraints of autocatalytic processes, we concluded that an origins-of-life process based on autocatalytic transformation of C,H,O-substrates was constrained to using the most reactive organic molecules that contain alpha- or beta-carbonyl groups, since small autocatalytic domains of plausible catalytic power that used less reactive substrates could not carry out chemical transformations fast enough to prevent catastrophic efflux (escape) of reaction intermediates. Knowledge of the kinetics of organic transformations is useful, not only in constraining the chemistry of the earliest autocatalytic process related to the origin of life, but also in establishing the relative reactivity of organic molecules on the early Earth and other planets that may or may not be related to the origin of life.

  15. Equilibrium hydrate formation conditions for hydrogen sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride

    SciTech Connect

    Majumdar, A.; Mahmoodaghdam, E.; Bishnoi, P.R.

    2000-02-01

    Natural gas components such as hydrogen sulfide, carbon dioxide, and ethane form gas hydrates of structure I under suitable temperature and pressure conditions. Information on such conditions is vital to the oil and gas industry in order to design and operate processing equipment and pipelines so that hydrate formation is avoided. Incipient equilibrium hydrate formation conditions for hydrogen sulfide, carbon dioxide, and ethane in aqueous solutions of ethylene glycol and sodium chloride were experimentally obtained in the temperature range 264--290 K and the pressure range 0.23--3.18 MPa. A variable-volume sapphire cell was used for the measurements.

  16. Optimum conditions for composites fiber coating by chemical vapor infiltration

    SciTech Connect

    Griffiths, S.K.; Nilson, R.H.

    1997-04-01

    A combined analytical and numerical method is employed to optimize process conditions for composites fiber coating by chemical vapor infiltration (CVI). For a first-order deposition reaction, the optimum pressure yielding the maximum deposition rate at a preform center is obtained in closed form and is found to depend only on the activation energy of the deposition reaction, the characteristic pore size, and properties of the reactant and product gases. It does not depend on the preform specific surface area, effective diffusivity or preform thickness, nor on the gas-phase yield of the deposition reaction. Further, this optimum pressure is unaltered by the additional constraint of a prescribed deposition uniformity. Optimum temperatures are obtained using an analytical expression for the optimum value along with numerical solutions to the governing transport equations. These solutions account for both diffusive and advective transport, as well as both ordinary and Knudsen diffusion. Sample calculations are presented for coating preform fibers with boron nitride.

  17. Adsorption of anionic dyes from aqueous solutions using chemically modified straw.

    PubMed

    Zhang, Wenxuan; Li, Haijiang; Kan, Xiaowei; Dong, Lei; Yan, Han; Jiang, Ziwen; Yang, Hu; Li, Aimin; Cheng, Rongshi

    2012-08-01

    The effective disposal of redundant straw is a significant work for environmental protection and full utilization of resource. In this work, the wheat straw has been modified by etherification to prepare a kind of quaternary ammonium straw adsorbents. The adsorption behaviors of the modified straw for methyl orange (MO) and acid green 25(AG25) were studied in both batch and column systems. The adsorption capacity of the straw for both dyes improved evidently after modification. The maximal MO and AG25 uptakes were more than 300 and 950 mg g(-1), respectively. Furthermore, the adsorption equilibrium, kinetics and column studies all indicated that the adsorption behavior was a monolayer chemical adsorption with an ion-exchange process. In addition, after adsorption of anionic dyes, the used adsorbents were successfully applied to adsorb a cationic dye directly at suitable conditions in the secondary adsorption. This was due to the altered surface structures of the used adsorbents. PMID:22609712

  18. Epoxidized natural rubber toughened aqueous resole type liquefied EFB resin: Physical and chemical characterization

    NASA Astrophysics Data System (ADS)

    Amran, Umar Adli; Zakaria, Sarani; Chia, Chin Hua

    2013-11-01

    A preliminary study on the reaction between aqueous resole type resinified liquefied palm oil empty fruit bunches fibres (RLEFB) with epoxidized natural rubber (ENR). Liquefaction of empty fruit bunches (EFB) is carried out at different ratio of phenol to EFB (P:EFB). Resole type phenolic resin is prepared using sodium hydroxide (NaOH) as the catalyst with the ratio of liquefied EFB (LEFB) to formaldehyde (LEFB:F) of 1:1.8. 50% epoxidation of epoxidized natural rubber (ENR-50) is used to react with resole resin by mixing with ENR with aqueous resole resin. The cured resin is characterized with FT-IR and SEM. Aqueous system have been found to be unsuitable medium in the reaction between resin and ENR. This system produced a highly porous product when RLEFB/ENR resin is cured.

  19. Chemical extraction of arsenic from contaminated soil under subcritical conditions.

    PubMed

    Oh, Seok-Young; Yoon, Myong-Keun; Kim, Ick-Hyun; Kim, Ju Yup; Bae, Wookeun

    2011-07-15

    In this research, we investigated a chemical extraction process, under subcritical conditions, for arsenic (As)-contaminated soil in the vicinity of an abandoned smelting plant in South Korea. The total concentration of As in soil was 75.5 mg/kg, 68% of which was As(+III). X-ray photoelectron spectroscopy analysis showed that the possible As(+III)-bearing compounds in the soil were As(2)O(3) and R-AsOOH. At 20°C, 100 mM of NaOH could extract 26% of the As from the soil samples. In contrast, 100 mM of ethylenediaminetetraacetic acid (EDTA) and citric acid showed less than 10% extraction efficiency. However, as the temperature increased to 250 and 300°C, extraction efficiencies increased to 75-91% and 94-103%, respectively, regardless of the extraction reagent used. Control experiments with subcritical water at 300°C showed complete extraction of As from the soil. Arsenic species in the solution extracted at 300°C indicated that subcritical water oxidation may be involved in the dissolution of As(+III)-bearing minerals under given conditions. Our results suggest that subcritical water extraction/oxidation is a promising option for effective disposal of As-contaminated soil. PMID:21601910

  20. Chemical durability of hollandite ceramic for conditioning cesium

    NASA Astrophysics Data System (ADS)

    Angeli, Frédéric; McGlinn, Peter; Frugier, Pierre

    2008-10-01

    The aqueous corrosion behavior of Cs-doped hollandite ceramic (BaCs 0.28Fe 0.82Al 1.46Ti 5.72O 16) was studied using several different static experimental protocols, with leachants of varying pH, and at different surface area to volume ratios, for periods ranging from six months to three years. All leach tests were carried out at 90 °C. X-ray diffraction (XRD) and scanning electron microscopy (SEM), coupled with energy dispersive X-ray spectroscopy (EDS), were used to characterize the surfaces of the hollandite before and after leaching. The most pronounced elemental releases, and corresponding changes to surface composition and microstructure, was evident at low pH, in particular pH 1. Cs and Ba releases were highest at low pH, with surface alteration exhibited by the formation of secondary rutile (prevalent at pH 1) and Al- and Ba-depleted hollandite (prevalent at pH 2). After rapid initial Cs release, the alteration rate was extremely low over the pH range from 2 to 10, as well as in pure water experiments with a sample-surface-area-to-solution-volume ratio ranging from 0.1 cm -1 to 1200 cm -1. The rates were about 10 -5 g m -2 d -1, corresponding to alteration thicknesses of a few nanometers per year. Higher rates (5 × 10 -3 g m -2 d -1) were observed only under very acidic conditions (pH 1). Congruency in Cs and Ba releases occurred only at pH 1, with incongruency between the two elements increasing with increasing pH. There were no apparent solubility constraints on Cs releases regardless of the SA/ V ratio, whereas geochemical modeling suggested that Ba releases could have been affected by the formation of BaCO 3, particularly at high SA/ V ratios. Extended leaching (with the leachant renewed once after 261 days of leaching) confirmed the high durability of hollandite with altered thicknesses of less than one nanometer per year over the last two years. Whilst Cs depletion of the hollandite surface was evidenced when leachates were replenished with the fresh deionised water, the presence of a soluble Ba-bearing secondary phase was inferred.

  1. FINAL REPORT. CHEMICAL SPECIATION OF INORGANIC COMPOUNDS UNDER HYDROTHERMAL CONDITIONS

    EPA Science Inventory

    We have conducted measurements at 400 degrees C of the oxidation of Cr (III) to Cr (VI) by
    NO3-/NO2-. These spectra are to the best of our knowledge the first reported in situ spectroscopic observation of homogeneous aqueous redox chemistry at temperatures beyond the critical...

  2. CHEMICAL TRANSFORMATION MODULES FOR EULERIAN ACID DEPOSITION MODELS. VOLUME 2. THE AQUEOUS-PHASE CHEMISTRY

    EPA Science Inventory

    This study focuses on the review and evaluation of mechanistic and kinetic data for aqueous-phase reactions that lead to the production of acidic substances in the environment. The intent of this research is to provide a framework that can be used to develop a state-of-the-art aq...

  3. Effectiveness of chemical dispersants under breaking wave conditions

    SciTech Connect

    Mackay, D.

    1995-06-01

    A study is described in which the effectiveness of Corexit 9527 on Alaskan North Slope crude oil was assessed by conducting laboratory and wave basin tests. Three laboratory dispersant test systems were used: the MNS, Labofina and EXDET procedures. It was concluded that for the present purposes the EXDET system was most suitable, and it was used for subsequent tests. The dependence of effectiveness on dispersant to oil ratio, extent of weathering, temperature, water salinity, energy level and the presence of emulsified water (mousse) were determined. The results were used to guide a subsequent program of tests at the Esso Resources Canada Ltd. Wave Basin in Calgary in which the effectiveness was determined under breaking wave conditions. From the results a correlating equation was developed to express effectiveness as a function of dispersant to oil ratio and delay time between dispersant application and the onset of breaking waves. Significant quantities of oil were dispersed under breaking wave conditions, even at what are conventionally regarded as low dispersant to oil ratios. The implications of the results for assessing the actual and potential extent of chemical dispersion following the Exxon Valdez spill in March 1989 are discussed. Assuming that the dispersion efficiencies from the wave basin could have been achieved at the incident, it is believed that because of the onset of the storm with breaking wave conditions some 60 hours after the grounding, approximately 38% of the spilled oil could have been dispersed had available dispersants been applied to the spilled oil in the days following the grounding.

  4. Parameterizing the equilibrium distribution of chemicals between the dissolved, solid particulate matter, and colloidal matter compartments in aqueous systems

    USGS Publications Warehouse

    Pankow, J.F.; McKenzie, S.W.

    1991-01-01

    The manner in which a chemical material partitions among the dissolved (D), participate (P), and colloidal (C) phases affects both its chemical and physical behavior in the aquatic environment. The fractions of the chemical that are present in each of these three phases will be determined by the values of two simple parameters, KpSp/??w and KcSc/??w. The variables Kp and Kc are the particle/water and colloid/water partition constants (mL/g), respectively, Sp and Sc are the volume concentrations of particulate and colloidal material (mg/L), respectively, and ??w is the fractional volume of the system that is aqueous. This parameterization allows a rapid overview of how partitioning (1) changes as a function of chemical partitioning properties and water type, (2) affects apparent partition constants (i.e., Kpapp values) computed between the particulate phase and the remainder of the system, and (3) causes Kpapp values to become independent of chemical properties at high values of KcSc/??w. ?? 1991 American Chemical Society.

  5. Development of chemical indicators of aqueous alteration on Mars with applications to the 2004 MER landing sites

    NASA Astrophysics Data System (ADS)

    Greenwood, J. P.; Blake, R. E.

    2003-12-01

    Data collected by the Mars Odyssey Gamma Ray Spectrometer (GRS) and Mars Exploration Rover Alpha Particle X-ray Spectrometers (MER-APXS) will allow for unprecedented chemical information to be obtained from the Martian surface. Phosphorous and iron are two elements that should be measured with some accuracy by MER-APXS (as opposed to MPF). The well-known affinity of iron oxide/hydroxides for sorption of phosphate in oceans, lakes, rivers, and soils will be used to assess the utility of P/Fe (in conjunction with other elements and element ratios measurable by MER-APXS) as an indicator of aqueous activity at the two 2004 MER landing sites. Iron oxide/hydroxides are also an effective sink for Th in terrestrial waters; thus, GRS data may also be valuable in evaluating the nature of aqueous alteration (or lack thereof) at the MER landing sites. For example, the hematite-bearing deposit in Sinus Meridiani (2S, 4W) has a high Th concentration and low K/Th, suggesting that sorption of Th by specular hematite in aqueous solution may have occurred at some point in the geologic history of this region of Mars. Experiments on the sorptive properties of specular hematite and palagonite for PO4 and Th will be used to develop a model for the role of water in formation of deposits at the two MER landing sites.

  6. CHEMICAL SYNTHESIS USING 'GREENER' ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The chemical research during the last decade has witnessed a paradigm shift towards "environmentally-friendly chemistry" more popularly known as "green chemistry" due to the increasing environmental concerns and legislative requirements to curb the release of chemical waste into ...

  7. Hydrolysis and photolysis of diacylhydrazines-type insect growth regulator JS-118 in aqueous solutions under abiotic conditions.

    PubMed

    Hu, J-Y; Liu, C; Zhang, Y-C; Zheng, Z-X

    2009-05-01

    JS-118 is a diacylhydrazines-type insect growth regulator which is now used extensively in China. The hydrolysis and photolysis of the pesticide JS-118 in aqueous solutions have been assessed under natural and controlled conditions in this project. Hydrolysis experimental results show that JS-118 is quite stable in aqueous solutions in dark, with no significant variations be observed in degradation under various conditions. Abiotic hydrolysis is relatively unimportant compared to photolysis. The rate of photodecomposition of JS-118 in aqueous solutions follows first-order kinetics both in UV radiation and natural sunlight. The degradation rates are faster under UV light than sunlight, with the half-lives (t (1/2) = ln2/k) of 6.00-10.85 min and 6.63-10.16 day, respectively. Under UV light, two major photoproducts are detected, and tentatively identified according to HPLC-MS spectral information as N-t-butyl-N-(3,5-dimethylbenzoyl) and 3,7-dimethyl-benzoatedihydrofuran. The corresponding photolysis pathways of JS-118 are also proposed. The results obtained indicate that direct photoreaction is an important dissipation pathway of JS-118 in natural water systems. PMID:19165405

  8. Arsenic mobility in soils contaminated with metallurgical wastes as a function of variable chemical conditions

    NASA Astrophysics Data System (ADS)

    Garcia Payne, D. G.; Villalobos, M.; Ceniceros, A.; Lopez, J. L.; Gutierrez, M.

    2008-12-01

    Arsenic is a pervasive contaminant of natural aqueous systems, such as groundwater and soils, its sources being both natural and anthropogenic. The present investigation was performed on soils contaminated with residues from ore processing activities and revealed the presence of arsenate [As(V)] species with a very low mobility, through natural attenuation processes. The stability of this attenuation was investigated by varying two specific equilibrium chemical conditions: pH and presence of bicarbonate ions. One-unit changes in equilibrium pH generally caused small increases in As mobility, whereas the presence of bicarbonate ions considerably increased this mobility. The results were compared to thermodinamic simulations of equilibrium conditions using the total elemental composition of each individual soil, but excluding sorption reactions. Close matches between experimental data and simulations revealed the predominance of solubility-controlled As mobility via heavy-metal arsenate solid formation. Bicarbonate ions were found to be highly unsuitable for extraction of sorbed arsenate fractions due to indirect As release from solid arsenates, via heavy-metal carbonate precipitation processes.

  9. Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions.

    PubMed

    Thoi, V Sara; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2013-03-21

    Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous-organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products. PMID:23034627

  10. Improved removal of malachite green from aqueous solution using chemically modified cellulose by anhydride.

    PubMed

    Zhou, Yanmei; Min, Yinghao; Qiao, Han; Huang, Qi; Wang, Enze; Ma, Tongsen

    2015-03-01

    Cellulose modified with maleic (M) and phthalic (P) anhydride, to be named CMA and CPA, were tested as feasible adsorbents for the removal of malachite green from aqueous solution. At the same time, the uptake ability of natural cellulose was also studied for comparison. The structure of material was characterized by FT-IR and XRD. The effects of solution pH, initial dye concentration, contact time and temperature were investigated in detail by batch adsorption experiments. The kinetic and isotherm studies suggested that the adsorption followed the pseudo-second-order model and Langmuir isotherm. The maximum adsorption capacity on CMA and CPA were 370 mg g(-1) and 111 mg g(-1), respectively. Furthermore, the thermodynamics studies indicated the spontaneous nature of adsorption of malachite green on adsorbents. All the studied results showed that the modified cellulose could be used as effective adsorption material for the removal of malachite green from aqueous solutions. PMID:25542168

  11. Radiation chemical behavior of aqueous butanal oxime solutions irradiated with helium ion beams

    NASA Astrophysics Data System (ADS)

    Costagliola, A.; Venault, L.; Deroche, A.; Garaix, G.; Vermeulen, J.; Omnee, R.; Duval, F.; Blain, G.; Vandenborre, J.; Fattahi-Vanani, M.; Vigier, N.

    2016-02-01

    Samples of butanal oxime in aqueous solution have been irradiated with the helion (4He2+) beam of the ARRONAX (Nantes) and the CEMHTI (Orléans) cyclotrons. The consumption yield of butanal oxime has been measured by gas-chromatography coupled with mass spectrometry. Yields of gaseous products (mainly H2) have also been measured by micro-gas-chromatography. Butanal oxime can react with H• radicals by abstraction mechanism to enhance H2 production. Yields of liquid phase products (hydrogen peroxide and nitrite ion) have been measured by colorimetric methods. Butanal oxime acts as a scavenger of OH• radical to inhibit the production of H2O2. The observation of the radiolytic products allows then to discuss a degradation mechanism of butanal oxime in aqueous solutions.

  12. Chemical passivation of InSb (100) substrates in aqueous solutions of sodium sulfide

    SciTech Connect

    Lvova, T. V. Dunaevskii, M. S.; Lebedev, M. V.; Shakhmin, A. L.; Sedova, I. V.; Ivanov, S. V.

    2013-05-15

    The elemental composition and electronic structure of both native-oxide-covered InSb (100) substrates and substrates treated in aqueous solutions of sodium sulfide are analyzed by X-ray photoelectron spectroscopy. It is found that, as a result of treatment in a 1 M aqueous solution of Na{sub 2}S and subsequent annealing in vacuum at 150 Degree-Sign C, the surface layer consisting of complex antimony and indium oxides of nonstoichiometric composition is removed completely with the formation of a continuous layer of chemisorbed sulfur atoms coherently bound to indium atoms. According to atomic-force microscopy data, no etching of the host substrate material occurs during sulfide passivation. A shift (by 0.37 eV) of the In-Sb bulk photoemission towards higher binding energies is found, which indicates that the surface Fermi level shifts deeper into the conduction band.

  13. Tertiary recovery process. [conditioning the research with a solution of a vinylpyrrolidone polymer, then an aqueous surfactant is injected and then waterflooding

    SciTech Connect

    Haltmar, W.C.; Lacey, E.S.

    1980-06-17

    A process for recovering hydrocarbons from a hydrocarbon-bearing formation penetrated by an injection well and a production well which comprises injecting an aqueous solution of a vinylpyrrolidone polymer into the formation to condition the reservoir, in a first step injecting an aqueous surfactant solution into the formation and recovering hydrocarbons via the said production well. The pretreatment of the formation with the vinylpyrrolidone polymer reduces the consumption or loss of surfactant and thus improves the efficiency of the process. Optionally, after the injection of the aqueous surfactant solution an aqueous drive fluid is injected into the formation.

  14. Localized Chemical Redistribution During Aqueous Alteration in CR2 Carbonaceous Chondrites EET 87770 and EET 92105

    NASA Technical Reports Server (NTRS)

    Burger, Paul V.; Brearley, Adrian J.

    2005-01-01

    Carbonaceous chondrites are primitive meteorites that are valuable because they preserve evidence of processes that occurred in the solar nebula and on asteroidal parent bodies. Among the carbonaceous chondrite groups, the CR group appears to contain a particularly pristine record of early solar system processes. Distinguishing characteristics of CR2 chondrites include a high abundance of chondrules (50-60 vol.%) and Fe, Ni metal (5-8 vol. %). These meteorites preserve evidence for varying degrees of aqueous alteration, manifested by progressive replacement of chondrule mesostasis by phyllosilicates. Recent studies have suggested that even in weakly altered chondrites, mass transfer occurred between chondrules and fine-grained matrices, implying that aqueous alteration must have followed lithification of the final meteorite parent body. Although petrographic characteristics of alteration in CR chondrites have been documented, mechanisms of alteration are still only poorly understood. For example, the relative rates and scales of elemental mobility as well as the sources and sinks for key elements are currently not constrained. An improved knowledge of these issues will contribute to an increased understanding of aqueous alteration reactions on meteorite parent bodies. This study expands on research conducted on Type IIA chondrules and chondrule fragments from two CR2 chondrites, EET 87770 and EET 92105. These chondrites have been weakly altered; chondrule mesostases show incipient alteration primarily where they are in direct contact with fine-grained matrices.

  15. Waste treatment process for removal of contaminants from aqueous, mixed-waste solutions using sequential chemical treatment and crossflow microfiltration, followed by dewatering

    DOEpatents

    Vijayan, S.; Wong, C.F.; Buckley, L.P.

    1994-11-22

    In processes of this invention aqueous waste solutions containing a variety of mixed waste contaminants are treated to remove the contaminants by a sequential addition of chemicals and adsorption/ion exchange powdered materials to remove the contaminants including lead, cadmium, uranium, cesium-137, strontium-85/90, trichloroethylene and benzene, and impurities including iron and calcium. Staged conditioning of the waste solution produces a polydisperse system of size enlarged complexes of the contaminants in three distinct configurations: water-soluble metal complexes, insoluble metal precipitation complexes, and contaminant-bearing particles of ion exchange and adsorbent materials. The volume of the waste is reduced by separation of the polydisperse system by cross-flow microfiltration, followed by low-temperature evaporation and/or filter pressing. The water produced as filtrate is discharged if it meets a specified target water quality, or else the filtrate is recycled until the target is achieved. 1 fig.

  16. Waste treatment process for removal of contaminants from aqueous, mixed-waste solutions using sequential chemical treatment and crossflow microfiltration, followed by dewatering

    DOEpatents

    Vijayan, Sivaraman; Wong, Chi F.; Buckley, Leo P.

    1994-01-01

    In processes of this invention aqueous waste solutions containing a variety of mixed waste contaminants are treated to remove the contaminants by a sequential addition of chemicals and adsorption/ion exchange powdered materials to remove the contaminants including lead, cadmium, uranium, cesium-137, strontium-85/90, trichloroethylene and benzene, and impurities including iron and calcium. Staged conditioning of the waste solution produces a polydisperse system of size enlarged complexes of the contaminants in three distinct configurations: water-soluble metal complexes, insoluble metal precipitation complexes, and contaminant-bearing particles of ion exchange and adsorbent materials. The volume of the waste is reduced by separation of the polydisperse system by cross-flow microfiltration, followed by low-temperature evaporation and/or filter pressing. The water produced as filtrate is discharged if it meets a specified target water quality, or else the filtrate is recycled until the target is achieved.

  17. Structure sensitive chemical reactivity by palladium concave nanocubes and nanoflowers synthesised by a seed mediated procedure in aqueous medium

    NASA Astrophysics Data System (ADS)

    Sreedhala, S.; Sudheeshkumar, V.; Vinod, C. P.

    2014-06-01

    Palladium nanocubes and their transformation to concave nanocubes and nanoflowers are realised by a seed mediated procedure in aqueous medium and at room temperature using cationic surfactants. The concave nanocubes and nanoflowers were found to be enclosed by high index facets. The under co-ordinated atoms present on the high index facets make these nanostructures chemically more active towards Suzuki coupling and Heck coupling reactions compared to the conventional nanocubes and spherical nanoparticles of similar size.Palladium nanocubes and their transformation to concave nanocubes and nanoflowers are realised by a seed mediated procedure in aqueous medium and at room temperature using cationic surfactants. The concave nanocubes and nanoflowers were found to be enclosed by high index facets. The under co-ordinated atoms present on the high index facets make these nanostructures chemically more active towards Suzuki coupling and Heck coupling reactions compared to the conventional nanocubes and spherical nanoparticles of similar size. Electronic supplementary information (ESI) available: Additional HRTEM images, UV-Vis spectra and details of TOF calculation. See DOI: 10.1039/c4nr01283f

  18. Tuning the luminescence and UV photosensing properties of ZnO nanorods by strategic aqueous chemical growth

    NASA Astrophysics Data System (ADS)

    Sett, Dipanwita; Basak, Durga

    2015-10-01

    Surface-adsorbed species play an important role in the photophysical properties of one-dimensional (1D) ZnO providing a scope to comprehend the change in these properties with growth techniques as well as parameters. We have shown an unprecedented change in the photoluminescence properties of aqueous chemically grown (ACG) ZnO nanorods (NRs) by positioning the substrate at different precursor column heights by exploiting a simple phenomenon of different amounts of dissolved O2 along the depth of a precursor solution with its surface exposed to air. As anticipated, the NRs grown at the bottom of the reaction vessel show more OH-related defects and/or adsorbed O2 than those grown nearer to the liquid-air interface, resulting in better crystalline quality, ultraviolet (UV)/visible (Vis) photoluminescence intensity and UV photocurrent properties in the latter. Therefore, one can easily tune the photophysical properties of similar 1D oxide NRs simply by varying the substrate position in a columnar reaction vessel used in aqueous chemical growth.

  19. Modeling the transport of organic chemicals between polyethylene passive samplers and water in finite and infinite bath conditions.

    PubMed

    Tcaciuc, A Patricia; Apell, Jennifer N; Gschwend, Philip M

    2015-12-01

    Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments. PMID:26109238

  20. Organic chemical degradation by remote study of the redox conditions

    NASA Astrophysics Data System (ADS)

    Fernandez, P. M.; Revil, A.; Binley, A. M.; Bloem, E.; French, H. K.

    2014-12-01

    Monitoring the natural (and enhanced) degradation of organic contaminants is essential for managing groundwater quality in many parts of the world. Contaminated sites often have limited access, hence non-intrusive methods for studying redox processes, which drive the degradation of organic compounds, are required. One example is the degradation of de-icing chemicals (glycols and organic salts) released to the soil near airport runways during winter. This issue has been broadly studied at Oslo airport, Gardermoen, Norway using intrusive and non-intrusive methods. Here, we report on laboratory experiments that aim to study the potential of using a self-potential, DCresistivity, and time-domain induced polarization for geochemical characterization of the degradation of Propylene Glycol (PG). PG is completely miscible in water, does not adsorb to soil particles and does not contribute to the electrical conductivity of the soil water. When the contaminant is in the unsaturated zone near the water table, the oxygen is quickly consumed and the gas exchange with the surface is insufficient to ensure aerobic degradation, which is faster than anaerobic degradation. Since biodegradation of PG is highly oxygen demanding, anaerobic pockets can exist causing iron and manganese reduction. It is hypothesised that nitrate would boost the degradation rate under such conditions. In our experiment, we study PG degradation in a sand tank. We provide the system with an electron highway to bridge zones with different redox potential. This geo-battery system is characterized by self-potential, resistivity and induced polarization anomalies. An example of preliminary results with self-potential at two different times of the experiment can be seen in the illustration. These will be supplemented with more direct information on the redox chemistry: in-situ water sampling, pH, redox potential and electrical conductivity measurements. In parallel, a series of batch experiments have been performed to study anoxic microbial degradation using gas and resistivity measurements.

  1. Effect of chemical exchange on radiation damping in aqueous solutions of the osmolyte glycine.

    PubMed

    Rodríguez, Juan Carlos; Jennings, Patricia A; Melacini, Giuseppe

    2002-06-01

    Radiation damping is of central relevance in NMR spectroscopy especially with the advent of ultrahigh-field magnets and of supersensitive probes. Furthermore, the recent realization that the combined effect of the distant dipole field and of radiation damping causes the resurrection of undesired crushed water magnetization emphasizes the need for a thorough understanding of all the factors affecting radiation damping. While the effects of pulsed-field gradients and of active feedback have been extensively investigated, the consequences on radiation damping of chemical exchange between water and co-solutes is not as well understood. Here it is demonstrated that the rate of water radiation damping is significantly affected by free glycine (Gly), a representative of an important class of biocompatible osmolytes often used at molar concentrations as protein stabilizers. The pH and temperature dependencies of this effect were investigated and rationalized in terms of radiation damping attenuation caused by incoherent dephasing occurring in the intermediate exchange regime. For instance, at pH 6.0 and at a temperature of 313 K the Gly NH3+/water exchange has the same dramatic effect on radiation damping as a series of repeated weak PFGs, increasing the water inversion-recovery zero-crossing delay from approximately 30 ms to approximately 2.3 s. In addition, under these conditions, the Gly NH3+/water exchange suppresses the resurrection of unwanted crushed water magnetization. When used in combination with PFGs and water flip-back schemes, glycine is therefore expected to tame chaotic dynamics and improve the reproducibility of the NMR experiments affected by it. PMID:12033843

  2. Reactions of the Re(CO)3(H2O)3(+) synthon with monodentate ligands under aqueous conditions.

    PubMed

    Franklin, Brenton R; Herrick, Richard S; Ziegler, Christopher J; Cetin, Anil; Barone, Natalie; Condon, Laura R

    2008-07-01

    The reactions of ammonia, pyridine (py), N-methyl imidazole (N-MeIm), tetrahydrothiophene (tht), and piperidine (pip) with Re(CO) 3(H 2O) 3 (+), 1 ( + ), were investigated employing aqueous conditions under atmospheric dioxygen. The reaction of [ 1]Br in aqueous ammonia led to [Re(CO) 3(NH 3) 3]Br ([ 2]Br) as the only product isolated. For the aqueous reactions of [ 1]Br with py, N-MeIm, and tht, mixtures of products are formed because of competition between the bromide and added ligand, even when the ligand is present in excess. Substitution of the PF 6 (-) anion for Br (-) leads to the clean formation of [Re(CO) 3L 3][PF 6] ([ 3][PF 6]-[ 5][PF 6]) for py, N-MeIm, and tht, respectively, as the only products observed. Reaction of [ 1][PF 6] with pip produces the dimeric species, (pip)(CO) 3Re(micro-OH) 2Re(CO) 3(pip), 6. Reactions of [ 1]Br were also performed in methanol for comparison purposes. The reaction with pip in this solvent led to the analogous dimer, (pip)(CO) 3Re(micro-OMe) 2Re(CO) 3(pip), 7; however, reactions with py, N-MeIm, and tht gave Re(CO) 3L 2Br, 8- 10, respectively, as the only products. The crystal structures of compounds [ 2]Br- 10 are reported. PMID:18510286

  3. The effect of precipitation conditions and aging upon characteristics of particles precipitated from aqueous solutions

    SciTech Connect

    Rard, J.A.

    1989-10-01

    Precipitation of a dissolved species from aqueous solutions is one of the techniques used to grow particles with certain size or composition characteristics. Various factors affecting the particle properties for sparingly soluble substances are briefly discussed here, including homogeneous versus heterogeneous nucleation, the effect of relative supersaturation on the number of nuclei and their relative size, particle growth by way of Ostwald Ripening, the Ostwald Step Rule and nucleation of metastable phases, diffusion-controlled versus surface reaction-controlled growth, incorporation of dopants into the precipitate, and dendritic growth. 13 refs.

  4. A purge and trap integrated microGC platform for chemical identification in aqueous samples.

    PubMed

    Akbar, Muhammad; Narayanan, Shree; Restaino, Michael; Agah, Masoud

    2014-07-01

    The majority of current micro-scale gas chromatography (μGC) systems focus on air sampling to detect volatile organic compounds (VOCs). However, purging the VOCs from a water sample using microsystems is an unchartered territory. Various organic compounds used in everyday life find their way to water bodies. Some of these water organic compounds (WOCs) persist or degrade slowly, threatening not just human existence but also aquatic life. This article reports the first micro-purge extractor (μPE) chip and its integration with a micro-scale gas chromatography (μGC) system for the extraction and analysis of water organic compounds (WOCs) from aqueous samples. The 2 cm × 3 cm μPE chip contains two inlet and outlet ports and an etched cavity sealed with a Pyrex cover. The aqueous sample is introduced from the top inlet port while a pure inert gas is supplied from the side inlet to purge WOCs from the μPE chip. The outlets are assigned for draining water from the chip and for directing purged WOCs to the micro-thermal preconcentrator (μTPC). The trapped compounds are desorbed from the μTPC by resistive heating using the on-chip heater and temperature sensor, are separated by a 2 m long, 80 μm wide, and 250 μm deep polydimethylsiloxane (OV-1) coated μGC separation column, and are identified using a micro-thermal conductivity detector (μTCD) monolithically integrated with the column. Our experiments indicate that the combined system is capable of providing rapid chromatographic separation (<1.5 min) for quaternary WOCs namely toluene, tetrachloroethylene (PCE), chlorobenzene and ethylbenzene with a minimum detection concentration of 500 parts-per-billion (ppb) in aqueous samples. The proposed method is a promising development towards the future realization of a miniaturized system for sensitive, on-site and real-time field analysis of organic contaminants in water. PMID:24837988

  5. Chemical Speciation of Inorganic Compounds under Hydrothermal Conditions

    SciTech Connect

    Edward A Stern; John Fulton

    2002-02-21

    Measurements of oxidation. These spectra are to the best of our knowledge the first reported in situ spectroscopic observation of homogeneous aqueous redox chemistry at temperatures beyond the critical temperature of waste. We also observed a time-dependence for the growth of the Cr(VI) XANES peak and have therefore obtained both kinetic information as well as structural information on the reactants and products at the reaction temperature. We feel that these new techniques, when employed on actual waste components will elucidate the underlying chemistry.

  6. CHEMICAL AND BIOLOGICAL TREATMENT OF THERMALLY CONDITIONED SLUDGE RECYCLE LIQUORS

    EPA Science Inventory

    The objective of this research project was to demonstrate and evaluate the feasibility of treating undiluted heat treatment liquor prior to its rerouting back to the head of the sewage treatment plant. Chemical and biological treatment processes were studied. Chemical treatment w...

  7. Multispecies reactive tracer test in an aquifer with spatially variable chemical conditions

    USGS Publications Warehouse

    Davis, J.A.; Kent, D.B.; Coston, J.A.; Hess, K.M.; Joye, J.L.

    2000-01-01

    A field investigation of multispecies reactive transport was conducted in a well-characterized, sand and gravel aquifer on Cape Cod, Massachusetts. The aquifer is characterized by regions of differing chemical conditions caused by the disposal of secondary sewage effluent. Ten thousand liters of groundwater with added tracers (Br, Cr(VI), and BDTA complexed with Pb, Zn, Cu, and Ni) were injected into the aquifer and distributions of the tracers were monitored for 15 months. Most of the tracers were transported more than 200 m; transport was quantified using spatial moments computed from the results of a series of synoptic samplings. Cr(VI) transport was retarded relative to Br; the retardation factor varied from 1.1 to 2.4 and was dependent on chemical conditions. At 314 days after the injection, dissolved Cr(VI) mass in the tracer cloud had decreased 85%, with the likely cause being reduction to Cr(III) in a suboxic region of the aquifer. Transport of the metal-EDTA complexes was affected by aqueous complexation, adsorption, and dissolution-precipitation reactions of Fe oxyhydroxide minerals in the aquifer sediments. Dissolved Pb-EDTA complexes disappeared from the tracer cloud within 85 days, probably due to metal exchange reactions with Fe and adsorbed Zn (present prior to the injection from contamination by the sewage effluent). About 30% of the Cu-EDTA complexes remained within the tracer cloud 314 days after injection, even though the thermodynamic stability of the Pb-EDTA complex is greater than Cu-EDTA. It is hypothesized that stronger adsorption of Pb2+ to the aquifer sediments causes the Pb-EDTA complex to disassociate to a greater degree than the Cu-EDTA complex. The mass of dissolved Zn-EDTA increased during the first 175 days of the tracer test to 140% of the mass injected, with the increase due to desorption of sewage-derived Zn. Dissolved Ni-EDTA mass remained nearly constant throughout the tracer test, apparently only participating in reversible adsorption reactions. The results of the field experiment provide a chemically complex data set that can be used in the testing of reactive transport models of flow coupled with chemical reactions.

  8. Methane aqueous fluids in montmorillonite clay interlayer under near-surface geological conditions: a grand canonical Monte Carlo and molecular dynamics simulation study.

    PubMed

    Rao, Qi; Leng, Yongsheng

    2014-09-18

    The grand-canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations are performed to investigate the methane aqueous fluids in Na-montmorillonite clay interlayer under near-surface geological temperature and pressure conditions (T = 300 K and P = 20-50 bar). The chemical potentials of water and methane under these T/P conditions are calculated using the Widom's insertion method. These chemical potentials are used in the GCMC simulations to determine the contents of different species in the clay interlayer, especially in those that correspond to the equilibrium stable spacing distances. Simulation results show that initial clay swelling is dominated by water adsorption into the clay interlayer, followed by the intercalation of methane as the basal spacing increases. However, it is found that this methane intercalation process is strongly influenced by the relative humidity and the total gas pressure of the system. High relative humidity may facilitate water molecules entering the clay interlayer region and inhibit the intercalation of methane molecules. MD simulations show that sodium ions are fully hydrated by water molecules and clay surface oxygen atoms, while methane molecules are not fully coordinated. This situation is attributed to the less water content in clay interlayer and the subsequent formation of methane dimer or trimer clusters due to the hydrophobic nature of small hydrocarbon molecules. PMID:25167085

  9. Atomistic Mechanisms of Chemical Mechanical Polishing of a Cu Surface in Aqueous H2O2: Tight-Binding Quantum Chemical Molecular Dynamics Simulations.

    PubMed

    Kawaguchi, Kentaro; Ito, Hiroshi; Kuwahara, Takuya; Higuchi, Yuji; Ozawa, Nobuki; Kubo, Momoji

    2016-05-11

    We applied our original chemical mechanical polishing (CMP) simulator based on the tight-binding quantum chemical molecular dynamics (TB-QCMD) method to clarify the atomistic mechanism of CMP processes on a Cu(111) surface polished with a SiO2 abrasive grain in aqueous H2O2. We reveal that the oxidation of the Cu(111) surface mechanically induced at the friction interface is a key process in CMP. In aqueous H2O2, in the first step, OH groups and O atoms adsorbed on a nascent Cu surface are generated by the chemical reactions of H2O2 molecules. In the second step, at the friction interface between the Cu surface and the abrasive grain, the surface-adsorbed O atom intrudes into the Cu bulk and dissociates the Cu-Cu bonds. The dissociation of the Cu-Cu back-bonds raises a Cu atom from the surface that is mechanically sheared by the abrasive grain. In the third step, the raised Cu atom bound to the surface-adsorbed OH groups is removed from the surface by the generation and desorption of a Cu(OH)2 molecule. In contrast, in pure water, there are no geometrical changes in the Cu surface because the H2O molecules do not react with the Cu surface, and the abrasive grain slides smoothly on the planar Cu surface. The comparison between the CMP simulations in aqueous H2O2 and pure water indicates that the intrusion of a surface-adsorbed O atom into the Cu bulk is the most important process for the efficient polishing of the Cu surface because it induces the dissociation of the Cu-Cu bonds and generates raised Cu atoms that are sheared off by the abrasive grain. Furthermore, density functional theory calculations show that the intrusion of the surface-adsorbed O atoms into the Cu bulk has a high activation energy of 28.2 kcal/mol, which is difficult to overcome at 300 K. Thus, we suggest that the intrusion of surface-adsorbed O atoms into the Cu bulk induced by abrasive grains at the friction interface is a rate-determining step in the Cu CMP process. PMID:27092706

  10. Composition and freezing of aqueous H2SO4/HNO3 solutions under polar stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Beyer, K. D.; Seago, S. W.; Chang, H. Y.; Molina, M. J.

    1994-01-01

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O 'dew point' is typically around 192-194 K at 100 mbar.

  11. Physical and chemical effects of direct aqueous advanced oxidation processing on green sand foundry mold materials

    NASA Astrophysics Data System (ADS)

    Clobes, Jason Kenneth

    Iron foundries using the common green sand molding process have increasingly been incorporating aqueous advanced oxidation (AO) systems to reduce the consumption of sand system bentonite clay and coal raw materials by and to decrease their volatile organic compound (VOC) emissions. These AO systems typically use a combination of sonication, ozone aeration, and hydrogen peroxide to treat and recycle slurries of sand system baghouse dust, which is rich in clay and coal. While the overall effects of AO on raw material consumption and organic emissions are known, the mechanisms behind these effects are not well understood. This research examined the effects of bench-scale direct aqueous AO processing on green sand mold materials at the micro level. Bench-scale AO processing, including acoustic sonication, ozone/oxygen aeration, and hydrogen peroxide dramatically decreased the particle sizes of both western bentonite and foundry sand system baghouse dust. Bench-scale AO processing was shown to effectively separate the clay material from the larger silica and coal particles and to extensively break up the larger clay agglomerates. The acoustic sonication component of AO processing was the key contributor to enhanced clay recovery. Acoustic sonication alone was slightly more effective than combined component AO in reducing the particle sizes of the baghouse dust and in the recovery of clay yields in the supernatant during sedimentation experiments. Sedimentation separation results correlated well with the increase in small particle concentrations due to AO processing. Clay suspension viscosity decreased with AO processing due to enhanced dispersion of the particles. X-ray diffraction of freeze-dried baghouse dust indicated that AO processing does not rehydrate calcined montmorillonite and does not increase the level of interlayer water hydration in the dry clays. Zeta potential measurements indicated that AO processing also does not produce any large changes in the surface charge of the small clay particles upon AO treatment.

  12. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    USGS Publications Warehouse

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  13. Chemical Analysis and Aqueous Solution Properties of Charged Amphiphilic Block Copolymers PBA-b-PAA Synthesized by MADIX

    SciTech Connect

    Jacquin,M.; Muller, P.; Talingting-Pabalan, R.; Cottet, H.; Berret, J.; Futterer, T.; Theodoly, O.

    2007-01-01

    We have linked the structural and dynamic properties in aqueous solution of amphiphilic charged diblock copolymers poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA, synthesized by controlled radical polymerization, with the physico-chemical characteristics of the samples. Despite product imperfections, the samples self-assemble in melt and aqueous solutions as predicted by monodisperse microphase separation theory. However, the PBA core are abnormally large; the swelling of PBA cores is not due to AA (the Flory parameter ?PBA/PAA, determined at 0.25, means strong segregation), but to h-PBA homopolymers (content determined by liquid chromatography at the point of exclusion and adsorption transition, LC-PEAT). Beside the dominant population of micelles detected by scattering experiments, capillary electrophoresis CE analysis permitted detection of two other populations, one of h-PAA, and the other of free PBA-b-PAA chains, that have very short PBA blocks and never self-assemble. Despite the presence of these free unimers, the self-assembly in solution was found out of equilibrium: the aggregation state is history dependant and no unimer exchange between micelles occurs over months (time-evolution SANS). The high PBA/water interfacial tension, measured at 20 mN/m, prohibits unimer exchange between micelles. PBA-b-PAA solution systems are neither at thermal equilibrium nor completely frozen systems: internal fractionation of individual aggregates can occur.

  14. Diffusion behavior of lysozyme in aqueous ammonium sulfate solutions under varying solution conditions as determined by dynamic light scattering

    SciTech Connect

    Fornefeld, U.M.; Kuehner, D.E.; Blanch, H.W.; Prausnitz, J.M. . Dept. of Chemical Engineering Lawrence Berkeley Lab., CA . Chemical Sciences Div.)

    1994-12-01

    As proteins gain significance in commercial applications such as pharmaceuticals, detergents, organic waste management and cosmetics, efficient and economical recovery of these valuable biomolecules is of increasing importance. the salting-out process has found widespread application in the area of protein separations. To date, salt-induced precipitation of proteins from complex aqueous solutions remains largely an empirical process; no comprehensive model exists to predict salting-out phase equilibria in protein solutions. Rational predictive models for salt-induced precipitation will therefore be of great value in protein purification, both on the preparative and the analytical scale. Any attempt to model theoretically salt-induced protein precipitation must include the known physics of protein interactions in aqueous solution. With this in mind, it is crucial to acknowledge that protein precipitation is fundamentally an aggregation process. In order to incorporate aggregation effects into ongoing efforts to model salting out of proteins, it is necessary to quantify the degree of aggregation as a function of solution conditions. Therefore, dynamic light scattering measurements were performed with a well-studied protein, hen-egg-white lysozyme, under several solution conditions.

  15. Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation - Part 2: Development of the chemical mechanism and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Ervens, B.; Renard, P.; Tlili, S.; Ravier, S.; Clément, J.-L.; Monod, A.

    2015-08-01

    Laboratory experiments of efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase were simulated in a box model. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. Upon model sensitivity studies, in which unconstrained rate constants were varied over several orders of magnitude, a set of reaction parameters was found that could reproduce laboratory data over a wide range of experimental conditions. This mechanism is the first that comprehensively describes such radical-initiated oligomer formation. This mechanism was implemented into a multiphase box model that simulates secondary organic aerosol (SOA) formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. While in laboratory experiments oxygen limitation might occur and lead to accelerated oligomer formation, such conditions are likely not met in the atmosphere. The comparison of predicted oligomer formation shows that MVK and MACR likely do negligibly contribute to total SOA as their solubilities are low and even reduced in aerosol water due to ionic strength effects (Setchenov coefficients). Significant contribution by oligomers to total SOA might only occur if a substantial fraction of particulate carbon acts as oligomer precursors and/or if oxygen solubility in aerosol water is strongly reduced due to salting-out effects.

  16. Nanofiltration and sensing of picomolar chemical residues in aqueous solution using an optical porous resonator in a microelectrofluidic channel

    NASA Astrophysics Data System (ADS)

    Huang, Lei; Guo, Zhixiong

    2012-02-01

    For the first time the use of a porous microresonator placed in a microelectrofluidic system for integrated functions of nanofiltration and sensing of small biomolecules and chemical analytes in extremely dilute solution was proposed and investigated. As an example, aminoglycosides in drug residues in food and livestock products were considered as the trace chemical analyte. The filtration process of the charged analyte in aqueous solution driven by an applied electrical field and the accompanying optical whispering-gallery modes in the resonator are modeled. The dynamic process of adsorption and desorption of the analyte onto the porous matrix is studied. Deposition of the analyte inside the porous structure will alter the material refractive index of the resonator, and thus induce an optical resonance frequency shift. By measuring the optical frequency shift, the analyte concentration as well as the absorption/desorption process can be analyzed. Through an intensive numerical study, a correlation between the frequency shift and the analyte concentration and the applied electrical voltage gradient was obtained. This reveals a linear relationship between the resonance frequency shift and the analyte concentration. The applied electrical voltage substantially enhances the filtration capability and the magnitude of the optical frequency shift, pushing the porous resonator-based sensor to function at the extremely dilute picomolar concentration level for small bio/chemical molecules down to the sub-nanometer scale. Moreover, use of the second-order whispering-gallery mode is found to provide better sensitivity compared with the first-order mode.

  17. Chemical and structural evaluation of activated carbon prepared from jute sticks for Brilliant Green dye removal from aqueous solution.

    PubMed

    Asadullah, Mohammad; Asaduzzaman, Mohammad; Kabir, Mohammad Shajahan; Mostofa, Mohammad Golam; Miyazawa, Tomohisa

    2010-02-15

    Activated carbons have been prepared from jute sticks by chemical activation using ZnCl(2) and physical activation using steam for the removal of Brilliant Green dye from aqueous solution. The activated carbons and charcoal prepared from jute sticks were characterized by evaluating the surface chemistry, structural features and surface morphology. The maximum BET surface area was obtained to be 2304 m(2)/g for chemical activated carbon (ACC) while it is 730 and 80 m(2)/g for steam activated carbon (ACS) and charcoal, respectively. The FT-IR spectra exhibited that the pyrolysis and steam activation of jute sticks resulted in the release of aliphatic and O-containing functional groups by thermal effect. However, the release of functional groups is the effect of chemical reaction in the ZnCl(2) activation process. A honeycomb-type carbon structure in ACC was formed as observed on SEM images. Although charcoal and ACC were prepared at 500 degrees C the ACC exhibited much lower Raman sensitivity due to the formation of condensed aromatic ring systems. Due to high surface area and high porous structure with abundance of functional groups, the ACC adsorbed dye molecules with much higher efficiency than those of ACS and charcoal. PMID:19815339

  18. Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

    PubMed

    Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

    2015-01-01

    Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C. PMID:25517211

  19. CH 4/NH 3/H 2O spark tholin: Chemical analysis and interaction with Jovian aqueous clouds

    NASA Astrophysics Data System (ADS)

    McDonald, Gene D.; Khare, Bishun N.; Reid Thompson, W.; Sagan, Carl

    1991-12-01

    The organic solid (tholin) produced by spark discharge in a CH 4 + NH 3 + H 2O atmosphere is investigated, along with the separable components of its water-soluble fraction. The chemistry of this material serves as a provisional model for the interaction of Jovian organic heteropolymers with the deep aqueous clouds of Jupiter. Intact (unhydrolyzed) tholin is resolved into four chemically distinct fractions by high-pressure liquid chromatography (HPLC). Gel filtration chromatography reveals abundant components at molecular weights ⋍600-700 and 200-300 Da. Gas chromatography/mass spectrometry of derivatized hydrolysis products of unfractionated tholin shows about 10% by mass protein and nonprotein amino acids, chiefly glycine, alanine, aspartic acid, β-alanine, and β-aminobutyric acid, and 12% by mass other organic acids and hydroxy acids. The stereospecificity of alanine is investigated and shown to be racemic. The four principal HPLC fractions yield distinctly different proportions of amino acids. Chemical tests show that small peptides or organic molecules containing multiple amino acid precursors are a possibility in the intact tholins, but substantial quantities of large peptides are not indicated. Candidate 700-Da molecules have a central unsaturated, hydrocarbon- and nitrile-rich core, linked by acid-labile (ester or amide) bonds to amino acid and carboxylic acid side groups. The core is probably not HCN "polymer." The concentration of amino acids from tholin hydrolysis in the lower aqueous clouds of Jupiter, about 0.1 μ M, is enough to maintain small populations of terrestrial microorganisms even if the amino acids must serve as the sole carbon source.

  20. Chemical Enrichment and Physical Conditions in IZw18*

    NASA Technical Reports Server (NTRS)

    Lebouteiller, V.; Heap, S.; Hubeny, I.; Kunth, D.

    2013-01-01

    Low-metallicity star-forming dwarf galaxies are prime targets to understand the chemical enrichment of the interstellar medium. The H I region contains the bulk of the mass in blue compact dwarfs, and it provides important constraints on the dispersal and mixing of heavy elements released by successive star-formation episodes. The metallicity of the H I region is also a critical parameter to investigate the future star-formation history, as metals provide most of the gas cooling that will facilitate and sustain star formation. Aims. Our primary objective is to study the enrichment of the H I region and the interplay between star-formation history and metallicity evolution. Our secondary obje ctive is to constrain the spatial- and time-scales over which the HI and H II regions are enriched, and the mass range of stars responsible for the heavy element production. Finally, we aim to examine the gas heating and cooling mechanisms in the H I region. Methods. We observed the most metal-poor star-forming galaxy in the Local Universe, I Zw 18, with the Cosmic Origin Spectrograph onboard Hubble. The abundances in the neutral gas are derived from far-ultraviolet absorption-lines (H I, CIII, CIIi*, N I, OI,...) and are compared to the abundances in the H II region. Models are constructed to calculate the ionization structure and the thermal processes. We investigate the gas cooling in the HIi region through physical diagnostics drawn from the fine-structure level of C+. Results. We find that H I region abundances are lower by a factor of approx 2 as compared to the H II region. There is no differential depletion on dust between the H I and H II region. Using sulfur as a metallicity tracer, we calculate a metallicity of 1/46 Z(solar) (vs. 1/31 Z(solar) in the H II region). From the study of the C/O, [O/Fe], and N/O abundance ratios, we propose that C, N, O, and Fe are mainly produced in massive stars. We argue that the H I envelope may contain pockets of pristine gas with a metallicity essentially null. Finally, we derive the physical conditions in the H I region by investigating the C II* absorption line. The cooling rate derived from C II* is consistent with collisions with H(sup 0) atoms in the diffuse neutral gas. We calculate the star-formation rate from the CII* cooling rate assuming that photoelectric effect on dust is the dominant gas heating mechanism. Our determination is in good agreement with the values in the literature if we assume a low dust-to-gas ratio (approx 2000 times lower than the Milky Way value).

  1. Chemical enrichment and physical conditions in I Zw 18

    NASA Astrophysics Data System (ADS)

    Lebouteiller, V.; Heap, S.; Hubeny, I.; Kunth, D.

    2013-05-01

    Context. Low-metallicity star-forming dwarf galaxies are prime targets to understand the chemical enrichment of the interstellar medium. The H i region contains the bulk of the mass in blue compact dwarfs, and it provides important constraints on the dispersal and mixing of heavy elements released by successive star-formation episodes. The metallicity of the H i region is also a critical parameter to investigate the future star-formation history, as metals provide most of the gas cooling that will facilitate and sustain star formation. Aims: Our primary objective is to study the enrichment of the H i region and the interplay between star-formation history and metallicity evolution. Our secondary objective is to constrain the spatial- and time-scales over which the H i and H ii regions are enriched, and the mass range of stars responsible for the heavy element production. Finally, we aim to examine the gas heating and cooling mechanisms in the H i region. Methods: We observed the most metal-poor star-forming galaxy in the Local Universe, I Zw 18, with the Cosmic Origin Spectrograph onboard Hubble. The abundances in the neutral gas are derived from far-ultraviolet absorption-lines (H i, C ii, C ii*, N i, O i, ...) and are compared to the abundances in the H ii region. Models are constructed to calculate the ionization structure and the thermal processes. We investigate the gas cooling in the H i region through physical diagnostics drawn from the fine-structure level of C+. Results: We find that H i region abundances are lower by a factor of ~2 as compared to the H ii region. There is no differential depletion on dust between the H i and H ii region. Using sulfur as a metallicity tracer, we calculate a metallicity of 1/46 Z⊙ (vs. 1/31 Z⊙ in the H ii region). From the study of the C/O, [O/Fe], and N/O abundance ratios, we propose that C, N, O, and Fe are mainly produced in massive stars. We argue that the H i envelope may contain pockets of pristine gas with a metallicity essentially null. Finally, we derive the physical conditions in the H i region by investigating the C ii* absorption line. The cooling rate derived from C ii* is consistent with collisions with H0 atoms in the diffuse neutral gas. We calculate the star-formation rate from the C ii* cooling rate assuming that photoelectric effect on dust is the dominant gas heating mechanism. Our determination is in good agreement with the values in the literature if we assume a low dust-to-gas ratio (~2000 times lower than the Milky Way value). Appendix A is available in electronic form at http://www.aanda.org

  2. Chemical Composition of Meridiani Sediments: Traces of Aqueous Past on Martian Surface

    NASA Astrophysics Data System (ADS)

    Brueckner, J.; Gellert, R.; D'Uston, C.; Treguier, E.; Squyres, S. W.

    2007-12-01

    Measurements of outcrop samples by the Alpha Particle X-Ray Spectrometer (APXS), onboard the NASA Mars Exploration Rover Opportunity at Meridiani, showed strong sulfur peaks in the x-ray spectra. Sulfur concentrations increased from natural (as is) rock surfaces over brushed to abraded rocks that turned out to be sulfur-loaded sediments. Along the 11-kilometer traverse of the rover many abraded surfaces could be measured by the APXS because the softness of the outcrops permitted grinding by the Rock Abrasion Tool (RAT) until today. All outcrop samples exhibited high sulfur concentrations of more than 6 weight percent; some samples exceeded 10 wt-% making S a major element and indicating a special history of these sediments. Element concentrations of all abraded rocks along the traverse were studied as function of sulfur content. A linear relationship with a negative slope was found for the silicon-sulfur pair. A similar relation holds for Al, Na, K, P, Ti, and Cr versus S. Iron shows a weak correlation with S (only a slight negative slope). Constant concentrations are exhibited by Mn and Ni. Calcium, Mg, and Zn, reveal a slight increase with increasing S contents (positive slope). During the first half of the traverse Mg and S are strongly correlated, later almost none. The formation of the sediments can be described by a two-component mixing model, where sulfur is mainly present in one component. The composition of the other component, the siliciclastic material, was extrapolated from above sample compositions to low S contents. The derived siliciclastic composition differs from encountered basaltic material, such as 'Bounce Rock' at Meridiani or the Adirondack Class rocks at Gusev crater, but, is similar to rocks discovered near Home Plate (Gusev). Best compositional matches are found for 'Masada Clod', 'Raquelme3', and others, which are significantly altered from an original basaltic composition. Apparently this composition type is wider spread on the Martian surface. The other mixing component contains various sulfates. Assuming large volcanic exhalations of sulfur, any original aqueous solution became very acidic. 'Normal' rocks were rapidly leached and gradually dissolved to form new compounds and large quantities of sulfates in an aqueous system. To bring the two components together, either wind and/or water did the transport. The small scatter of the concentration data points (mostly around a straight line) suggests that there was a concentration gradient in bodies of standing water on a kilometer-wide scale at least for a short period of time. The concentrations of many elements (Si, Al, Na, K, P, Ti, and Cr) are diluted by increasing sulfur contents. Hence, these elements were mainly part of the siliciclastic component. On the other hand, elements whose concentrations increase with increasing S (e.g. Ca, Mg, and Zn) were part of sulfates and of mafic minerals (in the siliciclastic component). Iron showing some dilution by sulfur was determined by Mössbauer spectroscopy to be present also as ferric sulfate. The above observations reveal that several elements formed sulfates in these sediments: Mg, Ca, Fe, and Zn. An aqueous system existed during the period of sediment formation and left unique traces in the sedimentary composition.

  3. 'GREENER' CHEMICAL SYNTHESES USING MICROWAVES UNDER SOLVENT-FREE CONDITIONS OR AQUEOUS MEDIA

    EPA Science Inventory

    A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...

  4. "GREENER" CHEMICAL SYNTHESES USING AN ALTERNATE REACTION CONDITIONS OR AQUEOUS MEDIA

    EPA Science Inventory

    A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...

  5. Abiotic Formation of Hydrocarbons Under Hydrothermal Conditions: Constraints from Chemical and Isotope Data

    SciTech Connect

    Fu, Q.; Lollar, Barbara Sherwood; Horita, Juske; Lacrampe-Couloume, Georges; Seyfried, W. E.

    2007-01-01

    To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO{sub 2} and H{sub 2}-bearing aqueous fluids were conducted at 400 C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C{sub 1}-C{sub 3} hydrocarbons and relatively large changes in dissolved CO{sub 2} and H{sub 2} concentrations, consistent with formation of additional hydrocarbon components beyond C{sub 3}. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an 'isotopic reversal' trend was not observed for {sup 13}C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant {sup 13}C depletion in CH{sub 4} suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C{sub 1}-C{sub 3} hydrocarbons and carbon species absorbed on mineral surfaces and in solution.

  6. EFFICIENT CHEMICAL TRANSFORMATIONS USING ALTERNATIVE REACTION CONDITIONS AND MEDIA

    EPA Science Inventory

    The diverse nature of chemical entities requires various green' strategic pathways in our quest towards attaining sustainability. A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable...

  7. Public Health Risk Conditioned by Chemical Composition of Ground Water

    NASA Astrophysics Data System (ADS)

    Yankovich, E.; Osipova, N.; Yankovich, K.; Matveenko, I.

    2016-03-01

    The article studies the public health potential risk originated from water consumption and estimated on the basis of the groundwater chemical composition. We have processed the results of chemical groundwater analysis in different aquifers of Tomsk district (Tomsk Oblast, Russia). More than 8400 samples of chemical groundwater analyses were taken during long-term observation period. Human health risk assessment of exposure to contaminants in drinking water was performed in accordance with the risk assessment guidance for public health concerning chemical pollution of the environment (Russian reference number: 2.1.10.1920-04-M, 2004). Identified potential risks were estimated for consuming water of each aquifer. The comparative analysis of water quality of different aquifers was performed on the basis of the risk coefficient of the total non-carcinogenic effects. The non-carcinogenic risk for the health of the Tomsk district population due to groundwater consumption without prior sanitary treatment was admitted acceptable. A rather similar picture is observed for all aquifers, although deeper aquifers show lower hazard coefficients.

  8. CHEMICAL SPECIATION OF INORGANIC COMPOUNDS UNDER HYDROTHERMAL CONDITIONS

    EPA Science Inventory

    This research will utilize the high-intensity x-rays available at the Advance Photon Source (APS) to study the inorganic chemistry occurring during the hydrothermal oxidation of tank waste and the chemistry associated with tank waste vitrification. Although the chemical conversio...

  9. Oxidative weathering chemical migration under variably saturated conditions and supergene copper enrichment

    SciTech Connect

    Xu, Tianfu; Pruess, K.; Brimhall, G.

    1999-04-01

    Transport of oxygen gas from the land surface through an unsaturated zone has a strong influence on oxidative weathering processes. Oxidation of sulfide minerals such as pyrite (FeS{sub 2}), one of the most common naturally occurring minerals, is the primary source of acid drainage from mines and waste rock piles. Here we present a detailed numerical model of supergene copper enrichment that involves the oxidative weathering of pyrite (FeS{sub 2}) and chalcopyrite (CuFeS{sub 2}), and acidification that causes mobilization of metals in the unsaturated zone, with subsequent formation of enriched ore deposits of chalcocite (CuS) and covellite (Cu{sub 2}S) in the reducing conditions below the water table. We examine and identify some significant conceptual and computational issues regarding the oxidative weathering processes through the modeling tool. The dissolution of gaseous oxygen induced by the oxidation reduces oxygen partial pressure, as well as the total pressure of the gas phase. As a result, the gas flow is modified, then the liquid phase flow. Results indicate that this reaction effect on the fluid flow may not be important under ambient conditions, and gas diffusion can be a more important mechanism for oxygen supply than gas or liquid advection. Acidification, mobilization of metals, and alteration of primary minerals mostly take place in unsaturated zone (oxidizing), while precipitation of secondary minerals mainly occurs in saturated zone (reducing). The water table may be considered as an interface between oxidizing and reducing zones. Moving water table due to change of infiltration results in moving oxidizing zone and redistributing aqueous chemical constitutes and secondary mineral deposits. The oxidative weathering processes are difficult to model numerically, because concentrations of redox sensitive chemical species such as O{sub 2}(aq), SO{sub 4}{sup 2-} and HS{sup -} may change over tens of orders of magnitude between oxidizing and reducing conditions. In order to simulate substantial reaction progress over geologic time, one can benefit from the quasi-stationary state (QSS) approximation. A significant saving of computing time using QSS is demonstrated through the example. In addition, changes in porosity and permeability due to mineral dissolution and precipitation are also addressed in some degree. Even though oxidative weathering is sensitive to many factors, this work demonstrates that our model provides a comprehensive suite of process modeling capabilities, which could serve as a prototype for oxidative weathering processes with broad significance for geoscientific, engineering, and environmental applications.

  10. Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions.

    PubMed

    Rowland, Glenn A; Bausch, Alexandra R; Grannas, Amanda M

    2011-05-01

    Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500?M hydrogen peroxide solution or locally-collected melted snow were measured inafield campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500?M hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration. PMID:21396757

  11. Molecular Dynamics Simulation of the Aggregation Patterns in Aqueous Solutions of Bile Salts at Physiological Conditions.

    PubMed

    Mustan, Fatmegyul; Ivanova, Anela; Madjarova, Galia; Tcholakova, Slavka; Denkov, Nikolai

    2015-12-24

    Classical molecular dynamics simulations are employed to monitor the aggregation behavior of six bile salts (nonconjugated and glycine- and taurine-conjugated sodium cholate and sodium deoxycholate) with concentration of 10 mM in aqueous solution in the presence of 120 mM NaCl. There are 150 ns trajectories generated to characterize the systems. The largest stable aggregates are analyzed to determine their shape, size, and stabilizing forces. It is found that the aggregation is a hierarchical process and that its kinetics depends both on the number of hydroxyl groups in the steroid part of the molecules and on the type of conjugation. The micelles of all salts are similar in shape-deformed spheres or ellipsoids, which are stabilized by hydrophobic forces, acting between the steroid rings. The differences in the aggregation kinetics of the various conjugates are rationalized by the affinity for hydrogen bond formation for the glycine-modified salts or by the longer time needed to achieve optimum packing for the tauro derivatives. Evidence is provided for the hypothesis from the literature that the entirely hydrophobic core of all aggregates and the enhanced dynamics of the molecules therein should be among the prerequisites for their pronounced solubilization capacity for hydrophobic substances in vivo. PMID:26605858

  12. Solvation of Ti(IV) in aqueous solution under ambient and supercritical conditions.

    PubMed

    van Sijl, Jelle; Allan, Neil L; Davies, Gareth R; van Westrenen, Wim

    2011-04-28

    We examine the structure of the hydrated Ti(IV) complex under both ambient and supercritical conditions using first-principles molecular dynamics. We find that an unanticipated fivefold coordination of Ti(IV) is favoured under ambient conditions, with rapid interconversions between square pyramidal and trigonal bipyramidal structures. At supercritical conditions the Ti coordination increases from five to six, adopting both octahedral and trigonal prismatic geometries. At 1000 K, the magnitude of the increase in the Ti to oxygen coordination number with increasing water density is similar to that of Li-O under comparable conditions. We present a detailed picture of the bonding in the hydrated Ti(IV) complex under both ambient and supercritical conditions. PMID:21423943

  13. [Studies on chemical constituents of aqueous extract of Lonicera japonica flower buds].

    PubMed

    Yu, Yang; Song, Wei-xia; Guo, Qing-lan; Lin, Sheng; Wang, Su-juan; Yang, Yong-chun; Shi, Jian-gong

    2015-09-01

    From an aqueous extract of Lonicera japonica flower buds, sixteen compounds were isolated by a combination of various chromatographic techniques including column chromatography over macroporous resin, MCI gel, silica gel, and sephadex LH-20 and reversed-phase HPLC. Their structures were elucidated by spectroscopic data analysis as 6'-O-acetylvogeloside (1), 6'-O-acetylsecoxyloganin (2), dichlorogelignate (3), guanosinyl-(3' --> 5')-adenosine monophosphate(GpA,4) , 5'-O-methyladenosine (5), 2'-O-methyladenosine (6), adenosine (7), syringin (8), methyl 4-O-β-D-glucopyranosyl caffeate (9), (-)-dihydrophaseic acid 4'-O-β-D-glucopyranoside (10), ketologanin (11), 7α-morroniside (12), 7β-morroniside (13), kingiside (14), cryptochlorogenic acid methyl ester (15), and 6-hydroxymethyl-3-pyridinol (16). All the compounds were obtained from this plant for the first time, compounds 1 and 2 are new compounds, 3 and 5 are new natural products, and 4 is the first example of dinucleoside monophosphate isolated from a plant extract. PMID:26978994

  14. Radiation Chemical and MR Studies of Aqueous Agarose Gels Containing Ferrous Ions.

    NASA Astrophysics Data System (ADS)

    Leghrouz, Amin Ahmad

    Aqueous agarose gels containing ferrous ions, in 0.05 N sulfuric acid have been studied after irradiation with 6-18 MeV electrons or ^{137} Cs gamma-rays. Such gels can sustain a radiolytic chain reaction, producing Fe ^{3+} with G(Fe^ {3+})-values up to 100 having been observed. The Fe^{3+} production is independent of dose rate between 0.434 and 3.74 Gy min ^{-1}. Dissolved oxygen is needed to maintain the chain reaction, and initial ferric yields are increased if the gel is oxygen saturated or if the ferrous concentration is decreased below 1 mM. The oxidation of ferrous to ferric alters the magnetic moment of the ion and its electron spin relaxation time, which in turn affects its ability to promote proton spin relaxation rates. Longitudinal proton magnetic relaxation rates are increased in proportion to ferric production, permitting visualization of dose levels in these gels by magnetic resonance imaging (MRI) techniques. Non-uniform dose distribution images of electron irradiated ferrous/agarose (FA) systems have been obtained using MRI. Images of radiation doses surrounding capillary tubes filled with radioactive material embedded in FA systems have also been obtained. In this work, another new method of using the ferrous/agarose gel system doped with xylenol orange to visualize the radiation dose distribution directly by eye has been developed. The color change developed depends both quantitatively and qualitatively on the concentrations of solutes in the gel.

  15. Aqueous chemical growth of alpha-Fe2O3-alpha-Cr203 nanocompositethin films

    SciTech Connect

    Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

    2001-06-30

    We are reporting here on the inexpensive fabrication and optical properties of an iron(III) oxide chromium(III) oxide nanocomposite thin film of corundum crystal structure. Its novel and unique-designed architecture consists of uniformed, well-defined and oriented nanorods of Hematite (alpha-Fe2O3) of 50 nm in diameter and 500nm in length and homogeneously distributed nonaggregated monodisperse spherical nanoparticles of Eskolaite (alpha-Cr2O3) of 250 nm in diameter. This alpha-Fe2O3 alpha-Cr2O3 nanocomposite thin film is obtained by growing, directly onto transparent polycrystalline conducting substrate, an oriented layer of hematite nanorods and growing subsequently, the eskolaite layer. The synthesis is carried out by a template-free, low-temperature, multilayer thin film coating process using aqueous solution of metal salts as precursors. Almost 100 percent of the light is absorbed by the composite film between 300 and 525 nm and 40 percent at 800 nm which yields great expectations as photoanode materials for photovoltaic cells and photocatalytic devices.

  16. Optical and chemical observations on gold-mercury nanoparticles in aqueous solution

    SciTech Connect

    Henglein, A.; Giersig, M.

    2000-06-01

    The {gamma}-radiolytic reduction of Hg{sup 2+} in aqueous solution in the presence of 0.3 M 2-propanol first leads to Hg{sub 2}{sup 2+} ({epsilon}{sub 237 nm} = 3.2 x 10{sup 4} M{sup {minus}1} cm{sup {minus}1}), and later to colloidal mercury. When the reduction is carried out in the presence of colloidal gold nanoparticles, Hg{sub 2}{sup 2+} does not appear as an intermediate, and Hg{sub 2}{sup 2+} formed in the absence of gold does not react with added gold colloid. These effects are understood in terms of the reaction of a precursor, Hg{sup +}, with the gold particles. The optical absorption spectra of the resulting mercury containing gold particles are reported for various Au/Hg ratios. The plasmon absorption band of gold is blue-shifted and damped, and a broad absorption band develops around 360 nm with increasing mercury content. The mercury of the composite particles is slowly reoxidized upon exposure of the solution to air. Excess Hg{sup 2+} ions in solution extract adsorbed mercury in the form of Hg{sub 2}{sup 2+}. Both the absorption spectra and electron micrographs of the gold particles are interpreted by a rather weak penetration of mercury into the particles and formation of a rather labile mercury layer around them.

  17. Structural, chemical and optical evaluation of Cu-doped ZnO nanoparticles synthesized by an aqueous solution method

    SciTech Connect

    Iribarren, A.; Hernández-Rodríguez, E.; Maqueira, L.

    2014-12-15

    Highlights: • Cu-doped ZnO nanoparticles obtained by chemical synthesis. • Substitutional or interstitial Cu into ZnO lead specific structural, chemical, and optical changes. • Incorporation efficiency of Cu atoms in ZnO as a function of the Cu concentration in the precursor dissolution. - Abstract: In this work a study of ZnO and Cu-doped ZnO nanoparticles obtained by chemical synthesis in aqueous media was carried out. Structural analysis gave the dominant presence of wurtzite ZnO phase forming a solid solution Zn{sub 1−x}Cu{sub x}O. For high Cu doping CuO phase is also present. For low Cu concentration the lattice shrinks due to Cu atoms substitute Zn atoms. For high Cu concentration the lattice enlarges due to predominance of interstitial Cu. From elemental analysis we determined and analyzed the incorporation efficiency of Cu atoms in Zn{sub 1−x}Cu{sub x}O as a function of the Cu concentration in the precursor dissolution. Combining structural and chemical results we described the Cu/Zn precursor concentrations r{sub w} in which the solid solution of Cu in ZnO is predominant. In the region located at r{sub w} ≈ 0.2–0.3 it is no longer valid. For Cu/Zn precursor concentration r{sub w} > 0.3 interstitial Cu dominates, and some amount of copper oxide appears. As the Cu concentration increases, the effective size of nanoparticles decreases. Photoluminescence (PL) measurements of the Cu-doped ZnO nanoparticles were carried out and analyzed.

  18. The decay of chemical weapons agents under environmental conditions

    SciTech Connect

    McGuire, R.R.; Haas, J.S.; Eagle, R.J.

    1993-04-09

    The rate and mechanism of decay of chemical agents in the environment was studied via live agent field trials at the chemical and Biological Defence Establishment, Porton Down, UK. The plan was to deposit the agents GD (Soman), VX, and H (sulfur mustard) on separate l-m{sup 2} plots on three successive days; i.e., Tuesday through Thursday. The depositions were to be made so as to give an areal concentration of 10 g/m{sup 2}. Four felt pads of approximately 25 cm{sup 2} each were placed at the corners of each of the test plots. These were subsequently extracted and analyzed by CBDE to determine the actual agent concentration. Samples for LLNL (two different types of soil, disks of silicone rubber gasket material, and short cylinders of concrete were to be contaminated and analyzed. Results are described.

  19. Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

    SciTech Connect

    Cooper, J.F.; Krueger, R.; Farmer, J.C.

    1995-10-11

    Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100 C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.

  20. Laser-induced chemical liquid phase deposition of copper from aqueous solutions without reducing agents

    SciTech Connect

    Kochemirovsky, V A; Tumkin, I I; Logunov, L S; Safonov, S V; Menchikov, Leonid G

    2012-08-31

    Laser-induced chemical liquid phase deposition of copper without a traditional reducing agent has been used for the first time to obtain conductive patterns on a dielectric surface having a reducing ability. It is shown that phenol-formaldehyde binder of the dielectric (glass fibre) can successfully play the role of a reducing agent in this process. The resulting copper sediments have low electrical resistance and good topology. (interaction of laser radiation with matter. laser plasmas)

  1. Experimental chlorine partitioning between forsterite, enstatite and aqueous fluid at upper mantle conditions

    NASA Astrophysics Data System (ADS)

    Fabbrizio, Alessandro; Stalder, Roland; Hametner, Kathrin; Günther, Detlef

    2013-11-01

    Cl partition coefficients between forsterite, enstatite and coexisting Cl-bearing aqueous fluids were determined in a series of high pressure and temperature piston cylinder experiments at 2 GPa between 900 and 1300 °C in the system MgO-SiO2-H2O-NaCl-BaO-C±CaCl2±TiO2±Al2O3±F. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA-ICP-MS. The chlorine content of forsterite and enstatite was measured by electron microprobe, and the nature of hydrous defects was investigated by infrared spectroscopy. Partition coefficients show similar incompatibility for Cl in forsterite and enstatite, with DClfo/fl = 0.0012 ± 0.0006, DClen/fl = 0.0018 ± 0.0008 and DClfo/en = 1.43 ± 0.71. The values determined for mineral/fluid partitioning are very similar to previously determined values for mineral/melt. Applying the new mineral/fluid partition coefficients to fluids in subduction zones, a contribution between 0.15% and 20% of the total chlorine from the nominally anhydrous minerals is estimated. Infrared spectra of experimental forsterite show absorption bands at 3525 and 3572 cm-1 that are characteristic for hydroxyl point defects associated with trace Ti substitutions, and strongly suggest that the TiO2 content of the system can influence the chlorine and OH incorporation via the stabilization of Ti-clinohumite-like point defects. The water contents for coexisting forsterite and enstatite in some runs were determined using unpolarized IR spectra and calculated water partition coefficients DH2O fo /en are between 0.01 and 0.5.

  2. Photochemical decomposition of dissolved hydroxylated polybrominated diphenyl ethers under various aqueous conditions.

    PubMed

    Bastos, Patricia Moreira; Eriksson, Johan; Bergman, Ake

    2009-10-01

    The area of fire protection has grown over the last decades with an increasing use of brominated flame retardants (BFRs). Some of the BFRs are phenolic compounds as applied, e.g. tetrabromobisphenol A and 2,4,6-tribromophenol. Others, like the polybrominated diphenyl ethers (PBDEs), can be metabolized to phenolic compounds, i.e. polybrominated phenoxyphenols (OH-PBDEs). OH-PBDEs, have to our knowledge never been commercially produced, but some are well known natural products, and found in high concentrations in biota. The present study is aimed to determine the susceptibility of OH-PBDEs to undergo photolysis when dissolved in water and to compare their reactivity with a couple of PBDE congeners. A previously developed method for studies of photolysis was applied and adapted to include OH-PBDEs in water at pH 7 and 11, water/methanol and water/hydrogen peroxide. The results indicate a change in reaction rates for the photolysis of OH-PBDE in different aqueous media and pH dependence. The results from the present study show that hydroxylated compounds rapidly undergo photolytic transformations in water. The OH-PBDEs are more rapidly transformed then PBDE congeners with similar numbers of bromine substituents. All the OH-PBDEs, independent of structure, are rapidly transformed, with approx. the same rate, when hydrogen peroxide is present, indicating another route of reaction. Polybrominated dibenzo-p-dioxins (PBDDs) are indicated as transformation products upon photolysis of OH-PBDEs with a favorable bromine substitution pattern. PMID:19726071

  3. Radiation-chemical and MR studies of aqueous agarose gels containing ferrous ions

    SciTech Connect

    Leghrous, A.A.

    1989-01-01

    Aqueous agarose gels containing ferrous ions, in 0.05 N sulfuric acid have been studied after irradiation with 6-18 MeV electrons or {sup 137}Cs {gamma}-rays. Such gels can sustain a radiolytic chain reaction, producing Fe{sup 3+} with G (Fe{sup 3+})-values up to 100 having been observed. The Fe{sup 3+} production is independent of dose rate between 0.434 and 3.74 Gy min{sup {minus}1}. Dissolved oxygen is needed to maintain the chain reaction, and initial ferric yields are increased if the gel is oxygen saturated or if the ferrous concentration is decreased below 1 mM. The oxidation of ferrous to ferric alters the magnetic moment of the ion and its electron spin relaxation time, which in turn affects its ability to promote proton spin relaxation rates. Longitudinal proton magnetic relaxation rates are increased in proportion to ferric production, permitting visualization of dose levels in these gels by magnetic resonance imaging (MRI) techniques. Non-uniform dose distribution images of electron irradiated ferrous/agarose (FA) systems have been obtained using MRI. Images of radiation doses surrounding capillary tubes filled with radioactive material embedded in PA systems have also been obtained. In this work, another new method of using the ferrous/agarose gel system doped with xylenol orange to visualize the radiation dose distribution directly by eye has been developed. The color change developed depends both quantitatively and qualitatively on the concentrations of solutes in the gel.

  4. Biosorption of Zinc from Aqueous Solution Using Chemically Treated Rice Husk

    PubMed Central

    Zheng, Ru; Zhao, Jiaying; Zhang, Yingchao; Wong, Po-keung; Ma, Fang

    2013-01-01

    In this study, adsorption of zinc onto the adsorbent (untreated rice husk and NaOH-treated rice husk) was examined. During the removal process, batch technique was used, and the effects of pH and contact time were investigated. Langmuir isotherm was applied in order to determine the efficiency of NaOH-treated rice husk used as an adsorbent. The zinc adsorption was fast, and equilibrium was attained within 30 min. The maximum removal ratios of zinc for untreated rice husk and NaOH-treated rice husk after 1.5 h were 52.3% and 95.2%, respectively, with initial zinc concentration of 25 mg/L and optimum pH of 4.0. Data obtained from batch adsorption experiments fitted well with the Langmuir isotherm model. Maximum adsorption capacity of zinc onto untreated rice husk and NaOH-treated rice husk was 12.41 mg/g, and 20.08 mg/g respectively, at adsorbent dosage of 1 g/L at 25°C. The nature of functional groups (i.e., amino, carboxyl, and hydroxyl) and metal ion interactions was examined by the FT-IR technique. It was concluded that the NaOH-treated rice husk had stronger adsorption capacity for Zn2+ compared with the untreated rice husk. The NaOH-treated rice husk is an inexpensive and environmentally friendly adsorbent for Zn2+ removal from aqueous solutions. PMID:23841065

  5. Transformation of anionically activated trifluoromethyl groups to heterocycles under mild aqueous conditions.

    PubMed

    Qiao, Jennifer X; Wang, Tammy C; Hu, Carol; Li, Jianqing; Wexler, Ruth R; Lam, Patrick Y S

    2011-04-01

    The (hetero)aromatic trifluoromethyl group is present in many biologically active molecules and is generally considered to be chemically stable. In this paper, a convenient one-step synthesis of C-C linked aryl-heterocycles or heteroaryl-heterocycles in good to excellent yields via the reaction of anionically activated trifluoromethyl groups with amino nucleophiles containing a second NH, OH, or SH nucleophile in 1 N sodium hydroxide is reported. The method has high functional group tolerability and is potentially useful in parallel synthesis. PMID:21381681

  6. Thermodynamic and chemical behavior of benzene under shock conditions

    NASA Astrophysics Data System (ADS)

    Maillet, Jean-Bernard; Pineau, Nicolas; Bourasseau, Emeric

    2007-06-01

    The thermodynamic and chemical behavior of benzene along its hugoniot curve is investigated using Molecular Dynamics simulations with reactive potentials. The simulated hugoniot curve is in good agreement with experimental data at low pressures. Moreover, the decomposition threshold is well reproduced. In the high pressure regime, reactive simulations show that benzene rapidly decomposes, but resulting pressures do not match experimental ones anymore. Simulations starting with diamond nanoparticules and hydrogen gas give good pressures along the hugoniot. These simulations seem to confirm the existence of carbon clusters with diamond structure in the decomposition products of benzene.

  7. DEFINITIVE SOX CONTROL PROCESS EVALUATIONS: AQUEOUS CARBONATE AND WELLMAN-LORD (ACID, ALLIED CHEMICAL, AND RESOX) FGD (FLUE GAS DESULFURIZATION) TECHNOLOGIES

    EPA Science Inventory

    The report gives results of economic evaluations of two processes: the Rockwell International aqueous carbonate process (ACP) and the Wellman-Lord process, the latter applied to a sulfuric acid plant, the Foster Wheeler Resox process, and the Allied Chemical coal reduction proces...

  8. APPLICATION OF STIR BAR SORPTIVE EXTRACTION TO ANALYSIS OF VOLATILE AND SEMIVOLATILE ORGANIC CHEMICALS OF POTENTIAL CONCERN IN SOLIDS AND AQUEOUS SAMPLES FROM THE HANFORD SITE

    SciTech Connect

    FRYE JM; KUNKEL JM

    2009-03-05

    Stir bar sorptive extraction was applied to aqueous and solid samples for the extraction and analysis of organic compounds from the Hanford chemicals of potential concern list, as identified in the vapor data quality objectives. The 222-S Laboratory analyzed these compounds from vapor samples on thermal desorption tubes as part of the Hanford Site industrial hygiene vapor sampling effort.

  9. Optimization of Aqueous Extraction Conditions for Recovery of Phenolic Content and Antioxidant Properties from Macadamia (Macadamia tetraphylla) Skin Waste

    PubMed Central

    Dailey, Adriana; Vuong, Quan V.

    2015-01-01

    The macadamia is native to Australia and is now grown commercially around the world. Macadamia skin, known as waste, has been generated abundantly, but this ample source has had limited uses as a byproduct. The aim of this study was to develop optimal aqueous extraction conditions for the recovery of phenolic compounds and antioxidant properties from macadamia skin using Response Surface Methodology (RSM). Water was selected for optimizing the extraction conditions because it is a cheap, safe, and environmentally friendly solvent. The results showed that the RSM models were reliable for the prediction and evaluation of the tested variables. Within the tested ranges, temperature (°C), time (min), and sample-to-solvent ratio (g/100 mL), and their interactions, did not significantly affect phenolic compound (TPC), flavonoid, proanthocyanidin, CUPRAC, and FRAP contents. However, the time and the sample-to-solvent ratio significantly affected DPPH antioxidant activity and the ratio significantly affected ABTS antioxidant capacity. The optimal extraction conditions for the recovery of phenolic compounds and antioxidant properties were predicted and validated at a temperature of 90 °C, a time of 20 min, and a sample-to-solvent ratio of 5 g/100 mL. At these conditions, an extract with TPC of 86 mg GAE/g, flavonoids of 30 mg RUE/g, and proanthocyanidins of 97 mg CAE/g could be prepared with potent antioxidant capacity. PMID:26783954

  10. Optimization of Aqueous Extraction Conditions for Recovery of Phenolic Content and Antioxidant Properties from Macadamia (Macadamia tetraphylla) Skin Waste.

    PubMed

    Dailey, Adriana; Vuong, Quan V

    2015-01-01

    The macadamia is native to Australia and is now grown commercially around the world. Macadamia skin, known as waste, has been generated abundantly, but this ample source has had limited uses as a byproduct. The aim of this study was to develop optimal aqueous extraction conditions for the recovery of phenolic compounds and antioxidant properties from macadamia skin using Response Surface Methodology (RSM). Water was selected for optimizing the extraction conditions because it is a cheap, safe, and environmentally friendly solvent. The results showed that the RSM models were reliable for the prediction and evaluation of the tested variables. Within the tested ranges, temperature (°C), time (min), and sample-to-solvent ratio (g/100 mL), and their interactions, did not significantly affect phenolic compound (TPC), flavonoid, proanthocyanidin, CUPRAC, and FRAP contents. However, the time and the sample-to-solvent ratio significantly affected DPPH antioxidant activity and the ratio significantly affected ABTS antioxidant capacity. The optimal extraction conditions for the recovery of phenolic compounds and antioxidant properties were predicted and validated at a temperature of 90 °C, a time of 20 min, and a sample-to-solvent ratio of 5 g/100 mL. At these conditions, an extract with TPC of 86 mg GAE/g, flavonoids of 30 mg RUE/g, and proanthocyanidins of 97 mg CAE/g could be prepared with potent antioxidant capacity. PMID:26783954

  11. Computational Study of the Cation-Modified GSH Peptide Interactions With Perovskite-Type BFO-(111) Membranes Under Aqueous Conditions

    NASA Astrophysics Data System (ADS)

    Bian, Liang; Dong, Fa-qin; Song, Mian-xin; Xu, Jin-bao; Zhang, Xiao-yan

    2015-06-01

    We elucidated a number of facets regarding glutathione (GSH)-bismuth ferrite (BiFeO3, BFO) interactions and reactivity that have previously remained unexplored on a molecular level. In this approach, the cation-modified reduced GSH (or oxidised glutathione (GS·)) formed on the (111)-oriented BiFeO3 membrane (namely BFO-(111)) can serve as an efficient quencher, and the luminescence mechanism is explained in aqueous conditions. Notably, we suggest the use of Fe2+↓ ion as an electron donor and K+ ion as an electron acceptor to exert a "gluing" effect on the glutamic acid (Glu) and glycine (Gly) side chains, producing an exposed sulfhydryl (-SH) configuration. This method may enable the rational design of a convenient platform for biosensors.

  12. Computational Study of the Cation-Modified GSH Peptide Interactions With Perovskite-Type BFO-(111) Membranes Under Aqueous Conditions.

    PubMed

    Bian, Liang; Dong, Fa-Qin; Song, Mian-Xin; Xu, Jin-Bao; Zhang, Xiao-Yan

    2015-12-01

    We elucidated a number of facets regarding glutathione (GSH)-bismuth ferrite (BiFeO3, BFO) interactions and reactivity that have previously remained unexplored on a molecular level. In this approach, the cation-modified reduced GSH (or oxidised glutathione (GS·)) formed on the (111)-oriented BiFeO3 membrane (namely BFO-(111)) can serve as an efficient quencher, and the luminescence mechanism is explained in aqueous conditions. Notably, we suggest the use of Fe(2+)↓ ion as an electron donor and K(+) ion as an electron acceptor to exert a "gluing" effect on the glutamic acid (Glu) and glycine (Gly) side chains, producing an exposed sulfhydryl (-SH) configuration. This method may enable the rational design of a convenient platform for biosensors. PMID:26061445

  13. Hydrothermal diamond anvil cell for XAFS studies of first-row transition elements in aqueous solutions up to supercritical conditions

    USGS Publications Warehouse

    Bassett, William A.; Anderson, Alan J.; Mayanovic, Robert A.; Chou, I.-Ming

    2000-01-01

    A hydrothermal diamond anvil cell (HDAC) has been modified by drilling holes with a laser to within 150 ??m of the anvil face to minimize the loss of X-rays due to absorption and scatter by diamond. This modification enables acquisition of K-edge X-ray absorption fine structure (XAFS) spectra from first-row transition metal ions in aqueous solutions at temperatures ranging from 25??C to 660??C and pressures up to 800 MPa. These pressure-temperature (P-T) conditions are more than sufficient for carrying out experimental measurements that can provide data valuable in the interpretation of fluid inclusions in minerals found in ore-forming hydrothermal systems as well as other important lithospheric processes involving water. (C) 2000 Elsevier Science B.V. All rights reserved.

  14. Effect of the glass composition on the chemical durability of zinc-phosphate-based glasses in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Massera, J.; Bourhis, K.; Petit, L.; Couzi, M.; Hupa, L.; Hupa, M.; Videau, J. J.; Cardinal, T.

    2013-01-01

    The chemical durability of glasses with the composition 40P2O5-55ZnO-1Ga2O3-4Ag2O and 41P2O5-51ZnO-8Ga2O3 (mol%) was studied by measuring the rates of aqueous dissolution in neutral, acidic and alkaline aqueous solutions and discussed as a function of the glass composition. The change in the pH of the solutions as a function of the immersion time of the samples was used to study the dissolution mechanism. Using XRD and SEM/EDXA, we showed that the dissolution in deionized (DI) water and HCl consists of the leaching of the phosphate chains into the medium along with (i) the formation of a hydrated layer with the composition Zn2P2O73H2O and also of AgCl agglomerates when immersed in HCl and (ii) a leaching out of P, Ga and Ag when immersed for more than 180 min in DI water and for more than 60 min in HCl. The dissolution in NaOH-Na2CO3 consists of a net consumption of the OH- along with the formation of layers of Zn3(PO4)2(H2O)4 and Zn(H2PO2)2H2O with no apparent diffusion of P, Ga and Ag when immersed for as long as 240 min. Increasing the Ga2O3 concentration in zinc-phosphate glass at the expense of Ag2O lowers the dissolution rate when immersed in DI water, HCl and NaOH-Na2CO3 probably due to a reinforcement of the glass network.

  15. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,

  16. Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

    Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

  17. Experimental investigation and modeling of uranium (VI) transport under variable chemical conditions

    USGS Publications Warehouse

    Kohler, M.; Curtis, G.P.; Kent, D.B.; Davis, J.A.

    1996-01-01

    The transport of adsorbing and complexing metal ions in porous media was investigated with a series of batch and column experiments and with reactive solute transport modeling. Pulses of solutions containing U(VI) were pumped through columns filled with quartz grains, and the breakthrough of U(VI) was studied as a function of variable solution composition (pH, total U(VI) concentration, total fluoride concentration, and pH-buffering capacity). Decreasing p H and the formation of nonadsorbing aqueous complexes with fluoride increased U(VI) mobility. A transport simulation with surface complexation model (SCM) parameters estimated from batch experiments was able to predict U(VI) retardation in the column experiments within 30%. SCM parameters were also estimated directly from transport data, using the results of three column experiments collected at different pH and U(VI) pulse concentrations. SCM formulations of varying complexity (multiple surface types and reaction stoichiometries) were tested to examine the trade-off between model simplicity and goodness of fit to breakthrough. A two-site model (weak- and strong-binding sites) with three surface complexation reactions fit these transport data well. With this reaction set the model was able to predict (1) the effects of fluoride complexation on U(VI) retardation at two different pH values and (2) the effects of temporal variability of pH on U(VI) transport caused by low p H buffering. The results illustrate the utility of the SCM approach in modeling the transport of adsorbing inorganic solutes under variable chemical conditions.

  18. NMR-based analysis of the chemical composition of Japanese persimmon aqueous extracts.

    PubMed

    Ryu, Shoraku; Furihata, Kazuo; Koda, Masanori; Wei, Feifei; Miyakawa, Takuya; Tanokura, Masaru

    2016-03-01

    Japanese persimmon (Diospyros kaki L.) is recognized as an outstanding source of biologically active compounds relating to many health benefits. In the present study, NMR spectroscopy provided a comprehensive metabolic overview of Japanese persimmon juice. Detailed signal assignments of Japanese persimmon juice were carried out using various 2D NMR techniques incorporated with broadband water suppression enhanced through T1 effects (BB-WET) or WET sequences, and 26 components, including minor components, were identified. In addition, most components were quantitatively evaluated by the integration of signals using conventional (1) H NMR and BB-WET NMR. This is the first detailed analysis combined with quantitative characterization of chemical components using NMR for Japanese persimmon. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26482562

  19. Evaluation of uncertainties in solid-aqueous-gas chemical equilibrium calculations

    NASA Astrophysics Data System (ADS)

    Novoselov, Alexey A.; Popov, Serguei; de Souza Filho, Carlos Roberto

    2015-06-01

    Thermodynamic calculations are traditionally carried out under the assumption of specified input parameters. Errors associated to the results are not often estimated. Here, we propose a novel algorithm that propagates the uncertainty intervals on thermodynamic constants to the uncertainty in chemical equilibrium compositions. The computing uses a dataset of uncertainties on thermodynamic parameters for minerals, solution species and gases consistent with the SUPCRT92 database. Also the algorithm of nonlinear optimization is thoroughly described and realized on a base of the CRONO software. This code can be incorporated into reactive mass transport models as a core for calculating equilibrium compositions. The performance of the algorithm is tested in an experimental system involving Mont Terri's Opalinus Clay interacting with pore water. Its effectiveness is also evaluated against Monte Carlo simulations and Latin Hypercube sampling.

  20. Removal of sparingly soluble organic chemicals from aqueous solutions with surfactant-coated ferrihydrite

    SciTech Connect

    Holsen, T.M.; Taylor, E.R.; Yong-Chan Seo; Anderson, P.R. )

    1991-09-01

    A surfactant, sodium dodecyl sulfate (SDS), was adsorbed onto ferrihydrite at low pH and desorbed at high pH. Adsorption isotherms of SDS on ferrihydrite yielded an S-shaped curve typical for surfactant adsorption on mineral surfaces. This behavior is due to the surfactant forming aggregate structures on the solid surface. SDS adsorption and desorption experiments revealed that both processes were fast, with equilibrium being reached within 1 h. Toluene, p-xylene, and trichloroethylene sorption experiments demonstrated that the SDS-coated ferrihydrite was able to remove these sparingly soluble organic chemicals (SSOCs) from solution. The amount of SSOC sorbed was directly related to the amount of SDS coating the ferrihydrite. The SSOC with the lowest solubility (p-xylene) had higher removals than the high-solubility SSOC (TCE).

  1. Solubility of AmOHCO{sub 3} in aqueous solution under atmospheric conditions

    SciTech Connect

    Nitsche, H.

    1987-12-01

    Modeling calculations on the solubility of americium have indicated that basic americium carbonate, and not americium trihydroxide, is the solubility-controlling solid in the pH range from 6 to 10 under the influence of atmospheric CO{sub 2}. The solubility of crystalline {sup 243}AmOHCO{sup 3} has been investigated in batch experiments in near-neutral and basic solutions as a function of dissolution time in 0.1 M NaClO{sup 4} at room temperature under oxic conditions. After the solutions reached steady-state conditions, the influence of dissolved solids on the americium concentration in the supernatant solution was studied by utilizing several experimental methods to separate the solution phase from the solid. The solids were characterized by X-ray powder diffraction analysis.

  2. Solubility of AmOHCO sub 3 in aqueous solution under atmospheric conditions

    SciTech Connect

    Nitsche, H.

    1987-12-01

    Modeling calculations on the solubility of americium have indicated that basic americium carbonate, and not americium trihydroxide, is the solubility-controlling solid in the pH range from 6 to 10 under the influence of atmospheric CO{sub 2}. The solubility of crystalline {sup 243}AmOHCO{sup 3} has been investigated in batch experiments in near-neutral and basic solutions as a function of dissolution time in 0.1 M NaClO{sup 4} at room temperature under oxic conditions. After the solutions reached steady-state conditions, the influence of dissolved solids on the americium concentration in the supernatant solution was studied by utilizing several experimental methods to separate the solution phase from the solid. The solids were characterized by X-ray powder diffraction analysis.

  3. Coordinating Chiral Ionic Liquids: Design, Synthesis, and Application in Asymmetric Transfer Hydrogenation under Aqueous Conditions

    PubMed Central

    Vasiloiu, Maria; Gaertner, Peter; Zirbs, Ronald; Bica, Katharina

    2015-01-01

    Hydrophilic coordinating chiral ionic liquids with an amino alcohol substructure were developed and efficiently applied to the asymmetric reduction of ketones. Their careful design and adaptability to the desired reaction conditions allow for these chiral ionic liquids to be used as the sole source of chirality in a ruthenium-catalyzed transfer hydrogenation reaction of aromatic ketones. When used in this reaction system, these chiral ionic liquids afforded excellent yields and high enantioselectivities. PMID:26279638

  4. Determination of the optimum conditions for boric acid extraction with carbon dioxide gas in aqueous media from colemanite containing arsenic

    SciTech Connect

    Ata, O.N.; Colak, S.; Copur, M.; Celik, C.

    2000-02-01

    The Taguchi method was used to determine optimum conditions for the boric acid extraction from colemanite ore containing As in aqueous media saturated by CO{sub 2} gas. After the parameters were determined to be efficient on the extraction efficiency, the experimental series with two steps were carried out. The chosen experimental parameters for the first series of experiments and their ranges were as follows: (1) reaction temperature, 25--70 C; (2) solid-to-liquid ratio (by weight), 0.091 to 0.333; (3) gas flow rate (in mL/min), 66.70--711; (4) mean particle size, {minus}100 to {minus}10 mesh; (5) stirring speed, 200--600 rpm; (6) reaction time, 10--90 min. The optimum conditions were found to be as follows: reaction temperature, 70 C; solid-to-liquid ratio, 0.091; gas flow rate, 711 (in mL/min); particle size, {minus}100 mesh; stirring speed, 500 rpm; reaction time, 90 min. Under these optimum conditions, the boric acid extraction efficiency from the colemanite containing As was approximately 54%. Chosen experimental parameters for the second series of experiments and their ranges were as follows: (1) reaction temperature, 60--80 C; (2) solid-to-liquid ratio (by weight), 0.1000 to 0.167; (3) gas pressure (in atm), 1.5; 2.7; (4) reaction time, 45--120 min. The optimum conditions were found to be as follows: reaction temperature, 70 C; solid-to-liquid ratio, 0.1; gas pressure, 2.7 atm; reaction time, 120 min. Under these optimum conditions the boric acid extraction efficiency from the colemanite ore was approximately 75%. Under these optimum conditions, the boric acid extraction efficiency from calcined colemanite ore was approximately 99.55%.

  5. Differing chemical weathering conditions in meltwater catchments of western Greenland

    NASA Astrophysics Data System (ADS)

    Deuerling, K. M.; Martin, J. B.; Gulley, J.

    2011-12-01

    Chemical weathering in the proglacial environment is limited by moisture availability rather than by temperature and proceeds at rates comparable to more temperate catchments of similar specific discharge. Moisture originates from two sources during the ablation season in proglacial environments: snow melt from non-glacierized catchments and directly from glacial melt. The magnitudes of these water sources create differences in stream size and ecology, which may result in different styles and rates of weathering due to differences in water rock interaction time and acid sources. We test this hypothesis through observations of specific conductance (SpC) and stable isotopes of water collected from streams in the Paakitsoq region of western Greenland in July 2011. In the Paakitsoq region, snow and glacier melt waters flow through distinct drainage basins with different types and amounts of vegetation. Basins that only receive water from snow melt have small clear streams that flow through vegetated marshlands. In contrast, basins where the greatest water flux is derived from glacial melt host larger turbid streams that drain across frontal moraines and continue along largely unvegetated flow paths. Snow and glacier end members can be separated by stable isotopic compositions (snow: δD: -107.3 %; δ18O: -14.8 % and glacier: δD: -229.8 %; δ18O: -29.7 %). Water isotopes from the two types of streams fall between the snow and glacier end member compositions, reflecting addition of snow melt to the turbid streams and isotopic fractionation of the snow as it melts. Isotopic compositions of water in the turbid streams lie along the global meteoric water line (GMWL), but isotopic compositions from the clear streams lie to the left of the GMWL and reflect preferential weathering in the more highly vegetated watersheds. The greatest amount of chemical weathering occurs in flat, marshy areas in the clear stream catchments, presumably as a result of decreased pH caused by plant metabolism and/or microbial reactions, lower specific discharge, and longer residence times. Higher chemical weathering rates in the clear streams are supported by field measurements of SpC that increase downstream from the snow source. SpC of turbid streams are lower than clear streams but increase downstream as they discharge to a single braided, turbid channel that flows ~20 km to the ocean. Future work on these samples will include analyses of major and trace elements, inorganic and organic carbon species, and Sr and Nd isotopes of water and compositions of rock, suspended and bedload sediments. These measurements will aid in understanding which phases contribute the most weathering products to the water and how these products interact with the local ecosystem, as well as quantify the delivery of weathering products to the ocean. Our results reflect the control of ecology on weathering in high latitude areas. This linkage of weathering to ecology suggests that weathering rates and magnitudes will vary with time through the ablation season depending on melt rate, residence time of water in the stream channels and ecosystems, and magnitude of primary productivity.

  6. Chemical water/rock interaction under reservoir condition

    SciTech Connect

    Watanabe, K.; Tanifuji, K.; Takahashi, H.; Wang, Y.; Yamasaki, N.; Nakatsuka, K.

    1995-01-26

    A simple model is proposed for water/rock interaction in rock fractures through which geothermal water flows. Water/rock interaction experiments were carried out at high temperature and pressure (200-350 C, 18 MPa) in order to obtain basic solubility and reaction rate data. Based on the experimental data, changes of idealized fracture apertures with time are calculated numerically. The results of the calculations show that the precipitation from water can lead to plugging of the fractures under certain conditions. Finally, the results are compared with the experimental data.

  7. Uniting Cheminformatics and Chemical Theory To Predict the Intrinsic Aqueous Solubility of Crystalline Druglike Molecules

    PubMed Central

    2014-01-01

    We present four models of solution free-energy prediction for druglike molecules utilizing cheminformatics descriptors and theoretically calculated thermodynamic values. We make predictions of solution free energy using physics-based theory alone and using machine learning/quantitative structure–property relationship (QSPR) models. We also develop machine learning models where the theoretical energies and cheminformatics descriptors are used as combined input. These models are used to predict solvation free energy. While direct theoretical calculation does not give accurate results in this approach, machine learning is able to give predictions with a root mean squared error (RMSE) of ∼1.1 log S units in a 10-fold cross-validation for our Drug-Like-Solubility-100 (DLS-100) dataset of 100 druglike molecules. We find that a model built using energy terms from our theoretical methodology as descriptors is marginally less predictive than one built on Chemistry Development Kit (CDK) descriptors. Combining both sets of descriptors allows a further but very modest improvement in the predictions. However, in some cases, this is a statistically significant enhancement. These results suggest that there is little complementarity between the chemical information provided by these two sets of descriptors, despite their different sources and methods of calculation. Our machine learning models are also able to predict the well-known Solubility Challenge dataset with an RMSE value of 0.9–1.0 log S units. PMID:24564264

  8. Immobilization of selenate by iron in aqueous solution under anoxic conditions and the influence of uranyl

    NASA Astrophysics Data System (ADS)

    Puranen, Anders; Jonsson, Mats; Dähn, Rainer; Cui, Daqing

    2009-08-01

    In proposed high level radioactive waste repositories a large part of the spent nuclear fuel (SNF) canisters are commonly composed of iron. Selenium is present in spent nuclear fuel as a long lived fission product. This study investigates the influence of iron on the uptake of dissolved selenium in the form of selenate and the effect of the presence of dissolved uranyl on the above interaction of selenate. The iron oxide, and selenium speciation on the surfaces was investigated by Raman spectroscopy. X-ray Absorption Spectroscopy was used to determine the oxidation state of the selenium and uranium on the surfaces. Under the simulated groundwater conditions (10 mM NaCl, 2 mM NaHCO 3, <0.1 ppm O 2) the immobilized selenate was found to be reduced to oxidation states close to zero or lower and uranyl was found to be largely reduced to U(IV). The near simultaneous reduction of uranyl was found to greatly enhance the rate of selenate reduction. These findings suggest that the presence of uranyl being reduced by an iron surface could substantially enhance the rate of reduction of selenate under anoxic conditions relevant for a repository.

  9. Transparent ZnO Films Deposited by Aqueous Solution Process Under Various pH Conditions

    NASA Astrophysics Data System (ADS)

    Hong, Jeong Soo; Wagata, Hajime; Ohashi, Naoki; Katsumata, Ken-ichi; Okada, Kiyoshi; Matsushita, Nobuhiro

    2015-08-01

    ZnO films were deposited using a spin-spray method with the source solution containing zinc nitrate and an oxidizing solution containing trisodium citrate onto glass substrates under various pH conditions. A ZnO film with a columnar structure was obtained at pH higher than 7.0, while no ZnO film was formed at a mixed solution pH of 6.7. The transparent and conductive ZnO film obtained from a mixed solution with pH 10.7 exhibited the lowest resistivity of 9.9 × 10-3 Ω cm with a high transmittance above 90%.

  10. Diffusion and polymerization of styrene in an aqueous solution of potassium persulfate under static conditions

    SciTech Connect

    Oganesyan, A.A.; Boyadzhyan, V.G.; Gritskova, I.A.; Gukasyan, A.V.; Matsoyan, S.G.; Pravednikov, A.N.

    1985-10-01

    The potassium persulfate-initiated polymerization of styrene in a mechanically agitated mixture of water and monomer leads to the formation of a stable, monodisperse latex. In order to explain the mechanism of the stabilization of the latex particles in this system, the authors present a detailed investigation of the polymerization of styrene in a specially constructed electrochemical cell under static conditions. A schematic of the cell is shown. Results show that the capacity of the electrical double layer on the platinum electrode remains constant with time in a system containing only a solution of electrolyte, either K/sub 2/SO/sub 4/ or K/sub 2/S/sub 2/O/sub 8/.

  11. Binding Selectivity of Macrocycle Ionophores in Ionic Liquids versus Aqueous Solution and Solvent-free Conditions.

    PubMed

    Gámez, Francisco; Hortal, Ana R; Hurtado, Paola; Avilés-Moreno, Juan R; Hamad, Said; Martínez-Haya, Bruno

    2015-12-01

    The understanding of supramolecular recognition in room-temperature ionic liquids (RTILs) is key to develop the full potential of these materials. In this work, we provide insights into the selectivity of the binding of alkali metal cations by standard cyclodextrin and calixarene macrocycles in RTILs. A direct laser desorption/ionization mass spectrometry approach is employed to determine the relative abundances of the inclusion complexes formed through competitive binding in RTIL solutions. The results are compared with the binding selectivities measured under solvent-free conditions and in water/methanol solutions. Cyclodextrins and calixarenes in which the peripheral OH groups are substituted by bulkier side groups preferentially bind to Cs(+) . Such specific ionophoric behavior is substantially enhanced by solvation effects in the RTIL. This finding is rationalized with the aid of quantum mechanical calculations, in terms of the conformational features and steric interactions that drive the solvation of the inclusion complexes by the bulky RTIL counterions. PMID:26346407

  12. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Arsenamide sodium aqueous injection. 522.144... § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name. dithio diacetic acid, sodium salt. (b... sodium. (c) Sponsor. See No. 050604 in § 510.600(c) of this chapter. (d) Conditions of use. (1) For...

  13. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Arsenamide sodium aqueous injection. 522.144... § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name. dithio diacetic acid, sodium salt. (b... sodium. (c) Sponsor. See No. 050604 in § 510.600(c) of this chapter. (d) Conditions of use. (1) For...

  14. Chemical speciation of the uranyl ion under alkaline conditions. Synthesis, structures, and oxo ligand exchange dynamics

    SciTech Connect

    Clark, D.L.; Conradson, S.D.; Donohoe, R.J.; Keogh, D.W.; Morris, D.E.; Palmer, P.D.; Tait, C.D.; Rogers, R.D.

    1999-04-05

    The aqueous chemistry of the uranyl(VI) ion (UO{sub 2}{sup 2+}) under acidic conditions is relatively well-known, and uranyl chemistry in near-neutral solutions has received considerable attention due to its importance in radioactive waste isolation and disposal. In contrast, aqueous solution chemistry of the uranyl ion under strongly alkaline conditions, such as those found in aging waste tanks within the DOE complex, is only poorly understood. The tetramethylammonium counterion was used to suppress formation of insoluble uranate salts, M{sub 2}U{sub 2}O{sub 7}, and allow for a detailed structural and spectroscopic characterization of UO{sub 2}(OH){sub n}{sup 2{minus}n} (n = 4, 5) under highly alkaline aqueous solution conditions. Single crystals of [Co(NH{sub 3}){sub 6}]{sub 2}[UO{sub 2}(OH){sub 4}]{sub 3}{center_dot}H{sub 2}O were obtained by cooling a dilute solution of Co(NH{sub 3}){sub 6}Cl{sub 3} and UO{sub 2}(NO{sub 3}){sub 2}{center_dot}6H{sub 2}O in 3.5 M (Me{sub 4}N)OH to 5 C.

  15. A phantom study on bladder and rectum dose measurements in brachytherapy of cervix cancer using FBX aqueous chemical dosimeter.

    PubMed

    Bansal, Anil K; Semwal, Manoj K; Arora, Deepak; Sharma, D N; Julka, P K; Rath, G K

    2013-06-01

    The ferrous sulphate-benzoic acid-xylenol orange (FBX) chemical dosimeter, due to its aqueous form can measure average volume doses and hence may overcome the limitations of point dosimetry. The present study was undertaken to validate the use of FBX dosimeter for rectum and bladder dose measurement during intracavitary brachytherapy (ICBT) and transperineal interstitial brachytherapy (TIB). We filled cylindrical polypropylene tubes (PT) and Foley balloons (FB) with FBX solution and used them as substitutes for rectum and bladder dose measurements respectively. A water phantom was fabricated with provision to place the Fletcher-type ICBT and MUPIT template applicators, and FBX filled PT and FB within the phantom. The phantom was then CT scanned for treatment planning and subsequent irradiation. Our results show that the average difference between DVH derived dose value and FBX measured dose is 3.5% (PT) and 13.7% (FB) for ICBT, and 9% (PT) and 9.9% (FB) for TIB. We believe that the FBX system should be able to provide accuracy and precision sufficient for routine quality assurance purposes. The advantage of the FBX system is its water equivalent composition, average volume dose measuring capability, and energy and temperature independent response as compared to TLD or semiconductor dosimeters. However, detailed studies will be needed with regards to its safety before actual in-vivo dose measurements are possible with the FBX dosimeter. PMID:22687710

  16. Flow and morphological conditions associated with the directional solidification of aqueous ammonium chloride

    SciTech Connect

    Magirl, C.S.; Incropera, F.P.

    1993-01-01

    Using 27% aq. NH[sub 4]Cl solutions as transparent analog, shadowgraphy and dye injection were used to observe flow and morphology in unidirectional solidification (UDS) from below. Dendritic crystals that form at the cold surface reject lighter, solute-deficient fluid, and instability is shown by finger-type double-diffusive convection. As the mushy two-phase region grows, perturbations at the liquidus interface cause localized remelting and downward development of channels. Solsutal plumes emanate from the channels, and in time, double-diffusive convection layers also form in the melt. When the solution is chilled at the sides as well as at the bottom, conditions are influenced by detachment and settling of crystals from the sidewall and by plumes from slanted channels. When a slow, oscillatory rocking motion is imposed on UDS, the freckle-type segregates in the final cast is suppressed. Within the melt, plumes and double-diffusive convection are eliminated. Inertially induced convection mixes the melt and produces a dense slurry. Although channels are eliminated from the bottom mushy region, overall heat transfer and macrosegregation in the cavity are unaffected by the slow rocking. Numerical simulations qualitatively predict trends in the field variables and provide insights on interdendritic flows and macrosegregation (freckle-, A-type segregates), although its quantitative predictions are hampered by simplifying assumptions.

  17. Flow and morphological conditions associated with the directional solidification of aqueous ammonium chloride. Annual performance report

    SciTech Connect

    Magirl, C.S.; Incropera, F.P.

    1993-01-01

    Using 27% aq. NH{sub 4}Cl solutions as transparent analog, shadowgraphy and dye injection were used to observe flow and morphology in unidirectional solidification (UDS) from below. Dendritic crystals that form at the cold surface reject lighter, solute-deficient fluid, and instability is shown by finger-type double-diffusive convection. As the mushy two-phase region grows, perturbations at the liquidus interface cause localized remelting and downward development of channels. Solsutal plumes emanate from the channels, and in time, double-diffusive convection layers also form in the melt. When the solution is chilled at the sides as well as at the bottom, conditions are influenced by detachment and settling of crystals from the sidewall and by plumes from slanted channels. When a slow, oscillatory rocking motion is imposed on UDS, the freckle-type segregates in the final cast is suppressed. Within the melt, plumes and double-diffusive convection are eliminated. Inertially induced convection mixes the melt and produces a dense slurry. Although channels are eliminated from the bottom mushy region, overall heat transfer and macrosegregation in the cavity are unaffected by the slow rocking. Numerical simulations qualitatively predict trends in the field variables and provide insights on interdendritic flows and macrosegregation (freckle-, A-type segregates), although its quantitative predictions are hampered by simplifying assumptions.

  18. Development of a functionalized polymeric ionic liquid monolith for solid-phase microextraction of polar endocrine disrupting chemicals in aqueous samples coupled to high-performance liquid chromatography.

    PubMed

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2015-09-01

    Ionic liquids (ILs) have been efficiently used as a "designer sorbent" in sample preparation. A novel 1-(3-aminopropyl)-3-(4-vinylbenzyl)imidazolium 4-styrenesulfonate IL monomer was synthesized and copolymerized with 1,6-di(3-vinylimidazolium) hexane bishexafluorophosphate IL as cross-linking agent to prepare a cross-linked polymeric ionic liquids (PILs) monolith. Coupled to high-performance liquid chromatography (HPLC), the PILs monolith was used as a solid-phase microextraction (SPME) sorbent to extract some polar endocrine disrupting chemical (EDCs) such as estrogens, bisphenol A, and phthalate esters in aqueous samples. Preparation and extraction conditions were investigated and optimized to obtain satisfactory extraction efficiency. Limits of detection (LODs) of the proposed method for three steroid estrogens and bisphenol A were 0.25 and 0.2 μg L(-1), respectively, which were lower than or comparable to some other sample preparation methods. Intra- and inter-day repeatability for all the analytes was 2.2-12%. The monolith-to-monolith repeatability was 7.4-15%. The extraction performance of the method for analysis of target estrogens in treated domestic wastewater was investigated and compared with a dispersive liquid-liquid microextraction (DLLME) method. The proposed SPME method provided better sensitivity and higher resistance to matrix interferences. PMID:26220716

  19. CHEMICAL TRANSFORMATIONS IN ACID RAIN. VOLUME 2. INVESTIGATION OF KINETICS AND MECHANISM OF AQUEOUS-PHASE PEROXIDE FORMATION

    EPA Science Inventory

    The aqueous-phase reactions of O3 with a number of species have been studied in an effort to identify pathways leading to the production of hydrogen peroxide in solution. The aqueous-phase systems studied included the decomposition of O3 in pure water and the interaction of O3 wi...

  20. A new method of reconstituting the P-T conditions of fluid circulation in an accretionary prism (Shimanto, Japan) from microthermometry of methane-bearing aqueous inclusions

    NASA Astrophysics Data System (ADS)

    Raimbourg, Hugues; Thiéry, Régis; Vacelet, Maxime; Ramboz, Claire; Cluzel, Nicolas; Le Trong, Emmanuel; Yamaguchi, Asuka; Kimura, Gaku

    2014-01-01

    In paleo-accretionary prisms and the shallow metamorphic domains of orogens, circulating fluids trapped in inclusions are commonly composed of a mixture of salt water and methane, producing two types of fluid inclusions: methane-bearing aqueous and methane-rich gaseous fluid inclusions. In such geological settings, where multiple stages of deformation, veining and fluid influx are prevalent, textural relationships between aqueous and gaseous inclusions are often ambiguous, preventing the microthermometric determination of fluid trapping pressure and temperature conditions. To assess the P-T conditions of deep circulating fluids from the Hyuga unit of the Shimanto paleo-accretionary prism on Kyushu, Japan, we have developed a new computational code, applicable to the H2O-CH4-NaCl system, which allows the characterization of CH4-bearing aqueous inclusions using only the temperatures of their phase transitions estimated by microthermometry: Tmi, the melting temperature of ice; Thyd, the melting temperature of gas hydrate and Th,aq, homogenization temperature. This thermodynamic modeling calculates the bulk density and composition of aqueous inclusions, as well as their P-T isochoric paths in a P-T diagram with an estimated precision of approximatively 10%. We use this computational tool to reconstruct the entrapment P-T conditions of aqueous inclusions in the Hyuga unit, and we show that these aqueous inclusions cannot be cogenetic with methane gaseous inclusions present in the same rocks. As a result, we propose that pulses of a high-pressure, methane-rich fluid transiently percolated through a rock wetted by a lower-pressure aqueous fluid. By coupling microthermometric results with petrological data, we infer that the exhumation of the Hyuga unit from the peak metamorphic conditions was nearly isothermal and ended up under a very hot geothermal gradient. In subduction or collision zones, modeling aqueous fluid inclusions in the ternary H2O-CH4-NaCl system and not simply in the binary H2O-NaCl is necessary, as the addition of even a small amount of methane to the water raises significantly the isochores to higher pressures. Our new code provides therefore the possibility to estimate precisely the pressure conditions of fluids circulating at depth.

  1. Evaluation of chemical seed treatments for control of stripe rust in wheat under controlled conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The study was conducted under controlled conditions in a greenhouse in Pullman, WA. Seed of winter wheat ‘PS 279’ and spring wheat ‘Lemhi’ were treated by chemical companies with various chemicals. Seed of the two susceptible cultivars without treatment were used as non-treated controls. Five seeds ...

  2. The Homocoupling Reaction of Aromatic Terminal Alkynes by a Highly Active Palladium(II)/AgNO₃ Cocatalyst in Aqueous Media Under Aerobic Conditions.

    PubMed

    Guo, Mengping; Chen, Bo; Lv, Meiyun; Zhou, Xiuling; Wen, Yongju; Shen, Xiuli

    2016-01-01

    A new and efficient Pd(II)/AgNO₃-cocatalyzed homocoupling of aromatic terminal alkynes is described. Various symmetrical 1,4-disubstituted-1,3-diynes are obtained in good to excellent yields. This protocol employs a loading with relatively low palladium(II) in aqueous media under aerobic conditions. PMID:27171071

  3. Mars aqueous chemistry experiment

    NASA Technical Reports Server (NTRS)

    Clark, Benton C.; Mason, Larry W.

    1993-01-01

    The Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. Progress for the first year MACE PIDDP is reported in two major areas of effort: (1) fluids handling concepts, definition, and breadboard fabrication and (2) aqueous chemistry ion sensing technology and test facility integration. A fluids handling breadboard was designed, fabricated, and tested at Mars ambient pressure. The breadboard allows fluid manipulation scenarios to be tested under the reduced pressure conditions expected in the Martian atmosphere in order to validate valve operations, orchestrate analysis sequences, investigate sealing integrity, and to demonstrate efficacy of the fluid handling concept. Additional fluid manipulation concepts have also been developed based on updated MESUR spacecraft definition. The Mars Aqueous Chemistry Experiment Ion Selective Electrode (ISE) facility was designed as a test bed to develop a multifunction interface for measurements of chemical ion concentrations in aqueous solution. The interface allows acquisition of real time data concerning the kinetics and heats of salt dissolution, and transient response to calibration and solubility events. An array of ion selective electrodes has been interfaced and preliminary calibration studies performed.

  4. Kinetics of organic transformations under mild aqueous conditions: implications for the origin of life and its metabolism

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2004-01-01

    The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

  5. XAFS measurements on zinc chloride aqueous solutions from ambient to supercritical conditions using the diamond anvil cell

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    1999-01-01

    The structure and bonding properties of metal complexes in subcritical and supercritical fluids are still largely unknown. Conventional high pressure and temperature cell designs impose considerable limitations on the pressure, temperature, and concentration of metal salts required for measurements on solutions under supercritical conditions. In this study, we demonstrate the first application of the diamond anvil cell, specially designed for x-ray absorption studies of first-row transition metal ions in supercritical fluids. Zn K-edge XAFS spectra were measured from aqueous solutions of 1-2m ZnCl2 and up to 6m NaCl, at temperatures ranging from 25-660 ??C and pressures up to 800 MPa. Our results indicate that the ZnCl42- complex is predominant in the 1m ZnCl2/6m NaCl solution, while ZnCl2(H2O)2 is similarly predominant in the 2m ZnCl2 solution, at all temperatures and pressures. The Zn-Cl bond length of both types of chlorozinc(II) complexes was found to decrease at a rate of about 0.01 A??/100 ??C.

  6. Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

    PubMed

    Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

    2013-11-01

    Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide. PMID:24245274

  7. Aqueous solution-chemical derived Nisbnd Al2O3 solar selective absorbing coatings. 2. Wetting agents and spreading of aqueous solutions on aluminum substrate

    NASA Astrophysics Data System (ADS)

    Li, Zhenxiang; Zhao, Jianxi

    2013-03-01

    Wettability of aluminum substrate by the aqueous solutions containing ethoxylated alcohol nonionic surfactants C12En- or Triton X-series was studied using dynamic contact angle measurements. The efficiency of wetting was found to strongly depend on the length of polyoxyethylene (POE) chain of C12En- or Triton X surfactants. For C12E4 that has a very short POE chain, it hardly made the aqueous solution spreading over aluminum. The others with a long POE chain were indeed very efficient in promoting the solution spreading. Moreover, all the spreading process could be completed within 10 s. The single-layer Nisbnd Al2O3 coatings were fabricated from the precursor solutions containing C12En- or Triton X surfactants and the reflectance spectra were measured by a UV/vis spectrophotometer equipped with an integrating sphere. The results indicated that the precursor solution with a long POE chain surfactant as wetting agent favored to fabricate a uniform film on the aluminum substrate and therefore to get a high solar absorptance.

  8. Polymerization of amino acids under high-pressure conditions: Implication to chemical evolution on the early Earth

    NASA Astrophysics Data System (ADS)

    Kakegawa, T.; Ohara, S.; Ishiguro, T.; Abiko, H.; Nakazawa, H.

    2008-12-01

    Prebiotic polymerization of amino acids is the most fundamental reaction to promote the chemical evolution for origin of life. Polymerization of amino acids is the dehydration reaction. This questions as to if submarine hydrothermal conditions, thus hydrated enironments, were appropreate for peptide formations. Our previous experiments implied that non-aqueous and high-pressure environments (more than 20 MPa) would be suitable for polymerization of amino acids (Ohara et al., 2006). This leads to the hypothesis that the first peptides may have formed in the Hadean oceanic crustal environments, where dehydration proceeded with availability of appropriate temperatures and pressures. In the present study, experiments simulating the crustal conditions were performed with various pressures (1-175 MPa) and temperatures (100- 200 C degree) using autoclaves. Purified powders (100 mg) of alanine, glycine, valine and aspartic acid were used in the experiments without mixing water in order to examine the solid-solid reactions. The products were analyzed using HPLC and LC-MS. Results indicate that: (1) longer time is required to form peptide compared to those of previous aqueous experiments; (2) pressure has a role to limit the production of melanoidine and cyclic amino acids, which are inhibitors for elongation of peptides; (3) glycine was polymerized up to 11-mer, which was not formed in any previous experiments without catalyses; (4) valine was polymerized up to 3-mer; and (5) aspartic acid was polymerized to 4-mer, accompanied with production of other amino acids. It is noteworthy that high-pressure environments favor all examined polymerization reactions. Such situations would have happened inside of deep oceanic crusts of the early Earth.

  9. Chemical Compositional Indications of Aqueous Alteration for Whitewater Lake Boxworks, Veneers and Veins at Cape York, Mars

    NASA Astrophysics Data System (ADS)

    Clark, Benton; Gellert, R.; Squyres, S.; Arvidson, R.; Yen, A.; Rice, J.; Athena Science Team

    2013-10-01

    An area of partially-veneered, flat-lying rocks which also includes boxwork and linear veins contains a variety of compositions which are each indicative of minor to major aqueous alteration processes in the Cape York rim of Endeavour Crater. As analyzed by APXS x-ray fluorescence spectroscopy, the sets of unique elemental compositions correspond variously to Al-Si rich clays in boxwork veins, with Fe- and Cl-enriched salt veneers (Esperance samples); swarms of Ca sulfate veins (Ortiz samples); and, as indicated by remote sensing, mafic smectite alteration products in veneers (Chelmsford covering Azilda samples). Multiple offset analyses by APXS reveal clear trends and associations of certain elements, allowing inferences of mineralogies. In contrast to the acidic environment deduced for the genesis of the multiple-sulfate Burns formation sediments and shallow ferric-rich sulfate deposits beneath soils, these alteration products formed at more near-neutral pH, often with major chemical segregations and requiring high water-rock ratios comparable to a wide range of eminently habitable terrestrial environments. Several of these compositions are also rated high with respect to their potential for preservation of organic materials and biomarkers. Within distances of just tens of meters inside this so-called Whitewater Lake unit, this broad diversity exemplifies the tantalizing opportunities as well as challenges for future sample return missions to the red planet, which in this case could also be expanded to include nearby samples of Burns Fm sandstones, hematite concretions, light-toned spherules (Kirkwood), large gypsum veins (Homestake), martian global soils and surface dust.

  10. Weathering and dissolution rates among Pb shot pellets of differing elemental compositions exposed to various aqueous and soil conditions.

    PubMed

    Takamatsu, Takejiro; Murata, Tomoyoshi; Koshikawa, Masami K; Watanabe, Mirai

    2010-07-01

    The present study was performed to investigate the weathering and dissolution rates of Pb shot pellets differing in elemental composition (Pb, Sb, and As) exposed under various aqueous and soil conditions using five commercial shot pellet preparations. Upon immersion in distilled water, the dissolution rates of shot pellets, calculated from the difference in weight before versus after immersion, decreased with increasing Sb + As contents and the dominant precipitate was hydrocerussite. These subsidiary ingredients may be related to the difficulty of metallic Pb oxidation (transformation to PbO). Weight losses standardized by the amount of rainfall upon exposure to rainfall on open grassland and under canopies of Japanese cedar (Cryptomeria japonica) and bamboo-leafed oak (Quercus myrsinaefolia) were 1.11, 1.07, and 7.35 mg g pellets(-1) year(-1) L(-1), respectively, and was also related to Sb + As contents in shot pellets. However, annual dissolution rates of Pb standardized by the amount of rainfall as the soluble fraction at the same sites were 0.72, 0.33, and 0.40 mg Pb g pellets(-1) year(-1) L(-1) in the same order. These trends seemed to be related to the rainfall pH, which induces precipitation of Pb dissolved as PbCO(3) under conditions of higher pH at the Q. myrsinaefolia site or organic matter released from leaves, etc., which can form metal complexes. Dissolution rates of shot pellets buried in soils (Cambisol, Fluvisol, Regosol, Andosol) also seemed to be related to the soil pH and dissolved organic matter contents but were about sixfold faster than those with exposure to rainfall. PMID:20039167

  11. Degradation of (-)-epicatechin and procyanidin B2 in aqueous and lipidic model systems. first evidence of "chemical" flavan-3-ol oligomers in processed cocoa.

    PubMed

    De Taeye, Cédric; Cibaka, Marie-Lucie Kankolongo; Jerkovic, Vesna; Collin, Sonia

    2014-09-10

    Despite the key role of flavan-3-ols in many foods, very little is yet known concerning the modification of their chemical structures through food processes. Degradation of model media containing (-)-epicatechin and procyanidin B2, either separately or together, was monitored by RP-HPLC-DAD-ESI(-)-MS/MS. Medium composition (aqueous or lipidic) and temperature (60 and 90 °C) were studied. In aqueous medium at 60 °C, (-)-epicatechin was mainly epimerized to (-)-catechin, but it was also oxidized to "chemical" dimers, a "chemical" trimer, and dehydrodi(epi)catechin A. Unlike oxidation, epimerization was enhanced at 90 °C. In lipidic medium, epimerization proved slow but degradation was faster. Procyanidin B2 likewise proved able to epimerize, especially at 90 °C and in aqueous medium. At high temperature only, the interflavan linkage was cleaved, yielding the same compounds as those found in the monomer-containing model medium. Oxidation to procyanidin A2 was also evidenced. With little epimerization and slow oxidation even at 90 °C, procyanidin B2 proved more stable in lipidic medium. Synergy was also observed: in the presence of the monomer, the dimer degradation rate increased 2-fold at 60 °C. This work states for the first time the presence of newly formed flavan-3-ol oligomers in processed cocoa. PMID:25167469

  12. Transport of Chemical Vapors from Subsurface Sources to Atmosphere as Affected by Shallow Subsurface and Atmospheric Conditions

    NASA Astrophysics Data System (ADS)

    Rice, A. K.; Smits, K. M.; Hosken, K.; Schulte, P.; Illangasekare, T. H.

    2012-12-01

    Understanding the movement and modeling of chemical vapor through unsaturated soil in the shallow subsurface when subjected to natural atmospheric thermal and mass flux boundary conditions at the land surface is of importance to applications such as landmine detection and vapor intrusion into subsurface structures. New, advanced technologies exist to sense chemical signatures at the land/atmosphere interface, but interpretation of these sensor signals to make assessment of source conditions remains a challenge. Chemical signatures are subject to numerous interactions while migrating through the unsaturated soil environment, attenuating signal strength and masking contaminant source conditions. The dominant process governing movement of gases through porous media is often assumed to be Fickian diffusion through the air phase with minimal or no quantification of other processes contributing to vapor migration, such as thermal diffusion, convective gas flow due to the displacement of air, expansion/contraction of air due to temperature changes, temporal and spatial variations of soil moisture and fluctuations in atmospheric pressure. Soil water evaporation and interfacial mass transfer add to the complexity of the system. The goal of this work is to perform controlled experiments under transient conditions of soil moisture, temperature and wind at the land/atmosphere interface and use the resulting dataset to test existing theories on subsurface gas flow and iterate between numerical modeling efforts and experimental data. Ultimately, we aim to update conceptual models of shallow subsurface vapor transport to include conditionally significant transport processes and inform placement of mobile sensors and/or networks. We have developed a two-dimensional tank apparatus equipped with a network of sensors and a flow-through head space for simulation of the atmospheric interface. A detailed matrix of realistic atmospheric boundary conditions was applied in a series of experiments. Water saturation, capillary pressure, air and soil temperature, and relative humidity were continuously monitored. Aqueous TCE was injected into the tank below the water table and allowed to volatilize. TCE concentration exiting the tank head space was measured through interval sampling by direct injection into a gas chromatograph. To quantify the transient concentration of TCE vapor in the soil pore space a novel use of Solid Phase Micro-Extraction (SPME) was developed. Results from our numerical simulations were compared with the experimental data, which demonstrated the importance of considering the interaction of the atmosphere with the subsurface in conceptualization and numerical model development. Results also emphasize that soil saturation and transient sorption have a significant effect on vapor transport through the vadose zone. Follow-up tests and detailed analyses are still underway. Additional applications of this work include carbon sequestration leakage, methane contamination in the shallow subsurface and environmental impact of hydraulic fracturing.

  13. Chemical Conditioning as an Approach to Ischemic Stroke Tolerance: Mitochondria as the Target

    PubMed Central

    Jin, Zhen; Wu, Jinzi; Yan, Liang-Jun

    2016-01-01

    It is well established that the brain can be prepared to resist or tolerate ischemic stroke injury, and mitochondrion is a major target for this tolerance. The preparation of ischemic stroke tolerance can be achieved by three major approaches: ischemic conditioning, hypoxic conditioning and chemical conditioning. In each conditioning approach, there are often two strategies that can be used to achieve the conditioning effects, namely preconditioning (Pre-C) and postconditioning (Post-C). In this review, we focus on chemical conditioning of mitochondrial proteins as targets for neuroprotection against ischemic stroke injury. Mitochondrial targets covered include complexes I, II, IV, the ATP-sensitive potassium channel (mitoKATP), adenine dinucleotide translocase (ANT) and the mitochondrial permeability transition pore (mPTP). While numerous mitochondrial proteins have not been evaluated in the context of chemical conditioning and ischemic stroke tolerance, the paradigms and approaches reviewed in this article should provide general guidelines on testing those mitochondrial components that have not been investigated. A deep understanding of mitochondria as the target of chemical conditioning for ischemic stroke tolerance should provide valuable insights into strategies for fighting ischemic stroke, a leading cause of death in the world. PMID:27005615

  14. Influence of Variable Environmental Conditions on Presence and Concentration of Energetic Chemicals Near Soil Surface in the Vadoze Zone

    NASA Astrophysics Data System (ADS)

    Anaya, A. A.; Padilla, I. Y.

    2008-12-01

    Many explosive-related compounds (ERCs) are found near the soil-atmospheric surface in sites containing buried explosive devices, such as landmines and unexploded ordnance, detonation-residual, and munitions residues from explosive manufacturing facilities. Accurate assessment of the fate and transport processes is essential for predicting their movement to the surface, groundwater, or any other important environmental compartment. The transport processes controlling the direction and magnitude of the movement, and chemical and physical processes controlling the fate of the chemicals vary with environmental conditions. This research addresses the effect of variable rainfall, evaporation, temperature, and solar radiation on fate and transport of 2,4,6-Trinitrotoluene (TNT), 2,4-Dinitrotoluene (DNT), and other related chemicals in partially saturated soil. Experiments have been conducted in a laboratory-scale 3D SoilBed placed inside an environmental chamber equipped with rainfall and solar radiation simulators, and temperature control settings. The SoilBed was packed with a sandy soil. Experiments have been conducted by burying a TNT/DNT source, simulating a landmine, and applying different rainfall and light radiation cycles while monitoring DNT, TNT, and other related ERCs solute concentrations temporally and spatially within the SoilBed. Experiments include different source characteristics, rainfall intensities, temperatures, and radiation cycles to evaluate their effect on the detection and movement of ERC in soils in both aqueous and vapor phases. Temporal and spatial data has been analyzed comparatively and quantitatively. Comparative analysis was developed using surfer®- and voxler®-generated images and 3D visualization models applying spatial interpolation and masking methods. Single and multi-variable statistical analysis has been employed to determine the most important factors affecting the fate, transport and detection of ERC near soil-atmospheric surfaces. Results show that rainfall, radiation, and temperature variations influence the presence, transport, and concentrations of TNT and DNT near the soil surface. Higher concentrations are observed near the end of rainfall events, both in the aqueous and gaseous phases. Higher rainfall intensity results in higher presence and concentrations. Lower TNT and DNT concentrations than their solubility limit indicate rate-limited mass transfer, dissolution limitations, and dilution processes. Radiation events and higher atmospheric temperatures result in greater presence and concentrations of DNT and TNT, indicating influence of these factors on fate and transport processes. TNT degradation by-products measured mostly in the upper segments of the SoilBed, suggest degradation processes resulting from radiation-induced conditions near the soil-atmospheric surface. Although the ERC source consists of equal mass of TNT and DNT, greater detection density and concentrations are observed for DNT. A generalized linear mixed statistical model has been applied to quantify the effect of environmental conditions on ERC detection and concentrations. The statistical analysis indicates that rainfall events and related water contents are the most influential factors affecting the presence and concentrations of ERCs in the aqueous and gaseous phase. Solar radiation, and related heat flux, is the second most influential parameter. Although atmospheric temperature influence the presence and concentration of ERCs in soils, it is the least influential parameter.

  15. Electrochemical efficacy of a carboxylated multiwalled carbon nanotube filter for the removal of ibuprofen from aqueous solutions under acidic conditions.

    PubMed

    Bakr, Ahmed Refaat; Rahaman, Md Saifur

    2016-06-01

    This study provides insight into the efficiency of a functionalized multiwalled carbon nanotube filter for the removal of an anti-inflammatory drug, ibuprofen, through conventional filtration and electrochemical filtration processes. A comparison was made between carboxylated multiwalled carbon nanotubes (MWNTs-COOH) and pristine multiwalled carbon nanotubes (MWNTs) in order to emphasize the enhanced performance of MWNTs-COOH for the removal of ibuprofen using an electrochemical filtration process under acidic conditions. Ibuprofen-removal trials were evaluated based on absorbance values obtained using a UV/Vis spectrophotometer, and possible degradation products were identified using liquid chromatography mass spectrometry (LC-MS). The results exhibited near complete removal of ibuprofen by MWNTs-COOH at lower applied potentials (2 V), at lower flow rates, and under acidic conditions, which can be attributed to the generation of superoxides and their active participation in simultaneous degradation of ibuprofen, and its by-products, under these conditions. At higher applied potential (3 V), the possible participation of both bulk indirect oxidation reactions, and direct electron transfer were hypothesized for the removal behavior over time (breakthrough). At 3 V under acidic conditions, near 100% removal of the target molecule was achieved and was attributed to the enhanced generation of electroactive species toward bulk chemical reactions and a possible contribution from direct electron transfer under these conditions. The degradation by-products of ibuprofen were effectively removed by allowing longer residence time during the filtration process. Moreover, the effect of temperature was studied, yet showed a non-significant effect on the overall removal process. PMID:27035389

  16. Serpentinization, iron oxidation, and aqueous conditions in an ophiolite: Implications for hydrogen production and habitability on Mars

    NASA Astrophysics Data System (ADS)

    Greenberger, Rebecca N.; Mustard, John F.; Cloutis, Edward A.; Pratt, Lisa M.; Sauer, Peter E.; Mann, Paul; Turner, Kathryn; Dyar, M. Darby; Bish, David L.

    2015-04-01

    Molecular hydrogen produced through iron oxidation during formation of serpentine and magnetite can sustain terrestrial subsurface ecosystems. The Fe3+ in serpentine partitions into octahedral and tetrahedral sites differently as serpentinization proceeds, and tetrahedral Fe3+ is present toward the end of serpentinization. We map Fe oxidation states in a serpentinite to determine the degree to which serpentinization progressed and where hydrogen production has been maximized to assess habitability at an abandoned chrysotile mine in Norbestos, Quebec, in association with the Canadian Space Agency's Mars Methane Analogue Mission. We also analyzed stable isotopes of carbon and oxygen in carbonates to constrain the conditions of water-rock interaction during serpentinization. Iron oxidation and coordination was determined through field imaging of rock walls with a visible hyperspectral imager (420-720 nm), and samples collected from imaged rocks and elsewhere in the mine were imaged in the laboratory (420-1100 nm). Sample chemistry, mineralogy, and oxidation state were determined with laboratory measurements of visible through mid-infrared reflectance spectra, major element chemistry, mineralogy, and Mössbauer spectroscopy. Mapping with hyperspectral imaging of outcrops and hand samples shows that tetrahedral Fe3+ is common in serpentinites at this site, and results are confirmed through other measurements. Major element chemistry and mineralogy are consistent with serpentine plus minor carbonate. Carbonate samples show an exceptional range in δ13C (-13.14 to + 16.12 ‰ VPDB) and δ18O (-15.48 to - 3.20 ‰ VPDB) that vary with location in the mine. Carbonates south of a shear zone (δ13C more positive) likely formed during periods of serpentinization in a carbon-limited reservoir closed to carbon addition but open to methane escape. Carbonates in a shear zone (δ13C more negative) probably formed later at low temperatures through CO2-metasomatism or atmospheric weathering, and isotopic trends are consistent with kinetic fractionation. The extensive presence of tetrahedral Fe3+ in serpentine shows the system liberally produced H2 while the isotope systematics have implications for preservation of indicators of the aqueous conditions that formed serpentinites on Mars and their habitability.

  17. Extrusion conditions affect chemical composition and in vitro digestion of select food ingredients.

    PubMed

    Dust, Jolene M; Gajda, Angela M; Flickinger, Elizabeth A; Burkhalter, Toni M; Merchen, Neal R; Fahey, George C

    2004-05-19

    An experiment was conducted to determine the effects of extrusion conditions on chemical composition and in vitro hydrolytic and fermentative digestion of barley grits, cornmeal, oat bran, soybean flour, soybean hulls, and wheat bran. Extrusion conditions altered crude protein, fiber, and starch concentrations of ingredients. Organic matter disappearance (OMD) increased for extruded versus unprocessed samples of barley grits, cornmeal, and soybean flour that had been hydrolytically digested. After 8 h of fermentative digestion, OMD decreased as extrusion conditions intensified for barley grits and cornmeal but increased for oat bran, soybean hulls, and wheat bran. Total short-chain fatty acid production decreased as extrusion conditions intensified for barley grits, soybean hulls, and soybean flour. These data suggest that the effects of extrusion conditions on ingredient composition and digestion are influenced by the unique chemical characteristics of individual substrates. PMID:15137844

  18. Effects of physical conditioning on heat tolerance in chemical-defense gear. Master's thesis

    SciTech Connect

    Nauss, M.M.

    1986-06-01

    Today the threat of chemical warfare is real. The only effective defense is the use of chemical defense gear and gas masks. Since they render chemical-warfare gases and liquids impermeable to penetration, they also prohibit sweat evaporation in conditions of thermal stress and thus, contribute to heat illness development. Historically, it has been the hot, humid tropics where United Nation's peacekeeping forces have been called, thus the use of chemical-defense gear in these regions is a realistic possibility and heat illness could affect the outcome of any mission carried out there. The human body only operates within a narrow range of core temparatures, and heat illness is the result of a breakdown in homeostasis. Many factors influence heat tolerance, thus maintaining core temperature within a safe range. Adequate hydration, acclimitization to heat, low body weight, young age, low alcohol intake, and physical fitness all contribute to heat tolerance. This proposal attempts to look specifically at the effect of physical conditioning on heat tolerance in chemical-defense gear as a possible solution to the heat-stress problem noted in this gear. Trainee graduates attending technical training schools at Lackland AFB, Texas, will be tested for maximum oxygen uptake (VO/2max) and heat tolerance time (HTT) in chemical defense gear on bicycle ergometers at Brooks AFB, Texas. Half of these subjects will be physically conditioned for 12 weeks.

  19. Sampling of Organic Solutes in Aqueous and Heterogeneous Environments Using Oscillating Excess Chemical Potentials in Grand Canonical-like Monte Carlo-Molecular Dynamics Simulations

    PubMed Central

    2015-01-01

    Solute sampling of explicit bulk-phase aqueous environments in grand canonical (GC) ensemble simulations suffer from poor convergence due to low insertion probabilities of the solutes. To address this, we developed an iterative procedure involving Grand Canonical-like Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Each iteration involves GCMC of both the solutes and water followed by MD, with the excess chemical potential (μex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the μex of the water and solutes over the GCMC-MD iterations, solute exchange probabilities and the spatial distributions of the solutes improved. The utility of the oscillating-μex GCMC-MD method is indicated by its ability to approximate the hydration free energy (HFE) of the individual solutes in aqueous solution as well as in dilute aqueous mixtures of multiple solutes. For seven organic solutes: benzene, propane, acetaldehyde, methanol, formamide, acetate, and methylammonium, the average μex of the solutes and the water converged close to their respective HFEs in both 1 M standard state and dilute aqueous mixture systems. The oscillating-μex GCMC methodology is also able to drive solute sampling in proteins in aqueous environments as shown using the occluded binding pocket of the T4 lysozyme L99A mutant as a model system. The approach was shown to satisfactorily reproduce the free energy of binding of benzene as well as sample the functional group requirements of the occluded pocket consistent with the crystal structures of known ligands bound to the L99A mutant as well as their relative binding affinities. PMID:24932136

  20. Method of using an aqueous chemical system to recover hydrocarbon and minimize wastes from sludge deposits in oil storage tanks

    SciTech Connect

    Goss, M.L.

    1992-02-04

    This patent describes a process for separating and removing a hydrocarbon, water and solid components of sludge deposited in an oil storage tank. It comprises: introducing a sufficient amount of a nonionic surfactant in an aqueous solution to form a layer of the solution above the sludge layer; the nonionic surfactant comprising: C{sub 8}-C{sub 12} alkylphenol-ethylene oxide adducts of about 55%-75% by weight ethylene oxide, and at least one castor oil-ethylene oxide adduct of about 55%-75% by weight ethylene oxide; the nonionic surfactant being present in a quantity sufficient to separate hydrocarbon component from the sludge without forming an emulsion, adding a diluent, immiscible with the aqueous layer, for extracting the hydrocarbons, and separately draining the diluent layer and aqueous layer from the tank.

  1. Physico-chemical properties of alginate/shellac aqueous-core capsules: Influence of membrane architecture on riboflavin release.

    PubMed

    Ben Messaoud, Ghazi; Sánchez-González, Laura; Probst, Laurent; Jeandel, Carole; Arab-Tehrany, Elmira; Desobry, Stéphane

    2016-06-25

    To enhance physico-chemical properties of alginate liquid-core capsules, shellac was incorporated into the membrane (composite capsules) or as an additional external layer (coated capsules). The influence of pH, coating time, shellac concentration and preparation mechanism (acid or calcium precipitation) were investigated. Results showed that shellac significantly influenced the capsules properties. The feasibility of shellac incorporation was closely related to the preparation conditions as confirmed by Infrared spectroscopy. Optical, fluorescence and scanning electron microscopy, highlighted different capsules and membranes architectures. In contrast to simple and composite capsules, coated capsules showed a pH-dependent release of the entrapped vitamin especially after shellac crosslinking with calcium. Heating of coated capsules above the glass transition temperature investigated by Differential Scanning Calorimetry, led to irreversible structural change due to thermoplastic behavior of shellac and enhanced riboflavin retention under acidic conditions. This global approach is useful to control release mechanism of low molecular weight molecules from macro and micro-capsules. PMID:27083835

  2. Facile stabilization of cyclodextrin metal-organic frameworks under aqueous conditions via the incorporation of C60 in their matrices.

    PubMed

    Li, Haiqing; Hill, Matthew R; Huang, Runhong; Doblin, Christian; Lim, Seng; Hill, Anita J; Babarao, Ravichandar; Falcaro, Paolo

    2016-05-21

    A facile method to improve the stability of γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) in an aqueous environment has been developed through the incorporation of hydrophobic C60 in their matrices, and the resulting hybrid materials were exploited for drug delivery applications. PMID:27055670

  3. Estimation of octanol/water partition coefficient and aqueous solubility of environmental chemicals using molecular fingerprints and machine learning methods

    EPA Science Inventory

    Octanol/water partition coefficient (logP) and aqueous solubility (logS) are two important parameters in pharmacology and toxicology studies, and experimental measurements are usually time-consuming and expensive. In the present research, novel methods are presented for the estim...

  4. Detection of aqueous phase chemical warfare agent degradation products by negative mode ion mobility time-of-flight mass spectrometry [IM(tof)MS].

    PubMed

    Steiner, Wes E; Harden, Charles S; Hong, Feng; Klopsch, Steve J; Hill, Herbert H; McHugh, Vincent M

    2006-02-01

    The use of negative ion monitoring mode with an atmospheric pressure ion mobility orthogonal reflector time-of-flight mass spectrometer [IM(tof)MS] to detect chemical warfare agent (CWA) degradation products from aqueous phase samples has been determined. Aqueous phase sampling used a traditional electrospray ionization (ESI) source for sample introduction and ionization. Certified reference materials (CRM) of CWA degradation products for the detection of Schedule 1, 2, or 3 toxic chemicals or their precursors as defined by the chemical warfare convention (CWC) treaty verification were used in this study. A mixture of six G-series nerve related CWA degradation products (EMPA, IMPA, EHEP, IHEP, CHMPA, and PMPA) and their related collision induced dissociation (CID) fragment ions (MPA and EPA) were found in each case to be clearly resolved and detected using the IM(tof)MS instrument in negative ion monitoring mode. Corresponding ions, masses, drift times, K(o) values, and signal intensities for each of the CWA degradation products are reported. PMID:16413205

  5. Chemistry of the system: Al2O3(c)minus HCL aqueous. [chemical reactions resulting from propellant combustion of rocket propellants

    NASA Technical Reports Server (NTRS)

    Tyree, S. Y., Jr.

    1975-01-01

    In order to study exhaust gas chemistry for the space shuttle, the vapor pressure of 2 to 1 weight mixtures of 3-M hydrochloric acid and Al2O3 was studied over a l80 minute reaction period at 31 C. The Al2O3 sample was one of high surface area furnished by NASA Langley Research Center. A brief review is given for aqueous aluminum chemistry, and the chemical reactions of combustion products (exhaust gases) of aluminum propellant binders for the space shuttle are listed.

  6. Effects of biomass types and carbonization conditions on the chemical characteristics of hydrochar

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Effects of biomass types (sugar beet pulp vs. bark mulch) and hydrothermal carbonization (HTC) processing conditions (temperature, residence time, and the phase of reaction medium) on the chemical characteristics of hydrochars were examined by elemental analysis, advanced solid-state nuclear magneti...

  7. ACCURACY OF PESTICIDE REFERENCE STANDARD SOLUTIONS. PART II. CHEMICAL STABILITY UNDER FOUR STORAGE CONDITIONS

    EPA Science Inventory

    A study was undertaken to assess the long-term chemical stability of dilute standard pesticide solutions of 4 compound classes. The solutions were studied under 4 storage conditions: freezer at -15C; refrigerator at 3C; ambient temperature in the dark; and ambient temperature on ...

  8. Physical Conditions and Chemical Structure of the PNe NGC 2440 and NGC 2371-72

    NASA Astrophysics Data System (ADS)

    Olguìn, L.; Vázquez, R.; Cook, R.; Benítez, G.

    2002-02-01

    We present preliminary results of the physical conditions and chemical abundances determined through the planetary nebulae (PNe) NGC 2440 and NGC 2371-72. We have used low-dispersion long-slit spectra of regions defined by main axes and bright knots.

  9. F-18 labeling protocol of peptides based on chemically orthogonal strain-promoted cycloaddition under physiologically friendly reaction conditions.

    PubMed

    Sachin, Kalme; Jadhav, Vinod H; Kim, Eun-Mi; Kim, Hye Lan; Lee, Sang Bong; Jeong, Hwan-Jeong; Lim, Seok Tae; Sohn, Myung-Hee; Kim, Dong Wook

    2012-08-15

    We introduce the high-throughput synthesis of various (18)F-labeled peptide tracers by a straightforward (18)F-labeling protocol based on a chemo-orthogonal strain-promoted alkyne azide cycloaddition (SPAAC) using aza-dibenzocyclootyne-substituted peptides as precursors with (18)F-azide synthon to develop peptide based positron emission tomography (PET) molecular imaging probes. The SPAAC reaction and subsequent chemo-orthogonal purification reaction with azide resin proceeded quickly and selectively under physiologically friendly reaction conditions (i.e., toxic chemical reagents-free, aqueous medium, room temperature, and pH ≈7), and provided four (18)F-labeled tumor targetable bioactive peptides such as cyclic Arg-Gly-Asp (cRGD) peptide, bombesin (BBN), c-Met binding peptide (cMBP), and apoptosis targeting peptide (ApoPep) in high radiochemical yields as direct injectable solutions without any HPLC purification and/or formulation processes. In vitro binding assay and in vivo PET molecular imaging study using the (18)F-labeled cRGD peptide also demonstrated a successful application of our (18)F-labeling protocol. PMID:22770524

  10. Noble metals as permanent chemical modifiers for the determination of mercury in environmental reference materials using solid sampling graphite furnace atomic absorption spectrometry and calibration against aqueous standards

    NASA Astrophysics Data System (ADS)

    da Silva, Alessandra Furtado; Welz, Bernhard; Curtius, Adilson J.

    2002-12-01

    Iridium, palladium, rhodium and ruthenium, thermally deposited on the platform, were investigated as permanent modifiers for the determination of mercury in ash, sludge, marine and river sediment reference materials, ground to a particle size of 50 μm, using solid sampling graphite furnace atomic absorption spectrometry. A total mass of 250 μg of each modifier was applied using 25 injections of 20 μl of modifier solution (500 mg l -1), and executing a temperature program for modifier conditioning after each injection. The performance of palladium was found to be most consistent, taking the characteristic mass as the major criterion, resulting in an excellent correlation between the measured integrated absorbance values and the certified mercury contents. Mercury was found to be lost in part from aqueous solutions during the drying stage in the presence of all the investigated permanent modifiers, as well as in the presence of the palladium and magnesium nitrates modifier added in solution. A loss-free determination of mercury in aqueous solutions could be reached only after the addition of potassium permanganate, which finally made possible the use of aqueous standards for the direct analysis of solid samples. A characteristic mass of 55-60 pg Hg was obtained for the solid samples, using Pd as a permanent modifier, and also in aqueous solutions after the addition of permanganate. The results obtained for mercury in ash, sludge and sediment reference materials, using direct solid sapling and calibration against aqueous standards, as well as the detection limit of 0.2 mg kg -1 were satisfactory for a routine procedure.

  11. DETERMINATION OF STABLE VALENCE STATES OF CHROMIUM IN AQUEOUS AND SOLID WASTE MATRICES - EXPERIMENTAL VERIFICATION OF CHEMICAL BEHAVIOR

    EPA Science Inventory

    The objective of the research effort was to experimentally assess the chemical behavior of the stable species of chromium during the preparation, chemical manipulation, and spectrophotometric analyses of simulated and authentic environmental samples for hexavalent chromium. The d...

  12. QUANTITATIVE ANALYSIS OF AQUEOUS SPECIES USING RAMAN SPECTROMETRY AND EQUILIBRIUM MODEL CALCULATIONS

    EPA Science Inventory

    An analytical approach of quantifying various chemical species, using Raman spectrometry in conjunction with equilibrium modeling, has been tested on aqueous solutions containing Nd, Cu, and dipicolinic acid. Equilibrium modeling was used to select optimum conditions in simple so...

  13. Solubilization and desorption of PAHs in soil-aqueous system by biosurfactants produced from Pseudomonas aeruginosa P-CG3 under thermophilic condition.

    PubMed

    Cheng, K Y; Zhao, Z Y; Wong, J W C

    2004-10-01

    Surface-active agents (surfactants) can enhance bioremediation of soils contaminated with PAHs by reducing sorption of PAHs or increasing desorption rates. The effectiveness of nonionic surfactant (Tween 80) and biosurfactants to enhance the solubilization and desorption of phenanthrene (Phe) and pyrene (Pyr) in soil-aqueous systems under thermophilic conditions was investigated using batch studies. Tween 80 and biosurfactants produced from Pseudomonas aeruginosa strain, ATCC 9027 and a strain isolated in our laboratory, P-CG3 were tested in this study. The results showed that all the surfactants could effectively enhance the solubility of both Phe and Pyr under thermophilic condition (55 degrees C), which was linearly proportional to the concentrations of surfactants at concentrations above their respective critical micelle concentration (CMC). When the surfactants' concentrations in aqueous phase were above their respective CMCs, substantial amounts of PAHs were desorbed from soil into the aqueous phase. Among the three surfactants used, the biosurfactant produced from our own isolate, P-CG3 was more effective in enhancing the solubilization and desorption of PAHs, implying that it might have the potential to be further applied in the bioremediation of PAH contaminated soils. PMID:15551830

  14. Biodegradation of chemicals in a standardized test and in environmental conditions.

    PubMed

    Ahtiainen, Jukka; Aalto, Miia; Pessala, Piia

    2003-05-01

    The estimation of biodegradation rates is an important source of uncertainty in chemical risk assessment. The existing OECD tests for ready biodegradability have been developed to devise screening methods to determine whether a chemical is potentially easily biodegradable, rather than to predict the actual rate, of biodegradation in the environment. However, risk assessment needs degradation rates. In practice these rates are often estimated (default values) from ready biodegradability tests. These tests have many compromising arbitrary features compared to the situation in the real environment. One important difference is the concentration of the chemical. In wastewater treatment or in the environment many chemicals are present at ng l(-1) to microg l(-1) levels whereas in the tests the concentrations exceed 10-400 mg carbon per litre. These different concentrations of the chemical will lead to different growth kinetics and hence different biodegradation rates. At high concentrations the chemical, if it is degradable, can serve as a primary substrate and competent microorganisms will grow exponentially, resulting in a sigmoid biodegradation curve. At low environmental concentrations the chemical does not serve as a primary substrate, and therefore does not support significant growth of the degraders, and the substrate has a linear biodegradation rate. In this study the biodegradation rates of two reference chemicals, aniline and 4-chloroaniline, were compared in a standard method and in more realistic conditions at low concentrations, using 14C-labelled substances and different sources of inocula. Biomass evolution during the tests was monitored by adenosine triphosphate measurement and also on the basis of the residual 14C-activity in the particulate matter. The results partly support the thesis that low concentrations lead to different biodegradation kinetics compared to the concentrations used in the standard tests. Furthermore the biodegradation rates of the chemicals studied, particularly of 4-chloroaniline, in Finnish natural waters appeared to be lower than those reported in some other countries. PMID:12615106

  15. Chemical Modifications in Therapeutic Protein Aggregates Generated under Different Stress Conditions

    PubMed Central

    Luo, Quanzhou; Joubert, Marisa K.; Stevenson, Riki; Ketchem, Randal R.; Narhi, Linda O.; Wypych, Jette

    2011-01-01

    In this study, we characterized the chemical modifications in the monoclonal antibody (IgG2) aggregates generated under various conditions, including mechanical, chemical, and thermal stress treatment, to provide insight into the mechanism of protein aggregation and the types of aggregate produced by the different stresses. In a separate study, additional biophysical characterization was performed to arrange these aggregates into a classification system (Joubert, M. K., Luo, Q., Nashed-Samuel, Y., Wypych, J., and Narhi, L. O. (2011) J. Biol. Chem. 286, 25118–25133). Here, we report that different aggregates possessed different types and levels of chemical modification. For chemically treated samples, metal-catalyzed oxidation using copper showed site-specific oxidation of Met246, His304, and His427 in the Fc portion of the antibody, which might be attributed to a putative copper-binding site. For the hydrogen peroxide-treated sample, in contrast, four solvent-exposed Met residues in the Fc portion were completely oxidized. Met and/or Trp oxidation was observed in the mechanically stressed samples, which is in agreement with the proposed model of protein interaction at the air-liquid interface. Heat treatment resulted in significant deamidation but almost no oxidation, which is consistent with thermally induced aggregates being generated by a different pathway, primarily by perturbing conformational stability. These results demonstrate that chemical modifications are present in protein aggregates; furthermore, the type, locations, and severity of the modifications depend on the specific conditions that generated the aggregates. PMID:21518762

  16. Establishing physico-chemical reference conditions in Mediterranean streams according to the European Water Framework Directive.

    PubMed

    Sánchez-Montoya, María del Mar; Arce, Maria Isabel; Vidal-Abarca, María Rosario; Suárez, María Luisa; Prat, Narcís; Gómez, Rosa

    2012-05-01

    Type-specific physico-chemical reference conditions are required for the assessment of ecological status in the Water Framework Directive context, similarly to the biological and hydro-morphological elements. This directive emphasises that natural variability of quality elements in high status (reference condition) needs to be quantified. Mediterranean streams often present a marked seasonal pattern in hydrological, biological and geochemical processes which could affect physico-chemical reference conditions. This study establishes general physico-chemical reference conditions (oxygenation, nutrient, salinity and acidification conditions) for different Mediterranean stream types. 116 potential reference sites located in 23 Mediterranean catchments in Spain were sampled in spring, summer and autumn in 2003. All sites were subjected to a screening method for the selection of reference sites in Mediterranean streams (Mediterranean Reference Criteria) and classified using a pre-established stream typology that establishes five different stream types (temporary streams, evaporite-calcareous at medium altitude, siliceous headwaters, calcareous headwaters and large watercourses). Reference conditions (reference value and reference threshold equivalents to high-good class boundary) were calculated using two different methods according to the availability of reference sites: the reference site 75th percentile approach of all reference sites and the 25th percentile of the population approach. The majority of the studied potential reference sites (76 out of 116) were selected as reference sites. Regarding type-specific reference conditions, only siliceous headwaters could be considered different from the rest of stream types because lower conductivity and pH. All reference stream types presented seasonal differences as regards some parameters, except for temporary streams due to the high natural variation of this stream type. For those parameters which presented seasonal differences in a specific stream type, the least restrictive values were proposed as reference conditions. PMID:22386888

  17. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    PubMed

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-01

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red?S, and phenylboronic acid and alizarin red?S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a)?the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b)?the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)? RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH?5-11: B' + L' (K')? BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. PMID:25169423

  18. Effect of Rare Earth Oxide Content on Nanograined Base Metal Electrode Multilayer Ceramic Capacitor Powder Prepared by Aqueous Chemical Coating Method

    NASA Astrophysics Data System (ADS)

    Zhang, Yichi; Wang, Xiaohui; Kim, Jinyong; Li, Longtu

    2013-02-01

    The aqueous chemical coating route is highly effective in preparing BaTiO3 nanoparticles uniformly coated with additives. Such nanoparticles can be used to produce nano-grained temperature stable BaTiO3 ceramics with core-shell structure, fulfilling the need of next-generation ultrathin layer base metal electrode (BME) multilayer ceramic capacitors (MLCCs). Rare earth oxides are an important class of additives owing to their ability to fulfill both donor and acceptor roles. In this paper, the effects of Y2O3 and Ho2O3 co-dopant content on dielectric and microstructural properties were investigated. By applying chemical coating, BaTiO3-based high performance temperature stabilized ceramics with the average grain size of about 130 nm, which met the requirement of next generation BME MLCCs, were obtained.

  19. Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography.

    PubMed

    McGregor, Laura A; Gauchotte-Lindsay, Caroline; Daéid, Niamh Nic; Thomas, Russell; Daly, Paddy; Kalin, Robert M

    2011-07-22

    Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique. PMID:21652041

  20. Quantum chemical analysis of the energy of proton transfer from phenol and chlorophenols to H2O in the gas phase and in aqueous solution

    NASA Astrophysics Data System (ADS)

    Schrmann, Gerrit

    1998-12-01

    Proton transfer energies of phenol and 14 chlorophenols with H2O as a base are analyzed in the gas phase and in solution using quantum chemical methods at the semiempirical and ab initio level of computation. The effect of aqueous solution was accounted for by applying the density functional theory (DFT) implementation of the conductor-like screening model (COSMO) as well as semiempirical continuum-solvation models. The results reveal substantial and systematic overestimations of the free energies of proton transfer as derived from experimental solution-phase pKa data. This can be traced back to both deficiencies in the current model parameterization as well as to limitations of the underlying gas-phase quantum chemical models, which is further illustrated by additional complete-basis-set (CBS) calculations for the proton transfer reaction with phenol. In contrast, the relative pKa trend is reflected well by COSMO-DFT calculations with correlation coefficients (adjusted for degrees of freedom) of 0.96. Decomposition of the dissociation energy in aqueous solution into a gas-phase term and a term summarizing the solvation contributions provides new insights into the effect of solvation on proton transfer energies, and yields mechanistic explanations for the observed differences in the gas-phase and solution-phase acidity orders of various subgroups of the compounds.

  1. Relaxation of the structure of simple metal ion complexes in aqueous solutions at up to supercritical conditions

    USGS Publications Warehouse

    Mayanovic, Robert A.; Jayanetti, Sumedha; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2003-01-01

    Recently x-ray absorption fine structure (XAFS) studies of various ions in aqueous solutions showed a variation of cation-ligand bond lengths, often coupled with other structure changes, with increasing temperatures. Thus, the variations of the structure of several metal ion complexes with temperature based on observations from the X-ray absorption fine structure (XAFS) studies in the hope that it will stimulate the development of either first- principles theory or molecular dynamics simulations that might adequately describes these results are discussed.

  2. Modeling the kinetics of microbial degradation of deicing chemicals in porous media under flow conditions.

    PubMed

    Wehrer, Markus; Jaesche, Philipp; Totsche, Kai Uwe

    2012-09-01

    A quantitative knowledge of the fate of deicing chemicals in the subsurface can be provided by joint analysis of lab experiments with numerical simulation models. In the present study, published experimental data of microbial degradation of the deicing chemical propylene glycol (PG) under flow conditions in soil columns were simulated inversely to receive the parameters of degradation. We evaluated different scenarios of an advection-dispersion model including different terms for degradation, such as zero order, first order and inclusion of a growing and decaying biomass for their ability to explain the data. The general break-through behavior of propylene glycol in soil columns can be simulated well using a coupled model of solute transport and degradation with growth and decay of biomass. The susceptibility of the model to non-unique solutions was investigated using systematical forward and inverse simulations. We found that the model tends to equifinal solutions under certain conditions. PMID:22609860

  3. Effect of chemical reactions on the rate of hydrogen sulfide absorption in a drop of aqueous solution of sodium hydroxide

    SciTech Connect

    Aniskin, S.V.; Protod`yakonov, I.O.; Bessonov, N.M.

    1995-10-10

    The problem of gas treatment to remove hydrogen sulfide is currently one of the central problems of the chemical, petrochemical, pulp and paper, and other industries. The expression for determining the coefficient of acceleration of hydrogen sulfide absorption by a drop of sodium hydroxide solution through chemical reactions has been obtained.

  4. Relative toxicity of pyrolysis gases from materials - Effects of chemical composition and test conditions

    NASA Technical Reports Server (NTRS)

    Hilado, C. J.; Cumming, H. J.

    1978-01-01

    Relative toxicity test data on 270 materials are presented, based on test procedures developed at the University of San Francisco. The effects of chemical composition, using data on 13 types of synthetic polymers and eight types of fabrics, are discussed. Selected materials were evaluated using nine test conditions with the USF method, and using methods developed at the FAA Civil Aeromedical Institute, Douglas Aircraft Company and San Jose State University.

  5. Effects of chemical modifications in the partition behavior of proteins in aqueous two-phase systems: a case study with RNase A.

    PubMed

    González-Valdez, José; Rito-Palomares, Marco; Benavides, Jorge

    2013-01-01

    Chemical modification of proteins is gaining importance due to the improvement in properties and the broader range of applications that these protein conjugates have. Once modified, several purification strategies need to be applied to isolate the conjugates of interest. Aqueous two-phase systems (ATPS) are an attractive alternative for the primary recovery of proteins and their conjugates. However, to better understand which biochemical parameters affect in greater degree the partition behavior of these modified proteins in ATPS, it becomes necessary to characterize the partition behavior of different species. In this work, ribonuclease A (RNase A) was selected as a model protein to address the partition behavior of chemically modified proteins in ATPS. Native, mono-PEGylated, Uniblue A, Dabsyl Chloride, and Direct Red 83 chemically modified RNase A's were partitioned in 16 different polyethylene glycol (PEG)-potassium phosphate ATPS. Results suggest that while the effects of system design parameters govern the partition of native RNase A, the behavior of the chemically modified species is more influenced by the physicochemical characteristics of the modifying molecules, that in most cases promote partition toward the top polymer-rich phase with recovery percentages as high as 86%. It has been found that both, the hydrophobicity and molecular weight of the modifying species play a preponderant role in conjugate partition behavior since as hydrophobicity increases partition is promoted towards the PEG-rich phase balancing the effect of the molecular weight of the modifying molecules that tends to shift partition towards the salt rich phase. PMID:23296881

  6. Analysis of initial reactions of MALDI based on chemical properties of matrixes and excitation condition.

    PubMed

    Lai, Yin-Hung; Wang, Chia-Chen; Chen, Chiu Wen; Liu, Bo-Hong; Lin, Sheng Hsien; Lee, Yuan Tseh; Wang, Yi-Sheng

    2012-08-16

    This investigation concerns the initial chemical reactions that affect the ionization of matrixes in matrix-assisted laser desorption/ionization (MALDI). The study focuses on the relaxations of photon energy that occur on a comparable time scale to that of ionization, in which the available laser energy is shared and the ionization condition is changed. The relaxations include fluorescence, fragmentation, and nonradiative relaxation from the excited state to the ground state. With high absorption cross section and long excited-state lifetime, photoionization of matrix plays an important role if sufficient laser energy is used. Under other conditions, thermal ionization of the molecule in the ground state is predicted to be one of the important reactions. Evidence of change in the branching ratio of initial reactions with the matrix and the excitation wavelength was obtained with α-cyano-4-hydroxycinnamic acid, sinapinic acid, 2,5-dihydroxybenzoic acid, and 2,4,6-trihydroxyacetophenone. These matrixes are studied by obtaining their mixed crystal absorption spectra, fluorescence properties, laser-induced infrared emission, and product ions. The exact ionization pathway depends on the chemical properties of matrixes and the excitation conditions. This concept may explain the diversity of experimental results observed in MALDI experiments, which provides an insight into the ensemble of chemical reactions that govern the generation of ions. PMID:22799495

  7. Kinetics of OH-initiated oxidation of some oxygenated organic compounds in the aqueous phase under tropospheric conditions

    NASA Astrophysics Data System (ADS)

    Poulain, L.; Grubert, S.; François, S.; Monod, A.; Wortham, H.

    2003-04-01

    The interest for multiphase interactions of Volatile Organic Compounds (VOCs) in the troposphere has increased for a few years. Inside the clouds water droplets, soluble VOCs can be oxidized by free radicals thus modifying the droplet composition. This reactivity has an impact on the tropospheric oxidizing capacity as well as the aerosols' properties. In the present work, we measured aqueous phase OH-initiated oxidation rate constants of several oxygenated organic compounds relevant to the atmosphere or chosen as test compounds (ethanol, t-butanol, 1-butanol, iso-propanol, 1-propanol, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, phenol, ethyl ter-butyl ether (ETBE), n-propyl acetate, acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK), ethyl formate). Experiments took place in an aqueous phase photoreactor. The rate constants were determinated using the relative kinetic method. Different OH-radical sources were tested, as well as different reference compounds in order to detect any artifact. The results have shown validation of the experimental protocol on test compounds. The overall results allowed to propose a structure reactivity method in order to predict OH-oxidation rate constant of new compounds. Finally, tropospheric life times of the studied compounds were compared inside and outside a cloud.

  8. Chemically modified olive stone: a low-cost sorbent for heavy metals and basic dyes removal from aqueous solutions.

    PubMed

    Aziz, Abdellah; Ouali, Mohand Said; Elandaloussi, El Hadj; De Menorval, Louis Charles; Lindheimer, Marc

    2009-04-15

    In the present work, we have investigated the sorption efficiency of treated olive stones (TOS) towards cadmium and safranine removal from their respective aqueous solutions. TOS material was prepared by treatment of olive stones with concentrated sulfuric acid at room temperature followed up by a subsequent neutralization with 0.1 M NaOH aqueous solution. The resulting material has been thoroughly characterized by SEM, energy-dispersive X-ray (EDX), MAS (13)C NMR, FTIR and physicochemical parameters were calculated. The sorption study of TOS at the solid-liquid interface was investigated using kinetics, sorption isotherms, pH effect and thermodynamic parameters. The preliminary results indicate that TOS exhibit a better efficiency in terms of sorption capacities toward the two pollutants (128.2 and 526.3 mg/g for cadmium and safranine, respectively) than those reported so far in the literature. Moreover, the sorption process is ascertained to occur fast enough so that the equilibrium is reached in less than 15 min of contact time. The results found in the course of this study suggest that ion exchange mechanism is the most appropriate mechanism involved in cadmium and safranine removal. Finally, the sorption efficiency of TOS is compared to those of other low-cost sorbents materials yet described in the literature. PMID:18687522

  9. Effect of ethylene and temperature conditioning on sensory attributes and chemical composition of 'Comice' pears.

    PubMed

    Makkumrai, Warangkana; Sivertsen, Hanne; Sugar, David; Ebeler, Susan E; Negre-Zakharov, Florence; Mitcham, Elizabeth J

    2014-06-01

    'Comice' is among the pear varieties most difficult to ripen after harvest. Ethylene, cold temperature, and intermediate (10 °C) temperature conditioning have been successfully used to stimulate the ability of 'Comice' pears to ripen. However, the sensory quality of pears stimulated to ripen by different conditioning treatments has not been evaluated. In this study, a descriptive sensory analysis of 'Comice' pears conditioned to soften to 27, 18, and 9 N firmness with ethylene exposure for 3 or 1 days, storage at 0 °C for 25 or 15 days, or storage at 10 °C for 10 days was performed. Sensory attributes were then related to changes in chemical composition, including volatile components, water-soluble polyuronides, soluble solids content (SSC), and titratable acidity (TA). The sensory profile of fruit conditioned with ethylene was predominant in fibrous texture and low in fruity and pear aroma. Fruit conditioned at 0 °C was described as crunchy at 27 and 18 N firmness and became juicy at 9 N firmness. Fruit conditioned at 0 °C produced the highest quantity of alcohols and fewer esters than fruit conditioned at 10 °C, and they had higher fruity and pear aroma than fruit conditioned with ethylene, but lower than fruit conditioned at 10 °C. Fruit held at 10 °C were predominant in fruity and pear aroma and had the highest concentration of esters. Water-soluble polyuronides were strongly, positively correlated (r > 0.9) with sensory attributes generally associated with ripeness, including juiciness, butteriness, and sweetness and negatively correlated (r > -0.9) with sensory attributes generally associated with the unripe stage, such as firmness and crunchiness. However, water-soluble polyuronides were not significantly different among conditioning treatments. Sensory sweetness was not significantly correlated with SSC, but TA and SSC/TA were significantly correlated with sensory tartness. However, there were no significant differences among the conditioning treatments in sweet or sour taste perception when the fruit fully softened. The results indicate that the various methods of conditioning 'Comice' pear fruits for ripening had different effects on their sensory and chemical properties that may influence their sensory quality. PMID:24844943

  10. Physico-chemical changes of ZnO nanoparticles with different size and surface chemistry under physiological pH conditions.

    PubMed

    Gwak, Gyeong-Hyeon; Lee, Won-Jae; Paek, Seung-Min; Oh, Jae-Min

    2015-03-01

    We studied the physico-chemical properties of ZnO nanoparticles under physiological pH conditions (gastric, intestinal and plasma) as functions of their size (20 and 70 nm) and surface chemistry (pristine, L-serine, or citrate coating). ZnO nanoparticles were dispersed in phosphate buffered saline under physiological pH conditions and aliquots were collected at specific time points (0.5, 1, 4, 10 and 24 h) for further characterization. The pH values of the aqueous ZnO colloids at each condition were in the neutral to slightly basic range and showed different patterns depending on the original size and surface chemistry of the ZnO nanoparticles. The gastric pH condition was found to significantly dissolve ZnO nanoparticles up to 18-30 wt%, while the intestinal or plasma pH conditions resulted in much lower dissolution amounts than expected. Based on the X-ray diffraction patterns and X-ray absorption spectra, we identified partial phase transition of the ZnO nanoparticles from wurtzite to Zn(OH)2 under the intestinal and plasma pH conditions. Using scanning electron microscopy, we verified that the overall particle size and morphology of all ZnO nanoparticles were maintained regardless of the pH. PMID:25668417

  11. Process for the conversion of and aqueous biomass hydrolyzate into fuels or chemicals by the selective removal of fermentation inhibitors

    DOEpatents

    Hames, Bonnie R.; Sluiter, Amie D.; Hayward, Tammy K.; Nagle, Nicholas J.

    2004-05-18

    A process of making a fuel or chemical from a biomass hydrolyzate is provided which comprises the steps of providing a biomass hydrolyzate, adjusting the pH of the hydrolyzate, contacting a metal oxide having an affinity for guaiacyl or syringyl functional groups, or both and the hydrolyzate for a time sufficient to form an adsorption complex; removing the complex wherein a sugar fraction is provided, and converting the sugar fraction to fuels or chemicals using a microorganism.

  12. Chemical residence time and hydrological conditions influence treatment of fipronil in vegetated aquatic mesocosms.

    PubMed

    Kröger, Robert; Moore, Matthew T

    2011-01-01

    Fipronil, a phenyl-pyrazole insecticide, is often used in rice (Oryza sativa L.) production agriculture, with elevated runoff concentrations and loads having potential toxicological effects on downstream aquatic environments. This study evaluated two species of aquatic plants-broadleaf cattail (Typha latifolia L.) and powdery alligator-flag (Thalia dealbata Fraser ex Roscoe)-placed in series against a nonvegetated mesocosm in reducing concentrations and loads of fipronil, and associated metabolites. Vegetation type and hydrological condition (inundated vs. dry) were treatment effects used for comparison. The vegetated mesocosms significantly reduced higher loads and concentrations of fipronil, fipronil sulfone, and sulfide in both inundated and dry hydrological conditions over nonvegetated nesocosms. Under inundation conditions, vegetated mesocosms reduced >50% of influent fipronil concentrations and betweeen 60 and 70% of fipronil loads, which was significantly higher than the dry conditions (10-32% concentration and load). These results show that agricultural management strategies usingephemeral aquatic zones, such as drainage ditches, can be optimized to couple chemical applications with vegetation presence and hydrology to facilitate the reduction in chemical waste loads entering downstream aquatic ecosystems. Such reduction is critical for use with fipronil, where negative impacts have been demonstrated with several nontarget species. PMID:21520763

  13. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-09-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

  14. Aqueous-phase photooxidation of levoglucosan - a mechanistic study using Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS)

    NASA Astrophysics Data System (ADS)

    Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

    2014-04-01

    Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase, despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by Aerosol Time of Flight Chemical Ionization Mass Spectrometry (Aerosol-ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol-ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information to determine potential reaction mechanisms and sequences. As well, bond scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double bond equivalence to carbon ratio (DBE / #C). The trajectory of LG photooxidation on this plot suggests formation of poly-carbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an Aerosol Mass Spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol-ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

  15. MIPs in Aqueous Environments.

    PubMed

    Wan, Ying-chun; Ma, Hui-ting; Lu, Bin

    2015-01-01

    When organic solvent-compatible molecularly imprinted polymers (MIPs) are used in aqueous environment, how to reduce nonspecific binding is a major challenge. By modifying the binding solvents and introducing appropriate washing and elution steps, even relatively hydrophobic MIPs can gain optimal rebinding selectivity in aqueous conditions. Furthermore, water-compatible MIPs that can be used to treat aqueous samples directly have been prepared. The use of hydrophilic co-monomers, the controlled surface modification through controlled radical polymerization, and the new interfacial molecular imprinting methods are different strategies to prepare water-compatible MIPs. By combining MIPs with other techniques, both organic solvent-compatible and water-compatible MIPs can display better functional performances in aqueous conditions. Intensive studies on MIPs in aqueous conditions can provide new MIPs with much-improved compatibilities that will lead to more interesting applications in biomedicine and biotechnology. PMID:25796623

  16. Surface conditioning of chemical vapor deposited hexagonal boron nitride film for negative electron affinity

    NASA Astrophysics Data System (ADS)

    Loh, Kian Ping; Sakaguchi, Isao; Gamo, Mikka Nishitani; Tagawa, Shigeru; Sugino, Takashi; Ando, Toshihiro

    1999-01-01

    The surface conditions favoring a negative electron affinity (NEA) on hexagonal boron nitride (h-BN) grown by radio-frequency plasma-assisted chemical vapor deposition (CVD) have been investigated by ultraviolet photoelectron spectroscopy. The NEA condition on the h-BN film appears to be resistant to oxygen-plasma or in-vacuo atomic oxygen treatment. It is not certain whether the segregation of bulk hydrogen onto the surface helps to promote the NEA; the depth profile of the deposited film reveals about 0.01%-0.1% atomic concentration of hydrogen. High temperature annealing at 1100 °C results in a positive electron affinity surface (PEA). Reexposure of PEA surface to atomic hydrogen at room temperature regenerates the NEA condition. This is evident of the role of superficial hydrogen in promoting NEA on the h-BN film.

  17. Structure and antioxidant activity of β-lactoglobulin-glycoconjugates obtained by high-intensity-ultrasound-induced Maillard reaction in aqueous model systems under neutral conditions.

    PubMed

    Stanic-Vucinic, Dragana; Prodic, Ivana; Apostolovic, Danijela; Nikolic, Milan; Velickovic, Tanja Cirkovic

    2013-05-01

    Sonication is a new processing technology in the dairy industry. The aim of this study was to test glycation of β-lactoglobulin (BLG) in Maillard reaction (MR) induced by high-intensity ultrasound in aqueous solution under neutral conditions at 10-15 °C, which is not favourable for the MR. BLG was sonicated in the presence of glucose, galactose, lactose, fructose, ribose and arabinose. Formation of Maillard reaction products (MRPs) was monitored by mass spectrometry, spectrophotometry and fluorimetry. Ultrasound treatment resulted in formation of MRPs with all tested carbohydrates. Ribose induced the highest degree of modification resulting in 76% of BLG modified and an average of three anhydroribose units attached. Circular dichroism spectra analyses indicated only minor alterations in secondary and tertiary structures. MRP obtained by ultrasound exhibited 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activity and possessed increased iron-chelating activity and reducing power. High-intensity ultrasound efficiently promotes BLG-glycoconjugates formation by MR in aqueous solutions under non-denaturing conditions. PMID:23265528

  18. Chemical and structural properties of Jordanian zeolitic tuffs and their admixtures with urea and thiourea: Potential scavengers for phenolics in aqueous medium

    SciTech Connect

    Yousef, R.I.; Tutunji, M.F.; Derwish, G.A.W.; Musleh, S.M.

    1999-08-15

    Native Jordanian zeolitic tuffs, rich in phillipsite, were treated with urea and thiourea. The chemical and structural properties of the tuffs and their urea and thiourea admixtures were studied using SEM, XRF, XRD, and FTIR techniques, and their adsorption capacities were estimated by the methylene blue method. The urea and thiourea treatment has not affected the mineral constitution of the tuffs. The results revealed that urea and thiourea were linked by hydrogen bonding through the NH{sub 2} moiety to the zeolite substrate, with urea showing the strongest effect. Experiments were carried out to investigate the possible use of the prepared materials for the removal of phenol and chlorinated phenols from aqueous solutions. Although thiourea caused a reduction in the relative surface area, both urea and thiourea admixtures were more effective than the free zeolitic tuff in the removal of phenol and chlorinated phenols from water, with urea admixture displaying the largest removal capacity.

  19. High-sensitivity chemical derivatization NMR analysis for condition monitoring of aged elastomers.

    SciTech Connect

    Assink, Roger Alan; Celina, Mathias Christopher; Skutnik, Julie Michelle

    2004-06-01

    An aged polybutadiene-based elastomer was reacted with trifluoroacetic anhydride (TFAA) and subsequently analyzed via 19F NMR spectroscopy. Derivatization between the TFAA and hydroxyl functionalities produced during thermo-oxidative aging was achieved, resulting in the formation of trifluoroester groups on the polymer. Primary and secondary alcohols were confirmed to be the main oxidation products of this material, and the total percent oxidation correlated with data obtained from oxidation rate measurements. The chemical derivatization appears to be highly sensitive and can be used to establish the presence and identity of oxidation products in aged polymeric materials. This methodology represents a novel condition monitoring approach for the detection of chemical changes that are otherwise difficult to analyze.

  20. Chemical kinetic modeling of chlorinated hydrocarbons under stirred-reactor conditions

    SciTech Connect

    Pitz, W.J.; Westbrook, C.K.

    1990-10-04

    The combustin of chloroethane is modeled as a stirred reactor so that we can study critical emission characteristics of the reactor as a function of residence time. We examine important operating conditions such as pressure, temperature, and equivalence ratio and their influence on destructive efficiency of chloroethane and production of other chlorinated products. The model uses a detailed chemical kinetic mechanism that we have developed previously for C{sub 3} hydrocarbons. We have added to this mechanism the chemical kinetic mechanism for C{sub 2} chlorinated hydrocarbons developed by Senkan and coworkers. Some reactions have been added to Senkan's mechanism and some of the reaction-rate expressions have been updated to reflect recent developments in the literature. In the modeling calculations, sensitivity coefficients are determined to find which reaction-rate constants have the largest effect on destructive efficiency. 25 refs., 6 figs., 1 tab.

  1. On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

    USGS Publications Warehouse

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

  2. Purification characteristics of pothos for airborne chemicals in growing conditions and its evaluation

    NASA Astrophysics Data System (ADS)

    Sawada, Ayako; Oyabu, Takashi

    Plants have a purification capability to various kinds of airborne chemicals. The capability largely depends on the growing conditions of the plant. In this study, the capabilities of the plants growing in the following three conditions were examined: (a) put the subjective plant in a bowl of tap water, (b) put the one in a pot of growing water for over 1 year and (c) in the pot-soil. The room temperature and light intensity were changed in the experiments. As a result, it became obvious that the capability to formaldehyde varied in some degree according to room temperature. The capability decreased linearly in 12-25 C in the case of (a), it did not change largely in the case of (b) and it indicated maximum value at 21 C in the case of (c). The temperature belonged to optimal growth range of the plant. The capability-order is as follows: (a)<(b)<(c). The capability increased as the light intensity increased in each growth-condition. The capabilities to acetone, toluene and xylene were also examined. It became obvious that the capability became lower as the molecular weight of the chemical became larger.

  3. Validity conditions for stochastic chemical kinetics in diffusion-limited systems

    PubMed Central

    Gillespie, Daniel T.; Petzold, Linda R.; Seitaridou, Effrosyni

    2014-01-01

    The chemical master equation (CME) and the mathematically equivalent stochastic simulation algorithm (SSA) assume that the reactant molecules in a chemically reacting system are dilute and well-mixed throughout the containing volume. Here we clarify what those two conditions mean, and we show why their satisfaction is necessary in order for bimolecular reactions to physically occur in the manner assumed by the CME and the SSA. We prove that these conditions are closely connected, in that a system will stay well-mixed if and only if it is dilute. We explore the implications of these validity conditions for the reaction-diffusion (or spatially inhomogeneous) extensions of the CME and the SSA to systems whose containing volumes are not necessarily well-mixed, but can be partitioned into cubical subvolumes (voxels) that are. We show that the validity conditions, together with an additional condition that is needed to ensure the physical validity of the diffusion-induced jump probability rates of molecules between voxels, require the voxel edge length to have a strictly positive lower bound. We prove that if the voxel edge length is steadily decreased in a way that respects that lower bound, the average rate at which bimolecular reactions occur in the reaction-diffusion CME and SSA will remain constant, while the average rate of diffusive transfer reactions will increase as the inverse square of the voxel edge length. We conclude that even though the reaction-diffusion CME and SSA are inherently approximate, and cannot be made exact by shrinking the voxel size to zero, they should nevertheless be useful in many practical situations. PMID:24511926

  4. Chemical speciation of neptunium(VI) under strongly alkaline conditions. Structure, composition, and oxo ligand exchange.

    PubMed

    Clark, David L; Conradson, Steven D; Donohoe, Robert J; Gordon, Pamela L; Keogh, D Webster; Palmer, Phillip D; Scott, Brian L; Tait, C Drew

    2013-04-01

    Hexavalent neptunium can be solubilized in 0.5-3.5 M aqueous MOH (M = Li(+), Na(+), NMe4(+) = TMA(+)) solutions. Single crystals were obtained from cooling of a dilute solution of Co(NH3)6Cl3 and NpO2(2+) in 3.5 M [N(Me)4]OH to 5 °C. A single-crystal X-ray diffraction study revealed the molecular formula of [Co(NH3)6]2[NpO2(OH)4]3·H2O, isostructural with the uranium analogue. The asymmetric unit contains three distinct NpO2(OH)4(2-) ions, each with pseudooctahedral coordination geometry with trans-oxo ligands. The average Np═O and Np-OH distances were determined to be 1.80(1) and 2.24(1) Å, respectively. EXAFS data and fits at the Np L(III)-edge on solid [Co(NH3)6]2[NpO2(OH)4]3·H2O and aqueous solutions of NpO2(2+) in 2.5 and 3.5 M (TMA)OH revealed bond lengths nearly identical with those determined by X-ray diffraction but with an increase in the number of equatorial ligands with increasing (TMA)OH concentration. Raman spectra of single crystals of [Co(NH3)6]2[NpO2(OH)4]3·H2O reveal a ν1(O═Np═O) symmetric stretch at 741 cm(-1). Raman spectra of NpO2(2+) recorded in a 0.6-2.2 M LiOH solution reveal a single ν1 frequency of 769 cm(-1). Facile exchange of the neptunyl oxo ligands with the water solvent was also observed with Raman spectroscopy performed with (16)O- and (18)O-enriched water solvent. The combination of EXAFS and Raman data suggests that NpO2(OH)4(2-) is the dominant solution species under the conditions of study and that a small amount of a second species, NpO2(OH)5(3-), may also be present at higher alkalinity. Crystal data for [Co(NH3)6]2[NpO2(OH)4]3·H2O: monoclinic, space group C2/c, a = 17.344(4) Å, b = 12.177(3) Å, c = 15.273 Å, β = 120.17(2)°, Z = 4, R1 = 0.0359, wR2 = 0.0729. PMID:23485079

  5. Bake condition effect on hybrid lithography process for negative-tone chemically amplified resists

    NASA Astrophysics Data System (ADS)

    Pain, Laurent; Sala, F.; Higgins, C.; Dal'zotto, B.; Tedesco, Serge V.

    2000-06-01

    This paper presents the process optimization study of negative tone Chemically Amplified Resists (CAR) under E-Beam exposure. The importance of post apply bake temperature choice on resolution is underlined. The process study determines the process window in which optimal conditions of both post apply and post exposure bake steps are defined and present a method to define more precisely the thermal cross-linking onset. Finally lithographic performances of CARs are studied and we show that resolution can be pushed down to 40 nm.

  6. Infrared spectra and chemical abundance of methyl propionate in icy astrochemical conditions

    NASA Astrophysics Data System (ADS)

    Sivaraman, B.; Radhika, N.; Das, A.; Gopakumar, G.; Majumdar, L.; Chakrabarti, S. K.; Subramanian, K. P.; Raja Sekhar, B. N.; Hada, M.

    2015-04-01

    We carried out an experiment in order to obtain the infrared (IR) spectra of methyl propionate (CH3CH2COOCH3) in astrochemical conditions and present the IR spectra for future identification of this molecule in the interstellar medium (ISM). The experimental IR spectrum is compared with the theoretical spectrum, and an attempt was made to assign the observed peak positions to their corresponding molecular vibrations in condensed phase. Moreover, our calculations suggest that methyl propionate must be synthesized efficiently within the complex chemical network of the ISM and therefore be present in cold dust grains, awaiting identification.

  7. Carbon nanofiber aerogels for emergent cleanup of oil spillage and chemical leakage under harsh conditions.

    PubMed

    Wu, Zhen-Yu; Li, Chao; Liang, Hai-Wei; Zhang, Yu-Ning; Wang, Xin; Chen, Jia-Fu; Yu, Shu-Hong

    2014-01-01

    To address oil spillage and chemical leakage accidents, the development of efficient sorbent materials is of global importance for environment and water source protection. Here we report on a new type of carbon nanofiber (CNF) aerogels as efficient sorbents for oil uptake with high sorption capacity and excellent recyclability. Importantly, the oil uptake ability of the CNF aerogels can be maintained over a wide temperature range, from liquid nitrogen temperature up to ca. 400C, making them suitable for oil cleanup under harsh conditions. The outstanding sorption performance of CNF aerogels is associated with their unique physical properties, such as low density, high porosity, excellent mechanical stability, high hydrophobicity and superoleophilicity. PMID:24518262

  8. Iodine-xenon, chemical, and petrographie studies of Semarkona chondrules: Evidence for the timing of aqueous alteration

    USGS Publications Warehouse

    Swindle, T.D.; Grossman, J.N.; Olinger, C.T.; Garrison, D.H.

    1991-01-01

    We have performed INAA, petrographie, and noble gas analyses on seventeen chondrules from the Semarkona meteorite (LL3.0) primarily to study the relationship of the I-Xe system to other measured properties. We observe a range of ???10 Ma in apparent I-Xe ages. The three latest apparent ages fall in a cluster, suggesting the possibility of a common event. The initial 129I/127I ratio (R0) is apparently related to chondrule type and/or mineralogy, with nonporphyritic and pyroxene-rich chondrules showing evidence for lower R0'S (later apparent I-Xe ages) than porphyritic and olivine-rich chondrules. In addition, chondrules with sulfides on or near the surface have lower R0S than other chondrules. The 129Xe/132Xe ratio in the trapped Xe component anticorrelates with R0, consistent with evolution of a chronometer in a closed system or in multiple similar systems. On the basis of these correlations, we conclude that the variations in R0 represent variations in ages, and that later event(s), possibly aqueous alteration, preferentially affected chondrules with nonporphyritic textures and/or sulfide-rich exteriors about 10 Ma after the formation of the chondrules. ?? 1991.

  9. Iodine-xenon, chemical, and petrographic studies of Semarkona chondrules - Evidence for the timing of aqueous alteration

    NASA Technical Reports Server (NTRS)

    Swindle, T. D.; Grossman, J. N.; Olinger, C. T.; Garrison, D. H.

    1991-01-01

    The relationship of the I-Xe system of the Semarkona meteorite to other measured properties is investigated via INAA, petrographic, and noble-gas analyses on 17 chondrules from the meteorite. A range of not less than 10 Ma in apparent I-Xe ages is observed. The three latest apparent ages fall in a cluster, suggesting the possibility of a common event. It is argued that the initial I-129/I-127 ratio (R0) is related to chondrule type and/or mineralogy, with nonporphyritic and pyroxene-rich chondrules showing evidence for lower R0s than porphyritic and olivine-rich chondrules. Chondrules with sulfides on or near the surface have lower R0s than other chondrules. The He-129/Xe-132 ratio in the trapped Xe component anticorrelates with R0, consistent with the evolution of a chronometer in a closed system or in multiple systems. It is concluded that the variations in R0 represent variations in ages, and that later events, possibly aqueous alteration, preferentially affected chondrules with nonporphyritic textures and/or sulfide-rich exteriors about 10 Ma after the formation of the chondrules.

  10. Chemical relevance of the copper(II)— L-carnosine system in aqueous solution: A thermodynamic and spectrophotometric study

    NASA Astrophysics Data System (ADS)

    Daniele, Pier G.; Prenesti, Enrico; Zelano, Vincenzo; Ostacoli, Giorgio

    1993-08-01

    The copper(II)— L-carnosine (L -) system has been re-investigated in aqueous solution, at I = 0.1 mol dm -1, different temperatures (5⩽ t⩽45°C) and with metal to ligand ratios ranging from 3:1 to 1:3. Both potentiometry and visible spectrophotometry were employed. From an overall consideration of all experiments, [CuLH] 2+, [CuL] +, [CuLH -1]°, [Cu 2L 2H -2]° and [Cu 2LH -1] 2+ were recognized as the species which provide the best interpretation of experimental data. The complex formation constants, determined at different temperatures, allowed us to obtain reliable values of Δ H° and good estimates of Δ C° p. From visible spectrophotometric measurements, carried out at different pH and metal to ligand ratios, it was possible to calculate the electronic spectrum of each complex formed in solution. A structure is also proposed for each species, on the basis of thermodynamic and spectral results.

  11. Adsorption of nitrate from aqueous solution by magnetic amine-crosslinked biopolymer based corn stalk and its chemical regeneration property.

    PubMed

    Song, Wen; Gao, Baoyu; Xu, Xing; Wang, Fang; Xue, Nan; Sun, Shenglei; Song, Wuchang; Jia, Ruibao

    2016-03-01

    A novel adsorbent of magnetic amine-crosslinked biopolymer based corn stalk (MAB-CS) was synthesized and used for nitrate removal from aqueous solution. The characters and adsorption mechanisms of this bio-adsorbent were determined by using VSM, TGA, XRD, SEM, TEM, FT-IR and XPS, respectively. The results revealed that the saturated magnetization of MAB-CS reached 6.25 emu/g. Meanwhile, the studies of various factors indicated that this novel magnetic bio-adsorbent performed well over a considerable wide pH range of 6.0 ∼ 9.0, and the presence of PO4(3-) and SO4(2-) would markedly decrease the nitrate removal efficiency. Furthermore, the nitrate adsorption by MAB-CS perfectly fitted the Langmuir isotherm model (R(2)=0.997-0.999) and pseudo second order kinetic model (R(2)=0.953-0.995). The calculated nitrate adsorption capacity of MAB-CS was 102.04 mg/g at 318 K by Langmuir model, and thermodynamic study showed that nitrate adsorption is an spontaneous endothermic process. The regeneration experiments indicated its merit of regeneration and stability with the recovery efficient of 118 ∼ 147%. By integrating the experimental results, it was found that the removal of nitrate was mainly via electrostatic attraction and ion exchange. And this novel bio-adsorbent prepared in this work could achieve effective removal of nitrate and rapid separation from effluents simultaneously. PMID:26561752

  12. Chemical Processing in High-Pressure Aqueous Environments. 9. Process Development for Catalytic Gasification of Algae Feedstocks

    SciTech Connect

    Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.; Rotness, Leslie J.; Olarte, Mariefel V.; Zacher, Alan H.

    2012-07-26

    Through the use of a metal catalyst, gasification of wet algae slurries can be accomplished with high levels of carbon conversion to gas at relatively low temperature (350 C). In a pressurized-water environment (20 MPa), near-total conversion of the organic structure of the algae to gases has been achieved in the presence of a supported ruthenium metal catalyst. The process is essentially steam reforming, as there is no added oxidizer or reagent other than water. In addition, the gas produced is a medium-heating value gas due to the synthesis of high levels of methane, as dictated by thermodynamic equilibrium. As opposed to earlier work, biomass trace components were removed by processing steps so that they did not cause processing difficulties in the fixed catalyst bed tubular reactor system. As a result, the algae feedstocks, even those with high ash contents, were much more reliably processed. High conversions were obtained even with high slurry concentrations. Consistent catalyst operation in these short-term tests suggested good stability and minimal poisoning effects. High methane content in the product gas was noted with significant carbon dioxide captured in the aqueous byproduct in combination with alkali constituents and the ammonia byproduct derived from proteins in the algae. High conversion of algae to gas products was found with low levels of byproduct water contamination and low to moderate loss of carbon in the mineral separation step.

  13. Solvent effects on chemical processes. I: Solubility of aromatic and heterocyclic compounds in binary aqueous-organic solvents.

    PubMed

    Khossravi, D; Connors, K A

    1992-04-01

    The standard free energy change (delta G0) for equilibrium dissolution in binary solvent mixtures is written as a sum of effects arising from solvent-solvent interactions (the general medium effect), solvent-solute interactions (the solvation effect), and solute-solute interactions (the intersolute effect). The general medium effect is given by gA gamma, where g is a curvature correction factor to the surface tension (gamma) and A is the molecular cavity surface area. A new feature is the definition of gamma to be that value appropriate to the equilibrium mean solvation shell composition. The solvation effect is modeled by stoichiometric stepwise competitive equilibria between the two solvent components for the solute. The intersolute effect includes the crystal energy and solution phase interactions. In this work, water was solvent component 1, and various miscible organic cosolvents served as solvent component 2. Relating all data to the fully aqueous solution gives an explicit expression for delta M delta G0, the solvent effect on the free energy change, as a function of the mole fractions x1 and x2. This function is a binding isotherm. Nonlinear regression leads (for a two-step solvation scheme) to estimates of the solvation exchange constants K1 and K2 and the parameter gA. This relationship was applied to 44 systems comprising combinations of 31 solutes and eight organic cosolvents. Curve fits were good to excellent, and most of the parameter estimates had physically reasonable magnitudes. PMID:1308660

  14. Real-time detection of concealed chemical hazards under ambient light conditions using Raman spectroscopy.

    PubMed

    Cletus, Biju; Olds, William; Fredericks, Peter M; Jaatinen, Esa; Izake, Emad L

    2013-07-01

    Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for noninvasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs, and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper, and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than 1 min. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers, and customs checkpoints. PMID:23692353

  15. Optimizing chemical conditioning for odour removal of undigested sewage sludge in drying processes.

    PubMed

    Vega, Esther; Monclús, Hèctor; Gonzalez-Olmos, Rafael; Martin, Maria J

    2015-03-01

    Emission of odours during the thermal drying in sludge handling processes is one of the main sources of odour problems in wastewater treatment plants. The objective of this work was to assess the use of the response surface methodology as a technique to optimize the chemical conditioning process of undigested sewage sludges, in order to improve the dewaterability, and to reduce the odour emissions during the thermal drying of the sludge. Synergistic effects between inorganic conditioners (iron chloride and calcium oxide) were observed in terms of sulphur emissions and odour reduction. The developed quadratic models indicated that optimizing the conditioners dosage is possible to increase a 70% the dewaterability, reducing a 50% and 54% the emission of odour and volatile sulphur compounds respectively. The optimization of the conditioning process was validated experimentally. PMID:25438118

  16. Application of pervaporation and vapor permeation processes to separate aqueous ethanol solution through chemically modified Nylon 4 membranes

    SciTech Connect

    Wang, Y.H.; Teng, M.Y.; Lee, K.R.; Wang, D.M.; Lai, J.Y.

    1998-08-01

    The pervaporation performance of a Nylon 4 membrane, chemically grafted by N,N-dimethylaminoethyl methacrylate (DMAEM), DMAEM-g-N4, was studied by measurement of the permeation ratio and the pervaporation separation index. It was found that the water permselectivity and permeation rate for the chemically modified Nylon 4 membrane were higher than those of the unmodified Nylon 4 membrane. Optimum pervaporation results, a separation factor of 28.3, and a permeation rate of 439 g/m{sup 2}{center_dot}h, were obtained when the degree of grafting was 12.7%. It was also found that all the permeation ratios at low temperature were less than unity. In addition, compared with pervaporation, vapor permeation effectively increases the permselectivity of water.

  17. Surfactant concentration dependence of structure and photocatalytic properties of zinc oxide rods prepared using chemical synthesis in aqueous solutions.

    PubMed

    Usui, Hiroyuki

    2009-08-15

    The author prepared zinc oxide (ZnO) rods using chemical synthesis in surfactant solutions, and investigated the surfactant concentration dependence on their structure and photocatalytic properties. With increased surfactant concentration, the ZnO morphology changed from a single straight rod to radial-shaped rods, with progressive lattice shrinkage of ZnO crystals. In the emission bands of ultraviolet and yellow, the photoluminescence intensities were decreased with increasing surfactant concentration. These results suggest that the surfactant molecules impart the radial structure through chemical activation of the ZnO surface, which engenders formation of dense lattice defects. The photocatalytic activity was improved through a two-step growth of the radial-shaped rods because of the existence of good crystallinity and interstitial nanospaces of radial-shaped rods. PMID:19473665

  18. Combined physical and chemical methods to control lesser mealworm beetles under laboratory conditions.

    PubMed

    Wolf, Jônatas; Potrich, Michele; Lozano, Everton R; Gouvea, Alfredo; Pegorini, Carla S

    2015-06-01

    The lesser mealworm beetle, Alphitobius diaperinus (Panzer) (Coleoptera: Tenebrionidae), is an important insect pest. The insect acts as a disease vector and reservoir, negatively affecting the health of birds and humans, and harming poultry husbandry. Controlling the lesser mealworm is generally based on using synthetic chemical insecticides, which are sometimes ineffective, and is limited due to market concerns regarding the toxicity of chemical residues in food products. In this context, the present study aimed to evaluate the potential for the combination of physical and chemical methods to control A. diaperinus. Bioassays were conducted using poultry bedding and known populations of beetle adults and larvae. The treatments consisted of the isolated application of 400 g/m2 hydrated lime; 20% added moisture (distilled water); temperature increase to 45°C; an insecticide composed of cypermethrin, chlorpyrifos, and citronellal; and a combination of these factors. Beetle mortality was measured at 7 and 10 d of treatment. The hydrated lime and moisture treatments alone did not control A. diaperinus. Raising the temperature of the poultry bedding to 45°C effectively controlled both larvae (90±6%) and adults (90±4%). The use of insecticide provided adequate control of A. diaperinus in the conditions of the bioassay (93±2% and 68±5% for adults and larvae, respectively). The combination of the studied factors led to the total control of larvae and adults after 7 d of treatment. PMID:25834245

  19. Aqueous size-exclusion chromatographic separations of intact proteins under native conditions: Effect of pressure on selectivity and efficiency.

    PubMed

    De Vos, Jelle; Kaal, Erwin R; Swart, Remco; Baca, Martyna; Heyden, Yvan Vander; Eeltink, Sebastiaan

    2016-02-01

    The selectivity and separation efficiency of aqueous size-exclusion chromatographic separations of intact proteins were assessed for different flow rates, using columns packed with 3 and 5 μm silica particles containing 150 and 290 Å stagnant pores. A mixture of intact proteins with molecular weights ranging between 17 000 and 670 000 Da was used to construct the calibration curves. Both the model fit and the predictive properties, using a leave-one-out strategy, of different polynomial models (up to fifth order) were evaluated for different flow rates. The best compromise between model fit and predictive properties was obtained using a third-order polynomial model. The accuracy of the predictive properties decreased with 10% with an eightfold increase in the flow rate. No changes in retention factors (hence selectivity) were observed in the flow-rate range applied. A strong correlation between molecular weight and plate height was observed. Exclusion of large-molecular-weight proteins led to a significant reduction in the stationary-phase mass-transfer contribution to the total plate-height value, and this effect was also independent of the flow rate applied. The kinetic-performance limits, in terms of plate number and time, and optimal column-length particle-size combinations were determined at the maximum recommended operating pressure of the size-exclusion chromatography columns (20 MPa). Finally, the possibilities of method speed-up using ultra-high-pressure size-exclusion chromatography in combination with columns packed with sub-2 μm particles are discussed. PMID:26549319

  20. Role of roasting conditions in the profile of volatile flavor chemicals formed from coffee beans.

    PubMed

    Moon, Joon-Kwan; Shibamoto, Takayuki

    2009-07-01

    The volatile chemicals in dichloromethane extracts from green coffee beans, roasted at 230 degrees C for 12 min (light), at 240 degrees C for 14 min (medium), at 250 degrees C for 17 min (city), or at 250 degrees C for 21 min (French), were analyzed by gas chromatography and gas chromatography-mass spectrometry. Among the 52 volatile compounds identified, the major compounds were 5-hydroxymethylfurfural, furfuryl alcohol, and 6-methyl-3,5-dihydroxy-4H-pyran-4-one in light-roasted beans; furfuryl alcohol, 5-hydroxymethylfurfural, and gamma-butyrolactone in medium-roasted beans; furfuryl alcohol, gamma-butyrolactone, and 2-acetylpyrrole in city-raosted beans; and gamma-butyrolactone, furfuryl alcohol, and catechol in French-roasted beans. Furfural derivatives and furanones were yielded in relatively high concentrations under mild roasting conditions and then reduced at higher roasting intensities. More pyridines and pyrroles were formed by high roasting intensities than by mild roasting intensities. Chlorogenic acid degradation products, phenols, and a lactone were produced more by high roasting intensities than by low roasting intensities. The results of the present study suggest that controlling the roasting conditions according to the formation of particular chemicals can prepare a roasted coffee with preferable flavor. PMID:19579294

  1. Effects of biomass types and carbonization conditions on the chemical characteristics of hydrochars.

    PubMed

    Cao, Xiaoyan; Ro, Kyoung S; Libra, Judy A; Kammann, Claudia I; Lima, Isabel; Berge, Nicole; Li, Liang; Li, Yuan; Chen, Na; Yang, John; Deng, Baolin; Mao, Jingdong

    2013-10-01

    Effects of biomass types (bark mulch versus sugar beet pulp) and carbonization processing conditions (temperature, residence time, and phase of reaction medium) on the chemical characteristics of hydrochars were examined by elemental analysis, solid-state ¹³C NMR, and chemical and biochemical oxygen demand measurements. Bark hydrochars were more aromatic than sugar beet hydrochars produced under the same processing conditions. The presence of lignin in bark led to a much lower biochemical oxygen demand (BOD) of bark than sugar beet and increasing trends of BOD after carbonization. Compared with those prepared at 200 °C, 250 °C hydrochars were more aromatic and depleted of carbohydrates. Longer residence time (20 versus 3 h) at 250 °C resulted in the enrichment of nonprotonated aromatic carbons. Both bark and sugar beet pulp underwent deeper carbonization during water hydrothermal carbonization than during steam hydrothermal carbonization (200 °C, 3 h) in terms of more abundant aromatic C but less carbohydrate C in water hydrochars. PMID:24004410

  2. An evaluation of the chemical, radiological, and ecological conditions of West Lake on the Hanford site

    SciTech Connect

    Poston, T.M.; Price, K.L.; Newcomer, D.R.

    1991-03-01

    West Lake and its immediate surrounding basin represent a unique habitat that is dominated by highly saline water and soil. The basin offers a valuable research site for studies of a rare and complex wetland area in the desert. This report is an evaluation of the chemical, radiological, and ecological conditions at West Lake and describes how ground water influences site properties. The scope of this evaluation consisted of a sampling program in 1989 and a review of data from the perspective of assessing the impact of Hanford Site operations on the physical, chemical, and ecological conditions of West Lake and its surrounding basin. The water level in West Lake fluctuates in relation to changes in the water table. The connection between West Lake and ground water is also supported by the presence of {sup 3}H and {sup 99}Tc in the ground water and in the lake. There are relatively high concentrations of uranium in West Lake; the highest concentrations are found in the northernmost isolated pool. Analyses of water, sediment, vegetation, and soil indicate possible shifts of isotropic ratios that indicate a reduction of {sup 235}U. Uranium-236 was not detected in West Lake water; its presence would indicate neutron-activated {sup 235}U from fuel reprocessing at Hanford. Trace metals are found at elevated concentrations in West Lake. Arsenic, chromium, copper, and zinc were found at levels in excess of US Environmental Protection Agency water quality criteria. Levels of radiological and chemical contamination in the West Lake basin are relatively low. Concentrations of fission isotopes exceed those that could be explained by atmospheric fallout, but fall short of action levels for active waste management areas. 31 refs., 8 figs., 18 tabs.

  3. Chemical stimulation or glutamate injections in the nucleus of solitary tract enhance conditioned taste aversion.

    PubMed

    García-Medina, Nadia Edith; Vera, Gabriela; Miranda, María Isabel

    2015-02-01

    Taste memory depends on motivational and post-ingestional consequences after a single taste-illness pairing. During conditioned taste aversion (CTA), the taste and visceral pathways reach the nucleus of the solitary tract (NTS), which is the first relay in the CNS and has a vital function in receiving vagal chemical stimuli and humoral signals from the area postrema that receives peripheral inputs also via vagal afferent fibers. The specific aim of the present set of experiments was to determine if the NTS is involved in the noradrenergic and glutamatergic activation of the basolateral amygdala (BLA) during CTA. Using in vivo microdialysis, we examined whether chemical NTS stimulation induces norepinephrine (NE) and/or glutamate changes in the BLA during visceral stimulation with intraperitoneal (i.p.) injections of low (0.08 M) and high (0.3 M) concentrations of lithium chloride (LiCl) during CTA training. The results showed that strength of CTA can be elicited by chemical NTS stimulation (Ringer's high potassium solution; 110 mM KCl) and by intra-NTS microinjections of glutamate, immediately after, but not before, low LiCl i.p. injections that only induce a week aversive memory. However visceral stimulation (with low or high i.p. LiCl) did not induce significantly more NE release in the amygdala compared with the NE increment induced by NTS potassium depolarization. In contrast, high i.p. concentrations of LiCl and chemical NTS stimulation induced a modest glutamate sustained release, that it is not observed with low LiCl i.p. injections. These results indicate that the NTS mainly mediates the visceral stimulus processing by sustained releasing glutamate in the BLA, but not by directly modulating NE release in the BLA during CTA acquisition, providing new evidence that the NTS has an important function in the transmission of signals from the periphery to brain systems that process aversive memory formation. PMID:25251840

  4. The influence of a non-aqueous phase liquid (NAPL) and chemical oxidant application on perfluoroalkyl acid (PFAA) fate and transport.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2016-04-01

    One dimensional column experiments were conducted using saturated porous media containing residual trichloroethylene (TCE) to understand the effects of non-aqueous phase liquids (NAPLs) and chemical oxidation on perfluoroalkyl acid (PFAA) fate and transport. Observed retardation factors and data from supporting batch studies suggested that TCE provides additional sorption capacity that can increase PFAA retardation (i.e., decreased mobility), though the mechanisms remain unclear. Treatment with persulfate activated with FeCl2 and citric acid, catalyzed hydrogen peroxide (CHP), or permanganate did not result in oxidative transformations of PFAAs. However, impacts on PFAA sorption were apparent, and enhanced sorption was substantial in the persulfate-treated columns. In contrast, PFAA transport was accelerated in permanganate- and CHP-treated columns. Ultimately, PFAA transport in NAPL contaminated groundwater is likely influenced by porous media properties, NAPL characteristics, and water quality properties, each of which can change due to chemical oxidant treatment. For contaminated sites for which ISCO is a viable treatment option, changes to PFAA transport and the implications thereof should be included as a component of the remediation evaluation and selection process. PMID:26854608

  5. Study of CdS epitaxial films chemically deposited from aqueous solutions on InP single crystals

    SciTech Connect

    Froment, M.; Bernard, M.C.; Cortes, R.; Mokili, B.; Lincot, D.

    1995-08-01

    Epitaxial growth of cadmium sulfide on InP single crystals is achieved by chemical bath deposition (CBD) in ammonia solutions at near room temperature. A better understanding of the correlations between the deposition parameters (temperature, bath composition) and the epitaxial quality is obtained by using electron diffraction and transmission techniques, x-ray diffraction, in combination with Raman spectroscopy. They are supplemented by electrochemical impedance and photocurrent experiments which give information on energetic structures between InP and CBD-CdS. Direct relations between the substrate properties and the growth habits of the CdS film (hexagonal vs. cubic, epitaxial vs. polycrystalline) are found.

  6. Physico-chemical studies in the removal of Sr(II) from aqueous solutions using activated sericite.

    PubMed

    Lalhmunsiama; Tiwari, Diwakar; Lee, Seung-Mok

    2015-09-01

    Sericite, a mica based natural clay, was annealed at 800 °C for 4 h followed by acid activation using 3.0 mol/L of HCl at 100 °C in order to obtain activated sericite (AS). The activation of sericite causes a significant increase in specific surface area. Further, SEM images of the AS showed a disordered and heterogeneous surface structure with mesopores on its surface whereas the pristine sericite possessed a compact layered structure. The materials were further employed in the removal of Sr(II) from aqueous solutions in a batch reactor system. Removal of Sr(II) was studied as a function of pH, concentration of adsorbate, contact time, background electrolyte concentrations and dose of adsorbents using pristine sericite and AS. The removal of Sr(II) was favoured increasing the pH of the solution and the extent of Sr(II) removal was increased with increasing the sorbate concentration. Equilibrium sorption data obtained with pristine sericite were fitted well to Langmuir adsorption isotherm whereas the sorption data collected using AS better fitted to the Freundlich adsorption isotherm. The time dependence sorption data showed that the uptake of Sr(II) was very rapid and an apparent sorption equilibrium was achieved within 30 min and 60 min of contact for sericite and AS, respectively. The kinetic data were modelled to the pseudo-first order and pseudo-second order rate kinetics and sorption capacities as well as rate constants were evaluated. Increase in background electrolyte concentrations NaNO3 (0.001-0.1 mol/L) indicated that the presence of NaNO3 caused to decrease the percent removal of Sr(II) by sericite and AS. Furthermore, fixed-bed column reactor operations were performed to obtain the breakthrough data. The breakthrough data were fitted well to the non-linear Thomas equation. Therefore, the present study suggested that AS can be adequately applied for the removal of Sr(II) from the aquatic environment. PMID:26048059

  7. Chemical Reactivity of alpha-Pinene-derived Products in the Aqueous Phase: Implications on the Fate of Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Rindelaub, J. D.; Hostetler, M. A.; Lipton, M. A.; Shepson, P. B.

    2014-12-01

    The production of organic nitrates has significant atmospheric importance due to the impact on regional air quality by influencing NOx lifetimes and ozone formation. Additionally, these low volatility compounds readily partition into the particle phase and are important contributors to secondary organic aerosol. Once in the aerosol phase, organic nitrates undergo further chemical reactions that govern their fate in the atmosphere and, consequently, their impact on air quality. Recent research indicates that the presence of water on aerosol particles has a major impact on the reactivity of organic nitrates and that condensed phase hydrolysis leads to the destruction of organic nitrate species, depending on structure. Despite this knowledge, the chemical mechanisms, products, product reactivity and volatility are still uncertain, negatively impacting our understanding of aerosol phase processing and the contribution to air quality. To further understand the atmospheric impact of aerosol phase hydrolysis, we analyzed both condensed phase hydrolysis reactions involving alpha-pinene-derived standards and alpha-pinene photochemical chamber reaction filter samples, using a suite of spectroscopic and mass spectrometric techniques. We were able to measure the pH-dependent hydrolysis rate constants for several types of organic nitrates and identify specific reaction products. The chemistry involved exhibits a strong dependence on pH, providing important mechanistic clues. The results of this study will significantly contribute to our knowledge of aerosol phase chemistry and the impact on regional air quality with respect to the fate of organic nitrate species.

  8. Interpopulational Variations in Sexual Chemical Signals of Iberian Wall Lizards May Allow Maximizing Signal Efficiency under Different Climatic Conditions

    PubMed Central

    2015-01-01

    Sexual signals used in intraspecific communication are expected to evolve to maximize efficacy under a given climatic condition. Thus, chemical secretions of lizards might evolve in the evolutionary time to ensure that signals are perfectly tuned to local humidity and temperature conditions affecting their volatility and therefore their persistence and transmission through the environment. We tested experimentally whether interpopulational altitudinal differences in chemical composition of femoral gland secretions of male Iberian wall lizards (Podarcis hispanicus) have evolved to maximize efficacy of chemical signals in different environmental conditions. Chemical analyses first showed that the characteristics of chemical signals of male lizards differed between two populations inhabiting environments with different climatic conditions in spite of the fact that these two populations are closely related genetically. We also examined experimentally whether the temporal attenuation of the chemical stimuli depended on simulated climatic conditions. Thus, we used tongue-flick essays to test whether female lizards were able to detect male scent marks maintained under different conditions of temperature and humidity by chemosensory cues alone. Chemosensory tests showed that chemical signals of males had a lower efficacy (i.e. detectability and persistence) when temperature and dryness increase, but that these effects were more detrimental for signals of the highest elevation population, which occupies naturally colder and more humid environments. We suggest that the abiotic environment may cause a selective pressure on the form and expression of sexual chemical signals. Therefore, interpopulational differences in chemical profiles of femoral secretions of male P. hispanicus lizards may reflect adaptation to maximize the efficacy of the chemical signal in different climates. PMID:26121693

  9. Aerosol physical, chemical and optical properties observed in the ambient atmosphere during haze pollution conditions

    NASA Astrophysics Data System (ADS)

    Li, Zhengqiang; Xie, Yisong; Li, Donghui; Li, Kaitao; Zhang, Ying; Li, Li; Lv, Yang; Qie, Lili; Xu, Hua

    Aerosol’s properties in the ambient atmosphere may differ significantly from sampling results due to containing of abundant water content. We performed sun-sky radiometer measurements in Beijing during 2011 and 2012 winter to obtain distribution of spectral and angular sky radiance. The measurements are then used to retrieve aerosol physical, chemical and optical properties, including single scattering albedo, size distribution, complex refractive indices and aerosol component fractions identified as black carbon, brown carbon, mineral dust, ammonium sulfate-like components and water content inside particle matters. We found that during winter haze condition aerosol is dominated by fine particles with center radius of about 0.2 micron. Fine particles contribute about 93% to total aerosol extinction of solar light, and result in serious decrease of atmospheric visibility during haze condition. The percentage of light absorption of haze aerosol can up to about 10% among its total extinction, much higher than that of unpolluted conditions, that causes significant radiative cooling effects suppressing atmospheric convection and dispersion of pollutants. Moreover, the average water content occupies about one third of the ambient aerosol in volume which suggests the important effect of ambient humidity in the formation of haze pollution.

  10. Chitosan use in chemical conditioning for dewatering municipal-activated sludge.

    PubMed

    Zemmouri, H; Mameri, N; Lounici, H

    2015-01-01

    This work aims to evaluate the potential use of chitosan as an eco-friendly flocculant in chemical conditioning of municipal-activated sludge. Chitosan effectiveness was compared with synthetic cationic polyelectrolyte Sedipur CF802 (Sed CF802) and ferric chloride (FeCl₃). In this context, raw sludge samples from Beni-Messous wastewater treatment plant (WWTP) were tested. The classic jar test method was used to condition sludge samples. Capillary suction time (CST), specific resistance to filtration (SRF), cakes dry solid content and filtrate turbidity were analyzed to determine filterability, dewatering capacity of conditioned sludge and the optimum dose of each conditioner. Data exhibit that chitosan, FeCl₃and Sed CF802 improve sludge dewatering. Optimum dosages of chitosan, Sed CF802 and FeCl₃allowing CST values of 6, 5 and 9 s, were found, respectively, between 2-3, 1.5-3 and 6 kg/t ds. Both polymers have shown faster water removal with more permeable sludge. SRF values were 0.634 × 10¹², 0.932 × 10¹² and 2 × 10¹² m/kg for Sed CF802, chitosan and FeCl₃respectively. A reduction of 94.68 and 87.85% of the filtrate turbidity was obtained with optimal dosage of chitosan and Sed CF802, respectively. In contrast, 54.18% of turbidity abatement has been obtained using optimal dosage of FeCl₃. PMID:25812088

  11. Assessment Of Chemical Dispersant Effectiveness In A Wave Tank Under Regular Non-Breaking And Breaking Wave Conditions

    EPA Science Inventory

    Current chemical dispersant effectiveness tests for product selection are commonly performed with bench-scale testing apparatus. However, for the assessment of oil dispersant effectiveness under real sea state conditions, test protocols are required to have hydrodynamic conditio...

  12. Technical Note: Quantification of interferences of wet chemical HONO LOPAP measurements under simulated polar conditions

    NASA Astrophysics Data System (ADS)

    Kleffmann, J.; Wiesen, P.

    2008-11-01

    In the present pilot study, an optimized LOPAP instrument (LOng Path Absorption Photometer) for the detection of nitrous acid (HONO) in the atmosphere (DL 0.2 pptV) was tested at the high alpine research station Jungfraujoch at 3580 m altitude in the Swiss Alps under conditions comparable to polar regions. HONO concentrations in the range <0.5 50 pptV with an average of 7.5 pptV were observed at the Jungfraujoch. The diurnal profiles obtained exhibited clear maxima at noon and minima with very low concentration during the night supporting the proposed photochemical production of HONO. In good agreement with recent measurements at the South Pole, it was demonstrated, that interferences of chemical HONO instruments can significantly influence the measurements and lead to considerable overestimations, especially for low pollution level. Accordingly, the active correction of interferences is of paramount importance for the determination of reliable HONO data.

  13. Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

    NASA Technical Reports Server (NTRS)

    Johnson, R. E.

    1986-01-01

    Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

  14. Carbon nanofiber aerogels for emergent cleanup of oil spillage and chemical leakage under harsh conditions

    PubMed Central

    Wu, Zhen-Yu; Li, Chao; Liang, Hai-Wei; Zhang, Yu-Ning; Wang, Xin; Chen, Jia-Fu; Yu, Shu-Hong

    2014-01-01

    To address oil spillage and chemical leakage accidents, the development of efficient sorbent materials is of global importance for environment and water source protection. Here we report on a new type of carbon nanofiber (CNF) aerogels as efficient sorbents for oil uptake with high sorption capacity and excellent recyclability. Importantly, the oil uptake ability of the CNF aerogels can be maintained over a wide temperature range, from liquid nitrogen temperature up to ca. 400°C, making them suitable for oil cleanup under harsh conditions. The outstanding sorption performance of CNF aerogels is associated with their unique physical properties, such as low density, high porosity, excellent mechanical stability, high hydrophobicity and superoleophilicity. PMID:24518262

  15. Chemical Quantification of Atomic-Scale EDS Maps under Thin Specimen Conditions

    SciTech Connect

    Lu, Ping; Romero, Eric; Lee, Shinbuhm; MacManus-Driscoll, Judith L.; Jia, Quanxi

    2014-10-13

    We report our effort to quantify atomic-scale chemical maps obtained by collecting energy-dispersive X-ray spectra (EDS) using scanning transmission electron microscopy (STEM) (STEM-EDS). Under a thin specimen condition and when the EDS scattering potential is localized, the X-ray counts from atomic columns can be properly counted by fitting Gaussian peaks at the atomic columns, and can then be used for site-by-site chemical quantification. The effects of specimen thickness and X-ray energy on the Gaussian peak-width are investigated by using SrTiO3 (STO) as a model specimen. The relationship between the peak-width and spatial-resolution of an EDS map is also studied. Furthermore, the method developed by this work is applied to study a Sm-doped STO thin film and antiphase boundaries present within the STO film. We find that Sm atoms occupy both Sr and Ti sites but preferably the Sr sites, and Sm atoms are relatively depleted at the antiphase boundaries likely due to the effect of strain.

  16. Chemical Quantification of Atomic-Scale EDS Maps under Thin Specimen Conditions

    DOE PAGESBeta

    Lu, Ping; Romero, Eric; Lee, Shinbuhm; MacManus-Driscoll, Judith L.; Jia, Quanxi

    2014-10-13

    We report our effort to quantify atomic-scale chemical maps obtained by collecting energy-dispersive X-ray spectra (EDS) using scanning transmission electron microscopy (STEM) (STEM-EDS). Under a thin specimen condition and when the EDS scattering potential is localized, the X-ray counts from atomic columns can be properly counted by fitting Gaussian peaks at the atomic columns, and can then be used for site-by-site chemical quantification. The effects of specimen thickness and X-ray energy on the Gaussian peak-width are investigated by using SrTiO3 (STO) as a model specimen. The relationship between the peak-width and spatial-resolution of an EDS map is also studied. Furthermore,more » the method developed by this work is applied to study a Sm-doped STO thin film and antiphase boundaries present within the STO film. We find that Sm atoms occupy both Sr and Ti sites but preferably the Sr sites, and Sm atoms are relatively depleted at the antiphase boundaries likely due to the effect of strain.« less

  17. INITIAL CHEMICAL AND RESERVOIR CONDITIONS AT LOS AZUFRES WELLHEAD POWER PLANT STARTUP

    SciTech Connect

    Kruger, P.; Semprini, L.; Verma, S.; Barragan, R.; Molinar, R.; Aragon, A.; Ortiz, J.; Miranda, C.

    1985-01-22

    One of the major concerns of electric utilities in installing geothermal power plants is not only the longevity of the steam supply, but also the potential for changes in thermodynamic properties of the resource that might reduce the conversion efficiency of the design plant equipment. Production was initiated at Los Azufres geothermal field with wellhead generators not only to obtain electric energy at a relatively early date, but also to acquire needed information about the resource so that plans for large central power plants could be finalized. Commercial electric energy production started at Los Azufres during the summer of 1982 with five 5-MWe wellhead turbine-generator units. The wells associated with these units had undergone extensive testing and have since been essentially in constant production. The Los Azufres geothermal reservoir is a complex structural and thermodynamic system, intersected by at least 4 major parallel faults and producing geothermal fluids from almost all water to all steam. The five wellhead generators are associated with wells of about 30%, 60%, and 100% steam fraction. A study to compile existing data on the chemical and reservoir conditions during the first two years of operation has been completed. Data have been compiled on mean values of wellhead and separator pressures, steam and liquid flowrates, steam fraction, enthalpy, and pertinent chemical components. The compilation serves both as a database of conditions during the start-up period and as an initial point to observe changes with continued and increased production. Current plans are to add additional wellhead generators in about two years followed by central power plants when the data have been sufficiently evaluated for optimum plant design. During the next two years, the data acquired at the five 5-MWe wellhead generator units can be compared to this database to observe any significant changes in reservoir behavior at constant production.

  18. Chemical Characterization of Extrasolar Super-Earths - Interiors, Atmospheres, and Formation Conditions

    NASA Astrophysics Data System (ADS)

    Madhusudhan, Nikku; Lee, K.; Uts, I.; Mousis, O.

    2013-01-01

    Recent observations are allowing unprecedented measurements of masses and radii of low-mass transiting extrasolar planets, particularly super-Earths which are defined as planets with masses between 1 and 10 Earth masses. The observed masses, radii, and temperatures of super-Earths provide constraints on their interior structures, geophysical conditions, as well as their atmospheric compositions. Some of the most recently detected super-Earths span a wide gamut of possible compositions, from super-Mercuries and lava planets to water worlds with thick volatile envelopes. In this work, we report joint constraints on the interior and atmospheric compositions of several super-Earths and discuss their possible formation scenarios using new and comprehensive hybrid models of their interiors, non-gray atmospheres, and formation conditions. Our model constraints are based on the masses and visible radii, as well as the latest infrared measurements of transmission and emission spectrophotometry where available, in addition to revised estimates of the stellar parameters. We will present a comparative analysis of several transiting super-Earths currently known and will discuss in detail two super-Earths (GJ 1214b and 55 Cancri e) which have atmospheric data available and which represent two distinct end members in the thermo-chemical phase space of super-Earth conditions. We will also discuss the implications of our results for the diversity of geochemical and geophysical conditions on super-Earths. We will conclude with comments on new observational, theoretical, and experimental efforts that are critical to detailed characterization of super-Earths.

  19. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers observed during aqueous phase processing.

  20. Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA

    NASA Technical Reports Server (NTRS)

    Kawamura, K.; Nagahama, M.; Kuranoue, K.

    2005-01-01

    The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions. c2005 COSPAR. Published by Elsevier Ltd. All rights reserved.

  1. Application of Zero-Valent Iron Nanoparticles for the Removal of Aqueous Zinc Ions under Various Experimental Conditions

    PubMed Central

    Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2014-01-01

    Application of zero-valent iron nanoparticles (nZVI) for Zn2+ removal and its mechanism were discussed. It demonstrated that the uptake of Zn2+ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn2+ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn2+ removal by nZVI. The DO enhanced the removal efficiency of Zn2+. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn2+ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn2+ by nZVI because the existing H+ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn2+ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn2+ were higher than Cd2+. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn2+. PMID:24416439

  2. [Adsorption of calcium ion from aqueous solution using Na(+)-conditioned clinoptilolite for hot-water softening].

    PubMed

    Zhang, Shuo; Wang, Dong; Chen, Yuan-Chao; Zhang, Xing-Wen; Chen, Gui-Jun

    2015-02-01

    This work investigated adsorptive removal of calcium ion (Ca2+) by virtue of Na(+) -conditioned clinoptilolite simulating the process of softening for industrial hot-water system. Influential factors such as the activation/regeneration of sorbent and solution pH were tested. The kinetics/thermodynamics for adsorption of Ca2+ were analyzed and discussed. Results showed that: (1) The adsorption rate was in good agreement with the pseudo-second order kinetic models, and the process of adsorption better followed the Langmuir model; (2) Higher solution temperature allowed an enhanced efficiency on Ca2+ removal, albeit the maximum adsorption capacity of Na(+)-conditioned clinoptilolite was hardly affected; (3) The process of adsorption was dominated by chemisorption, and also characterized by entropy increase with spontaneous/endothermic nature; (4) Solution temperature was suggested to be controlled within the range of 6 to 10, and more than 9 times of sorbent regeneration could be ensured for an effective adsorption towards Ca2+ with initial concentration less than 20 mg x L(-1). It was demonstrated that the activated clinoptilolite should be a promising alternative adsorbent for industrial hot-water softening. PMID:26031107

  3. Atomistic Simulations of Chemical Reactivity of TATB Under Thermal and Shock Conditions

    SciTech Connect

    Manaa, M R; Reed, E J; Fried, L E

    2009-09-23

    The study of chemical transformations that occur at the reactive shock front of energetic materials provides important information for the development of predictive models at the grain-and continuum scales. A major shortcoming of current high explosives models is the lack of chemical kinetics data of the reacting explosive in the high pressure and temperature regimes. In the absence of experimental data, long-time scale atomistic molecular dynamics simulations with reactive chemistry become a viable recourse to provide an insight into the decomposition mechanism of explosives, and to obtain effective reaction rate laws. These rates can then be incorporated into thermo-chemical-hydro codes (such as Cheetah linked to ALE3D) for accurate description of the grain and macro scales dynamics of reacting explosives. In this talk, I will present quantum simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals under thermal decomposition (high density and temperature) and shock compression conditions. This is the first time that condensed phase quantum methods have been used to study the chemistry of insensitive high explosives. We used the quantum-based, self-consistent charge density functional tight binding method (SCC{_}DFTB) to calculate the interatomic forces for reliable predictions of chemical reactions, and to examine electronic properties at detonation conditions for a relatively long time-scale on the order of several hundreds of picoseconds. For thermal decomposition of TATB, we conducted constant volume-temperature simulations, ranging from 0.35 to 2 nanoseconds, at {rho} = 2.87 g/cm{sup 3} at T = 3500, 3000, 2500, and 1500 K, and {rho} = 2.9 g/cm{sup 3} and 2.72 g/cm{sup 3}, at T = 3000 K. We also simulated crystal TATB's reactivity under steady overdriven shock compression using the multi-scale shock technique. We conducted shock simulations with specified shock speeds of 8, 9, and 10 km/s for up to 0.43 ns duration, enabling us to track the reactivity of TATB well into the formation of several stable gas products, such as H{sub 2}O, N{sub 2}, and CO{sub 2}. Although complex chemical transformations are occurring continuously in the dynamical, high temperature, reactive environment of our simulations, a simple overall scheme for the decomposition of TATB emerges: Water is the earliest decomposition products to form, followed by a polymerization (or condensation) process in which several TATB remaining fragments are joined together, initiating the early step in the formation of high-nitrogen clusters, along with stable products such as N{sub 2} and CO{sub 2}. Remarkably, these clusters with high concentration of carbon and nitrogen (and little oxygen) remain dynamically stable for the remaining period of the simulations. Our simulations, thus, reveal a hitherto unidentified region of high concentrations of nitrogen-rich heterocyclic clusters in reacting TATB, whose persistence impede further reactivity towards final products of fluid N{sub 2} and solid carbon. These simulations also predict significant populations of charged species such as NCO{sup -}, H{sup +}, OH{sup -}, H{sub 3}O{sup +}, and O{sup -2}, the first such observation in a reacting explosive. Finally, A reduced four steps, global reaction mechanism with Arrhenius kinetic rates for the decomposition of TATB, along with comparative Cheetah decomposition kinetics at various temperatures has been constructed and will be discussed.

  4. Application of zero-valent iron nanoparticles for the removal of aqueous zinc ions under various experimental conditions.

    PubMed

    Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2014-01-01

    Application of zero-valent iron nanoparticles (nZVI) for Zn²⁺ removal and its mechanism were discussed. It demonstrated that the uptake of Zn²⁺ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn²⁺ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn²⁺ removal by nZVI. The DO enhanced the removal efficiency of Zn²⁺. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn²⁺ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn²⁺ by nZVI because the existing H⁺ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn²⁺ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn²⁺ were higher than Cd²⁺. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn²⁺. PMID:24416439

  5. Molecules in interstellar clouds. [physical and chemical conditions of star formation and biological evolution

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Hjalmarson, A.; Rydbeck, O. E. H.

    1981-01-01

    The physical conditions and chemical compositions of the gas in interstellar clouds are reviewed in light of the importance of interstellar clouds for star formation and the origin of life. The Orion A region is discussed as an example of a giant molecular cloud where massive stars are being formed, and it is pointed out that conditions in the core of the cloud, with a kinetic temperature of about 75 K and a density of 100,000-1,000,000 molecules/cu cm, may support gas phase ion-molecule chemistry. The Taurus Molecular Clouds are then considered as examples of cold, dark, relatively dense interstellar clouds which may be the birthplaces of solar-type stars and which have been found to contain the heaviest interstellar molecules yet discovered. The molecular species identified in each of these regions are tabulated, including such building blocks of biological monomers as H2O, NH3, H2CO, CO, H2S, CH3CN and H2, and more complex species such as HCOOCH3 and CH3CH2CN.

  6. Chemical composition and quantitative relationship between meteorological condition and fine particles in Beijing.

    PubMed

    Wang, Jing-Li; Zhang, Yuan-Hang; Shao, Min; Liu, Xu-Lin; Zeng, Li-Min; Cheng, Cong-Lan; Xu, Xiao-Feng

    2004-01-01

    The recent year's monitor results of Beijing indicated that the pollution level of fine particles PM2.5 showed an increasing trend. To understand pollution characteristics of PM2.5 and its relationship with the meteorological conditions in Beijing, a one-year monitoring of PM2.5 mass concentration and correspondent meteorological parameters was performed in Beijing in 2001. The PM2.5 levels in Beijing were very high, the annual average PM2.5 concentration in 2001 was 7 times of the National Ambient Air Quality Standards proposed by US EPA. The major chemical compositions were organics, sulfate, crustals and nitrate. It was found that the mass concentrations of PM2.5 were influenced by meteorological conditions. The correlation between the mass concentrations of PM2.5 and the relative humidity was found. And the correlation became closer at higher relative humidity. And the mass concentrations of PM2.5 were negtive-correlated to wind speeds, but the correlation between the mass concentration of PM2.5 and wind speed was not good at stronger wind. PMID:15559829

  7. Surface studies of niobium chemically polished under conditions for superconducting radiofrequency cavity production

    SciTech Connect

    Hui Tian; Michael Kelley; Charles Reece

    2005-11-14

    The performance of niobium superconducting radiofrequency accelerator cavities is strongly impacted by the topmost several nanometers of the active (interior) surface, especially by the final surface conditioning treatments. We examined the effect of the most commonly employed treatment, buffered chemical polishing (BCP), on polycrystalline niobium sheet over a range of realistic solution flow rates using electron back scatter diffraction (EBSD), stylus profilometry, atomic force microscopy, laboratory XPS and synchrotron (variable photon energy) XPS, seeking to collect statistically significant data sets. We found that the predominant general surface orientation is (100), but others are also present and at the atomic-level details of surface plane orientation are more complex. The post-etch surface exhibits micron-scale roughness, whose extent does not change with treatment conditions. The outermost surface consists of a few-nm thick layer of niobium pentoxide, whose thickness increases with solution flow rate to a maximum of 1.3 - 1.4 times that resulting from static solution. The standard deviation of the roughness measurements is ?? 30% and that of the surface composition is ?? 5%.

  8. Evaluating the potential for quantitative monitoring of in situ chemical oxidation of aqueous-phase TCE using in-phase and quadrature electrical conductivity

    NASA Astrophysics Data System (ADS)

    Hort, R. D.; Revil, A.; Munakata-Marr, J.; Mao, D.

    2015-07-01

    Electrical resistivity measurements can potentially be used to remotely monitor fate and transport of ionic oxidants such as permanganate (MnO4-) during in situ chemical oxidation (ISCO) of contaminants like trichloroethene (TCE). Time-lapse two-dimensional bulk conductivity and induced polarization surveys conducted during a sand tank ISCO simulation demonstrated that MnO4- plume movement could be monitored in a qualitative manner using bulk conductivity tomograms, although chargeability was below sensitivity limits. We also examined changes to in-phase and quadrature electrical conductivity resulting from ion injection, MnO2 and Cl- production, and pH change during TCE and humate oxidation by MnO4- in homogeneous aqueous solutions and saturated porous media samples. Data from the homogeneous samples demonstrated that inversion of the sand tank resistivity data using a common Tikhonov regularization approach was insufficient to recover an accurate conductivity distribution within the tank. While changes to in-phase conductivity could be successfully modeled, quadrature conductivity values could not be directly related to TCE oxidation product or MnO4- concentrations at frequencies consistent with field induced polarization surveys, limiting the utility of quadrature conductivity for monitoring ISCO.

  9. Aqueous Mesocosm Techniques Enabling the Real-Time Measurement of the Chemical and Isotopic Kinetics of Dissolved Methane and Carbon Dioxide.

    PubMed

    Chan, Eric W; Kessler, John D; Shiller, Alan M; Joung, DongJoo; Colombo, Frank

    2016-03-15

    Previous studies of microbially mediated methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on what factor(s) are limiting in these types of environments. These factors include the availability of methane, O2, trace metals, nutrients, the density of cell population, and the influence that CO2 production may have on pH. To look at this process in its entirety, we developed an automated mesocosm incubation system with a Dissolved Gas Analysis System (DGAS) coupled to a myriad of analytical tools to monitor chemical changes during methane oxidation. Here, we present new high temporal resolution techniques for investigating dissolved methane and carbon dioxide concentrations and stable isotopic dynamics during aqueous mesocosm and pure culture incubations. These techniques enable us to analyze the gases dissolved in solution and are nondestructive to both the liquid media and the analyzed gases enabling the investigation of a mesocosm or pure culture experiment in a completely closed system, if so desired. PMID:26916091

  10. Sodium Borohydride Reduction of Aqueous Silver-Iron-Nickel Solutions: a Chemical Route to Synthesis of Low Thermal Expansion-High Conductivity Ag-Invar Alloys

    NASA Astrophysics Data System (ADS)

    Sterling, E. A.; Stolk, J.; Hafford, L.; Gross, M.

    2009-07-01

    Thermal management is a critical concern in the design and performance of electronics systems. If heat extraction and thermal expansion are not properly addressed, the thermal mismatch among dissimilar materials may give rise to high thermal stresses or interfacial shear strains, and ultimately to premature system failure. In this article, we present a chemical synthesis process that yields Ag-Invar (64Fe-36Ni) alloys with a range of attractive properties for thermal management applications. Sodium borohydride reduction of an aqueous Ag-Fe-Ni metal salt solution produces nanocrystalline powders, and conventional powder processing converts this powder to fine-grained alloys. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy, thermomechanical analysis, and electrical conductivity measurements; thermal conductivity is estimated using the Wiedemann-Franz law. Sintering of Ag-Fe-Ni powders leads to the formation of two-phase silver-Invar alloys with low coefficients of thermal expansion (CTEs) and relatively high electrical conductivities. A sample of 50Ag-50Invar exhibits a CTE of 8.76 μm/(m· °C) and an estimated thermal conductivity of 236 W/(m·K). The Ag-Invar alloys offer thermodynamic stability and tailorable properties, and they may help address the need for improved packaging materials.

  11. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst.

    PubMed

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  12. Chemical equilibrium model for interfacial activity of crude oil in aqueous alkaline solution: the effects of pH, alkali and salt

    SciTech Connect

    Chan, M.; Yen, T.F.

    1980-11-01

    A chemical equilibrium model for interfacial activity of crude in aqueous alkaline solution is proposed. The model predicts the observed effects of pH and concentrations of alkali and salt on the interfacial tension (IFT). The model proposed was shown to describe the observed effects of acid content, pH, and sodium ions on the interfacial activity of crude oil in water. Once the pH of the interface reaches the pKa of the acids, sometimes with the help of addition of some salt, the IFT experiences a sudden steep drop to the range of 10/sup -2/ dynes/cm. After that, further addition of sodium either in the form of NaOH or NaCl is going to increase the IFT due to a shift of equilibriumn to the formation of undissociated soap. This was confirmed by the difference in the observed effect of sodium on the IFT of the extracted soap molecules which are dissociated easily and those which are associated highly and precipitated easily. These soap molecules have dissociation constant values ranging from below 10/sup -2/ to above one. 13 references.

  13. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    NASA Astrophysics Data System (ADS)

    Alnoor, Hatim; Chey, Chan Oeurn; Pozina, Galia; Liu, Xianjie; Khranovskyy, Volodymyr; Willander, Magnus; Nur, Omer

    2015-08-01

    Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (?-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  14. Four chemical methods of porcelain conditioning and their influence over bond strength and surface integrity

    PubMed Central

    Stella, João Paulo Fragomeni; Oliveira, Andrea Becker; Nojima, Lincoln Issamu; Marquezan, Mariana

    2015-01-01

    OBJECTIVE: To assess four different chemical surface conditioning methods for ceramic material before bracket bonding, and their impact on shear bond strength and surface integrity at debonding. METHODS: Four experimental groups (n = 13) were set up according to the ceramic conditioning method: G1 = 37% phosphoric acid etching followed by silane application; G2 = 37% liquid phosphoric acid etching, no rinsing, followed by silane application; G3 = 10% hydrofluoric acid etching alone; and G4 = 10% hydrofluoric acid etching followed by silane application. After surface conditioning, metal brackets were bonded to porcelain by means of the Transbond XP system (3M Unitek). Samples were submitted to shear bond strength tests in a universal testing machine and the surfaces were later assessed with a microscope under 8 X magnification. ANOVA/Tukey tests were performed to establish the difference between groups (α= 5%). RESULTS: The highest shear bond strength values were found in groups G3 and G4 (22.01 ± 2.15 MPa and 22.83 ± 3.32 Mpa, respectively), followed by G1 (16.42 ± 3.61 MPa) and G2 (9.29 ± 1.95 MPa). As regards surface evaluation after bracket debonding, the use of liquid phosphoric acid followed by silane application (G2) produced the least damage to porcelain. When hydrofluoric acid and silane were applied, the risk of ceramic fracture increased. CONCLUSIONS: Acceptable levels of bond strength for clinical use were reached by all methods tested; however, liquid phosphoric acid etching followed by silane application (G2) resulted in the least damage to the ceramic surface. PMID:26352845

  15. Electric Current Activated Combustion Synthesis and Chemical Ovens Under Terrestrial and Reduced Gravity Conditions

    NASA Technical Reports Server (NTRS)

    Unuvar, C.; Fredrick, D.; Anselmi-Tamburini, U.; Manerbino, A.; Guigne, J. Y.; Munir, Z. A.; Shaw, B. D.

    2004-01-01

    Combustion synthesis (CS) generally involves mixing reactants together (e.g., metal powders) and igniting the mixture. Typically, a reaction wave will pass through the sample. In field activated combustion synthesis (FACS), the addition of an electric field has a marked effect on the dynamics of wave propagation and on the nature, composition, and homogeneity of the product as well as capillary flow, mass-transport in porous media, and Marangoni flows, which are influenced by gravity. The objective is to understand the role of an electric field in CS reactions under conditions where gravity-related effects are suppressed or altered. The systems being studied are Ti+Al and Ti+3Al. Two different ignition orientations have been used to observe effects of gravity when one of the reactants becomes molten. This consequentially influences the position and concentration of the electric current, which in turn influences the entire process. Experiments have also been performed in microgravity conditions. This process has been named Microgravity Field Activated Combustion Synthesis (MFACS). Effects of gravity have been demonstrated, where the reaction wave temperature and velocity demonstrate considerable differences besides the changes of combustion mechanisms with the different high currents applied. Also the threshold for the formation of a stable reaction wave is increased under zero gravity conditions. Electric current was also utilized with a chemical oven technique, where inserts of aluminum with minute amounts of tungsten and tantalum were used to allow observation of effects of settling of the higher density solid particles in liquid aluminum at the present temperature profile and wave velocity of the reaction.

  16. Exceedingly Low Freezing Rates of Aqueous Hno3 and Hno3/h2so4 Droplets Under Polar Stratospheric Conditions

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Koop, T.; Luo, B.; Weers, U. G.; Peter, T.

    In the Arctic winter 1999/2000 large particles containing nitric acid were observed during in situ field measurements. These large particles are important for the deni- trification of the Arctic stratosphere. It has been proposed that such particles form by homogeneous nucleation of nitric acid hydrates from liquid stratospheric aerosol droplets. Homogeneous nucleation rates of NAT (Nitric Acid Trihydrate) and NAD (Nitric Acid Dihydrate) have been determined in laboratory experiments for binary HNO3/H2O solutions only at supersaturations much larger than observed in the stratosphere. Therefore, an extrapolation of such laboratory data is required for the modelling of stratospheric particle formation and subsequent denitrification. We will present new laboratory data of homogeneous nucleation rates of NAT and NAD from droplets consisting of both binary HNO3/H2O as well as ternary HNO3/H2O/H2SO4 solutions. Optical microscopy has been used to deduce the droplet freezing tempera- tures. The nature of the crystallized solids was identified by Raman spectroscopy. The freezing data have been analyzed within the framework of classical nucleation theory. Our results are consistent with previously published laboratory aerosol data. However, for stratospheric conditions, we infer homogeneous nucleation rates to be lower by orders of magnitude than the extrapolation currently in use. We conclude that homo- geneous nucleation of NAT and NAD is not sufficient to explain the observed number concentrations of large nitric acid containing particles in the stratosphere.

  17. Soil structure, colloids, and chemical transport as affected by short-term reducing conditions: a laboratory study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Upland soils in the Midwestern US often undergo reducing conditions when soils are temporally flooded during the spring and remain water saturated for days or weeks. Short-term reducing conditions change the chemistry of the soil and may affect soil structure and solution chemical transport. The eff...

  18. On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

    SciTech Connect

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I-Ming

    2008-09-25

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500 C and at pressures up to 480 MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L{sub 3}-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO{sub 3} aqueous solution at temperatures up to 500 C and at pressures up to 260 MPa shows that the Gd-O distance of the Gd{sup 3+} aqua ion decreases steadily at a rate of {approx} 0.007 {angstrom}/100 C whereas the number of coordinated H{sub 2}O molecules decreases from 9.0 {+-} 0.5 to 7.0 {+-} 0.4. The loss of water molecules in the Gd{sup 3+} aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb{sup 3+} aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd{sup 3+} aqua ion relative to other REEs. Gd L{sub 3}-edge XAFS measurements of 0.006m and 0.1m GdCl{sub 3} aqueous solutions at temperatures up to 500 C and pressures up to 480 MPa reveal that the onset of significant Gd{sup 3+}-Cl{sup -} association occurs around 300 C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} occur in the chloride solutions at higher temperatures, where {delta} {approx} 8 at 300 C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500 C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb{sup 3+} aquo ion and chloro complexes in aqueous solutions at up to 500 C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 {+-} 0.2 to 1.7 {+-} 0.3 in the 0.006m chloride solution and from 0.9 {+-} 0.7 to 1.8 {+-} 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500 C range. Conversely, the number of H{sub 2}O ligands of Gd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} complexes decreases steadily from 8.9 {+-} 0.4 to 5.8 {+-} 0.7 in the 0.006m GdCl{sub 3} aqueous solution and from 9.0 {+-} 0.5 to 5.3 {+-} 1.0 in the 0.1m GdCl{sub 3} aqueous solution at temperatures from 25 to 500 C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH{sub 2} bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction ({approx} 0.005 {angstrom}/100 C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids.

  19. Optimization of conditions for Cu(II) adsorption on D151 resin from aqueous solutions using response surface methodology and its mechanism study.

    PubMed

    Zhang, Hao; Xiong, Chunhua; Liu, Fang; Zheng, Xuming; Jiang, Jianxiong; Zheng, Qunxiong; Yao, Caiping

    2014-01-01

    An experimental study on the removal of Cu(II) from aqueous solutions by D151 resin was carried out in a batch system. The response surface methodology (RSM)-guided optimization indicated that the optimal adsorption conditions are: temperature of 35 °C, pH of 5.38, and initial Cu(II) concentration of 0.36 mg/mL, and the predicted adsorption capacity from the model reached 328.3 mg/g. At optimum adsorption conditions, the adsorption capacity of Cu(II) was 321.6 mg/g, which obtained from real experiments what were in close agreement with the predicted value. The adsorption isotherms data fitted the Langmuir model well, and the correlation coefficient has been evaluated. The calculation data of thermodynamic parameters (ΔG, ΔS, and ΔH) confirmed that the adsorption process was endothermic and spontaneous in nature. The desorption study revealed that Cu(II) can be effectively eluted by 1 mol/l HCl solution, and the recovery was 100%. Moreover, the characterization was undertaken by infrared (IR) spectroscopy. PMID:24960006

  20. SONOCHEMICAL DECHLORINATION OF HAZARDOUS WASTES IN AQUEOUS SYSTEMS. (R825513C004)

    EPA Science Inventory

    Physical processes resulting from ultrasonication of aqueous solutions and suspensions produce extreme conditions that can affect the chemistry of dissolved and suspended chemicals. The purpose of this work was to explore the use of sonochemistry in treating chlorinated chemic...

  1. Phytoplankton communities of polar regions-Diversity depending on environmental conditions and chemical anthropopressure.

    PubMed

    Kosek, Klaudia; Polkowska, Żaneta; Żyszka, Beata; Lipok, Jacek

    2016-04-15

    The polar regions (Arctic and Antarctic) constitute up to 14% of the biosphere and offer some of the coldest and most arid Earth's environments. Nevertheless several oxygenic phototrophs including some higher plants, mosses, lichens, various algal groups and cyanobacteria, survive that harsh climate and create the base of the trophic relationships in fragile ecosystems of polar environments. Ecosystems in polar regions are characterized by low primary productivity and slow growth rates, therefore they are more vulnerable to disturbance, than those in temperate regions. From this reason, chemical contaminants influencing the growth of photoautotrophic producers might induce serious disorders in the integrity of polar ecosystems. However, for a long time these areas were believed to be free of chemical contamination, and relatively protected from widespread anthropogenic pressure, due their remoteness and extreme climate conditions. Nowadays, there is a growing amount of data that prove that xenobiotics are transported thousands of kilometers by the air and ocean currents and then they are deposed in colder regions and accumulate in many environments, including the habitats of marine and freshwater cyanobacteria. Cyanobacteria (blue green algae), as a natural part of phytoplankton assemblages, are globally distributed, but in high polar ecosystems they represent the dominant primary producers. These microorganisms are continuously exposed to various concentration levels of the compounds that are present in their habitats and act as nourishment or the factors influencing the growth and development of cyanobacteria in other way. The most common group of contaminants in Arctic and Antarctic are persistent organic pollutants (POPs), characterized by durability and resistance to degradation. It is important to determine their concentrations in all phytoplankton species cells and in their environment to get to know the possibility of contaminants to transfer to higher trophic levels, considering however that some strains of microalgae are capable of metabolizing xenobiotics, make them less toxic or even remove them from the environment. PMID:26846983

  2. Iron isotope fractionation among magnetite, pyrrhotite, chalcopyrite, rhyolite melt and aqueous fluid at magmatic-hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Bilenker, L. D.; Simon, A.; Lundstrom, C.; Gajos, N.

    2012-12-01

    Fractionation of non-traditional stable isotopes (NTSI) such as Fe in magmatic systems is a relatively understudied subject. The fractionation of Fe stable isotopes has been quantified in some natural igneous samples, but there is a paucity of experimental data that could provide further insight into the causative processes of the observed fractionation. Substantial experimental work has been performed at higher temperatures pertaining to the formation of chondrites and the Earth's core, but only a handful of studies have addressed crustal rocks. To fill this knowledge gap, we performed isothermal, isobaric experiments containing mineral (e.g., magnetite, Fe-sulfides) and fluid, or mineral, rhyolite melt, and fluid assemblages to quantify equilibrium fractionation factors (α). These data, to our knowledge, are the first data that quantify the effect of a fluid phase on iron isotope fractionation at conditions appropriate for evolving magmatic systems. Charges were run inside gold capsules held in a René-41 cold seal vessel, and heated to 400, 600, or 800°C at 150 MPa for mineral-fluid, and 800°C and 100 MPa for mineral-melt-fluid runs. Use of the René vessel fixed the fO2 at the NNO buffer, an oxidation state consistent with arc magmas. The isotopic compositions of the starting and quenched phases were obtained by using a Multi-Collector Plasma Mass Spectrometer (MC-ICP-MS). Equilibrium was assessed by performing time-series runs and the three-isotope method, used only once before in a similar Fe isotope study. Correlation between Fe isotope mass and oxidation state is also being explored. Magnetite-fluid results indicate enrichment of heavy Fe isotopes in the mineral relative to the fluid, consistent with measurements of felsic igneous rocks. Magnetite-melt-fluid relationships are also consistent with measurements of natural samples. In the latter assemblage, over the course of the run, the rhyolite melt becomes heavy relative to the fluid while magnetite takes on a heavier Fe isotope signature than the starting value. These data corroborate the hypothesis that fluid exsolution caused the isotopic patterns observed in highly-differentiated igneous rocks. Further, owing to the ubiquitous importance of melt degassing as a critical process for the formation of magmatic-hydrothermal ore deposits, these data may be potentially serve as an exploration tool. This work contributes to our overall understanding of igneous processes by elucidating the Fe isotope fingerprints observed in the field as well as develop the laboratory techniques needed to study NTSI fractionation in magmatic systems and build a reliable dataset for interpretation of natural systems.

  3. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the experiments run to date suggest that the cement-pozzolans used will be an effective seal for CO2, as long as the well was properly installed and is initially undamaged.

  4. Aqueous Conditions and Habitability Associated with Formation of a Serpentinite: Using Analyses of Ferric Iron and Stable Carbon Isotopes to Reconstruct Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Greenberger, R. N.; Mustard, J. F.; Cloutis, E.; Pratt, L. M.; Sauer, P. E.; Mann, P.; Turner, K.; Dyar, M. D.

    2014-12-01

    Serpentine deposits on Mars have generated significant interest because byproducts of serpentinization, H2 and CH4, can be important energy sources for subsurface microbial communities. H2 is produced through Fe2+ oxidation to form magnetite and Fe3+-bearing serpentine. In serpentine, Fe3+ goes into octahedral sites first, then tetrahedral sites [Marcaillou et al., 2011, EPSL]. We use Fe oxidation state and coordination in an Early Ordovician serpentinite in Norbestos, Quebec, as proxies for H2 production and stable isotopes of carbonates to understand past aqueous conditions at the Canadian Space Agency's 2012 Mars Methane Analogue Mission site. Rock outcrops were imaged with a visible hyperspectral imager (420-720 nm), and samples were imaged in the laboratory with the same imager and a near infrared imager (650-1100 nm). Other analyses determined major element chemistry (ICP-AES and C analyses), mineralogy (XRD), Fe phases (Mössbauer spectroscopy), and stable isotopes of carbonates. Fe oxidation state and coordination (tetrahedral vs octahedral) were mapped in samples and outcrops using imaging data. We focused on locations with tetrahedral Fe3+ in serpentine as these are the most serpentinized sites with maximum H2 production. Carbonate samples from ~100-200 m south of a shear zone are enriched in 13C (δ13C up to +16.12‰ vs VPDB) resulting from production of CH4 depleted in 13C in a system closed to C addition but open to CH4 escape. This alteration occurred at elevated temperatures and low water/rock ratios. In the shear zone, lower δ13C values (most < +2‰) positively correlated with δ18O likely result from kinetic fractionation under recent low temperature conditions. Spectroscopy suggests that much of this deposit underwent advanced serpentinization to produce significant H2. Isotopic signatures of carbonates precipitated during serpentinization outside the shear zone illuminate the temperatures (elevated) and chemistries of fluids (high Ca2+, low CO2, alkaline) and gases (H2, CH4) in an ancient habitable environment. These results suggest that serpentinites identified on Mars, where there has been limited recent aqueous activity, could preserve evidence of fluid composition and levels of hydrogen production, providing a promising context to search for biosignatures.

  5. Phase transition and chemical decomposition of liquid carbon dioxide and nitrogen mixture under extreme conditions

    NASA Astrophysics Data System (ADS)

    Xiao-Xu, Jiang; Guan-Yu, Chen; Yu-Tong, Li; Xin-Lu, Cheng; Cui-Ming, Tang

    2016-02-01

    Thermodynamic and chemical properties of liquid carbon dioxide and nitrogen (CO2-N2) mixture under the conditions of extremely high densities and temperatures are studied by using quantum molecular dynamic (QMD) simulations based on density functional theory including dispersion corrections (DFT-D). We present equilibrium properties of liquid mixture for 112 separate density and temperature points, by selecting densities ranging from ρ = 1.80 g/cm3 to 3.40 g/cm3 and temperatures from T = 500 K to 8000 K. In the range of our study, the liquid CO2-N2 mixture undergoes a continuous transition from molecular to atomic fluid state and liquid polymerization inferred from pair correlation functions (PCFs) and the distribution of various molecular components. The insulator-metal transition is demonstrated by means of the electronic density of states (DOS). Project supported by the National Natural Science Foundation of China (Grant Nos. 11374217, 11135012, and 11375262) and the Joint Fund of the National Natural Science Foundation of China and the China Academy of Engineering Physics (Grant No. 11176020).

  6. Particle emissions from a marine engine: chemical composition and aromatic emission profiles under various operating conditions.

    PubMed

    Sippula, O; Stengel, B; Sklorz, M; Streibel, T; Rabe, R; Orasche, J; Lintelmann, J; Michalke, B; Abbaszade, G; Radischat, C; Gröger, T; Schnelle-Kreis, J; Harndorf, H; Zimmermann, R

    2014-10-01

    The chemical composition of particulate matter (PM) emissions from a medium-speed four-stroke marine engine, operated on both heavy fuel oil (HFO) and distillate fuel (DF), was studied under various operating conditions. PM emission factors for organic matter, elemental carbon (soot), inorganic species and a variety of organic compounds were determined. In addition, the molecular composition of aromatic organic matter was analyzed using a novel coupling of a thermal-optical carbon analyzer with a resonance-enhanced multiphoton ionization (REMPI) mass spectrometer. The polycyclic aromatic hydrocarbons (PAHs) were predominantly present in an alkylated form, and the composition of the aromatic organic matter in emissions clearly resembled that of fuel. The emissions of species known to be hazardous to health (PAH, Oxy-PAH, N-PAH, transition metals) were significantly higher from HFO than from DF operation, at all engine loads. In contrast, DF usage generated higher elemental carbon emissions than HFO at typical load points (50% and 75%) for marine operation. Thus, according to this study, the sulfur emission regulations that force the usage of low-sulfur distillate fuels will also substantially decrease the emissions of currently unregulated hazardous species. However, the emissions of soot may even increase if the fuel injection system is optimized for HFO operation. PMID:25202837

  7. Chemical looping combustion in a rotating bed reactor--finding optimal process conditions for prototype reactor.

    PubMed

    Håkonsen, Silje Fosse; Blom, Richard

    2011-11-15

    A lab-scale rotating bed reactor for chemical looping combustion has been designed, constructed, and tested using a CuO/Al(2)O(3) oxygen carrier and methane as fuel. Process parameters such as bed rotating frequency, gas flows, and reactor temperature have been varied to find optimal performance of the prototype reactor. Around 90% CH(4) conversion and >90% CO(2) capture efficiency based on converted methane have been obtained. Stable operation has been accomplished over several hours, and also--stable operation can be regained after intentionally running into unstable conditions. Relatively high gas velocities are used to avoid fully reduced oxygen carrier in part of the bed. Potential CO(2) purity obtained is in the range 30 to 65%--mostly due to air slippage from the air sector--which seems to be the major drawback of the prototype reactor design. Considering the prototype nature of the first version of the rotating reactor setup, it is believed that significant improvements can be made to further avoid gas mixing in future modified and up-scaled reactor versions. PMID:21970700

  8. Defect formation in aqueous environment: Theoretical assessment of boron incorporation in nickel ferrite under conditions of an operating pressurized-water nuclear reactor (PWR)

    NASA Astrophysics Data System (ADS)

    Rák, Zs.; Bucholz, E. W.; Brenner, D. W.

    2015-06-01

    A serious concern in the safety and economy of a pressurized water nuclear reactor is related to the accumulation of boron inside the metal oxide (mostly NiFe2O4 spinel) deposits on the upper regions of the fuel rods. Boron, being a potent neutron absorber, can alter the neutron flux causing anomalous shifts and fluctuations in the power output of the reactor core. This phenomenon reduces the operational flexibility of the plant and may force the down-rating of the reactor. In this work an innovative approach is used to combine first-principles calculations with thermodynamic data to evaluate the possibility of B incorporation into the crystal structure of NiFe2O4 , under conditions typical to operating nuclear pressurized water nuclear reactors. Analyses of temperature and pH dependence of the defect formation energies indicate that B can accumulate in NiFe2O4 as an interstitial impurity and may therefore be a major contributor to the anomalous axial power shift observed in nuclear reactors. This computational approach is quite general and applicable to a large variety of solids in equilibrium with aqueous solutions.

  9. Conditions and mechanisms for the formation of nano-sized Delafossite (CuFeO2) at temperatures ≤90 °C in aqueous solution

    NASA Astrophysics Data System (ADS)

    John, Melanie; Heuss-Aßbichler, Soraya; Ullrich, Aladin

    2016-02-01

    In this study, we present the mechanism of CuFeO2 formation in aqueous solution at low temperatures ≤90 °C, using sulfate salts as reactants. Furthermore, we demonstrate the influence of experimental conditions (alkalization, reaction and ageing temperature and time) on the synthesized nanoparticles. In all cases, GR-SO4, a Fe(II-III) layered double hydroxysulphate Fe2+4 Fe3+2 (Fe2+4Fe3+2(OH)12·SO4) and Cu2O precipitate first. During further OH- supply GR-SO4 oxidizes and forms Fe10O14(OH)2, Cu2O and CuFeO2 crystals. Due to the high pH furtherCuFeO2 crystals grow at the cost of the unstable intermediate products. The reaction rate increases with increasing ageing temperature, reaction pH and, in particular, NaOH concentrations in the solution. As a result, highly crystalline CuFeO2 (3R and 2H polytypes) nanoparticles showing hexagonal morphology can be synthesized at 70 °C within 10 h or at 50 °C within 1 week. The formation of 2H polytype is favored by additional OH- supply during the pH-stat time and rather low temperatures.

  10. Sonochemical dechlorination of hazardous wastes in aqueous systems

    SciTech Connect

    Catallo, W.J.; Junk, T.

    1995-12-31

    Physical processes resulting from ultrasonication of aqueous solutions and suspensions produce extreme conditions that can affect the chemistry of dissolved and suspended chemicals. The purpose of this work was to explore the use of sonochemistry in treating chlorinated chemicals in water. The compounds examined for susceptibility to aqueous sonochemical transformation were chlorpyrifos, 3,3{prime},4,4{prime}-tetrachloroazoxybenzene, 2-chlorobiphenyl, 2,4,8-trichlorodibenzofuran, lindane (hexachlorocyclohexane, {gamma}-isomer), hexachlorobenzene, aldrin, and a complex mixture of chlorinated olefins, paraffins, and aromatics from a Louisiana Superfund Site. It was fond that many chemicals were dechlorinated and/or otherwise transformed by sonochemical treatment under minimal conditions. Evidence for sonochemical transformation and dechlorination of the target chemicals and mixtures was obtained from controlled experiments measuring (1) increases in titratable chloride from sonochemical treatment, (2) decreases in pH, (3) changes in aqueous phase UV/visible absorption spectra, (4) changes in aqueous electrochemistry, and (5) generation of sonolysis products and/or decreases in target compounds vs appropriate control in internally standardized GC-MS analysis of extracts.

  11. Integrating 31P DOSY NMR spectroscopy and molecular mechanics as a powerful tool for unraveling the chemical structures of polyoxomolybdate-based amphiphilic nanohybrids in aqueous solution.

    PubMed

    Shestakova, Pavletta; Absillis, Gregory; Martin-Martinez, Francisco J; De Proft, Frank; Willem, Rudolph; Parac-Vogt, Tatjana N

    2014-04-25

    Novel organic-inorganic hybrids of various sizes were generated by reaction of 1,8-octanediphosphonic acid (ODP) and (NH4)6Mo7O24 in aqueous solution. The formation of rodlike hybrids with variable numbers of covalently bound ODP and polyoxomolybdate (POM) units can be tuned as a function of increasing (NH4)6Mo7O24 concentration at fixed ODP concentration. The chemical structure of the ODP/POM hybrids was characterized by (1)H, (31)P, and (95)Mo NMR spectroscopy. Heteronuclear (31)P DOSY (diffusion- ordered NMR spectroscopy) and molecular mechanics (MM) calculations were applied to determine the size and shape of the nanosized hybrids generated at various ODP/POM ratios. For this purpose, the structures of ODP/POM hybrids with variable numbers of ODP and POM units were optimized by MM and then approximated as cylinder-shaped objects by using a recently described mathematical algorithm. The thus-obtained cylinder length and diameter were further used to calculate the expected diffusion coefficients of the ODP/POM hybrids. Comparison of the calculated and experimentally determined diffusion coefficients led to the most probable ODP/POM hybrid length for each sample composition. The (31)P DOSY results show that the length of the hybrids increases with increasing POM concentration and reaches a maximum corresponding to an average of 8 ODP/7 POM units per chain at a sample composition of 20 mM ODP and 14 mM POM. With excess POM, above the latter concentration, the formation of shorter-chain hybrids terminated by Mo7 clusters at one or both ends was evidenced on further increasing the POM concentration. The results demonstrate that the combination of (31)P DOSY and MM, although virtually unexplored in POM chemistry, is a powerful innovative strategy for the detailed characterization of nanosized organic-inorganic POM-based hybrids in solution. PMID:24729454

  12. Evaluation of meat and bone meal combustion residue as lead immobilizing material for in situ remediation of polluted aqueous solutions and soils: "chemical and ecotoxicological studies".

    PubMed

    Deydier, E; Guilet, R; Cren, S; Pereas, V; Mouchet, F; Gauthier, L

    2007-07-19

    As a result of bovine spongiform encephalopathy (BSE) crisis, meat and bone meal (MBM) production can no longer be used to feed cattle and must be safely disposed of or transformed. MBM specific incineration remains an alternative that could offer the opportunity to achieve both thermal valorization and solid waste recovery as ashes are calcium phosphate-rich material. The aim of this work is to evaluate ashes efficiency for in situ remediation of lead-contaminated aqueous solutions and soils, and to assess the bioavailability of lead using two biological models, amphibian Xenopus laevis larvae and Nicotiana tabaccum tobacco plant. With the amphibian model, no toxic or genotoxic effects of ashes are observed with concentrations from 0.1 to 5 g of ashes/L. If toxic and genotoxic effects of lead appear at concentration higher than 1 mg Pb/L (1 ppm), addition of only 100 mg of ashes/L neutralizes lead toxicity even with lead concentration up to 10 ppm. Chemical investigations (kinetics and X-ray diffraction (XRD) analysis) reveals that lead is quickly immobilized as pyromorphite [Pb10(PO4)6(OH)2] and lead carbonate dihydrate [PbCO(3).2H2O]. Tobacco experiments are realized on contaminated soils with 50, 100, 2000 and 10000 ppm of lead with and without ashes amendment (35.3g ashes/kg of soil). Tobacco measurements show that plant elongation is bigger in an ashes-amended soil contaminated with 10000 ppm of lead than on the reference soil alone. Tobacco model points out that ashes present two beneficial actions as they do not only neutralize lead toxicity but also act as a fertilizer. PMID:17240054

  13. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    PubMed

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers. PMID:26652418

  14. Thermo-chemical ablation of heat shields under Earth reentry conditions

    NASA Astrophysics Data System (ADS)

    Keenan, James Anthony

    1994-04-01

    The process of ablation for earth atmospheric entry is modeled. The flowfield surrounding the ablator is modeled by an extended set of Navier-Stokes equations that include the effects of thermochemical nonequilibrium. This set of equations encompasses the conservation of mass for each chemical species, conservation of momentum, the conservation of vibrational energy, and the conservation of total energy. The heat conduction into the ablator material is modeled by using Fourier's Law of heat conduction and the heat equation. The flowfield and ablator are coupled by a thermochemical ablation model that includes a surface mass balance and a surface energy balance. The ablation model takes into account chemical reactions of the flowfield species with the surface material, surface material acting as a catalytic surface, and sublimation of the surface material. To solve the governing equations for the model, a computational fluid dynamics approach is used where the flowfield is solved using a modified Steger-Warming flux vector splitting scheme and the solid is solved using a centrally differenced scheme. A Gauss-Seidel line relaxation technique is implemented to speed numerical convergence. The flowfield model is verified by comparing to flowfield computations of other researchers and to experimental data. The ablator/heat shield model is validated by a direct comparison between an exact analytical solution and a numerical solution. The thermochemical ablation model is verified by comparing to the experimental results of the Passive Nosetip Technology (PANT) program. The model is used to calculate steady-state ablation data for sphere-cone reentry bodies. Two bodies with nose radii of 0.0127 m and 0.1270 m are tested at a velocity of 8 km/s. The ablator material is selected to be a commercial grade graphite. Due to the ablator selection, the flowfield is limited to 11 chemical species and two internal energy modes. A standard earth atmosphere is selected at altitudes ranging from 40 km to 80 km. The major results concern the thermochemical ablation model. Both oxidation and sublimation mechanisms are evident and are dependent on freestream conditions and the reentry body shape.

  15. Development of methods for on-line measurements of chemical conditions in compacted bentonite

    NASA Astrophysics Data System (ADS)

    Muurinen, A.; Carlsson, T.

    This work describes the development of an on-line method for studying the chemical conditions in compacted water-saturated bentonite. The equipment includes a squeezing cell, measurement electrodes, a reference electrode, and a data-logging system. IrO x wire was used for the pH measurements and Au and Pt wires for the redox measurements. The electrodes were made in-house at VTT. The reference electrode was a commercial leak-free electrode. The measurement electrodes were installed in the bentonite, while the reference electrode was placed in water outside the clay. The contact between the reference electrode and the measurement electrodes was established via the solution in a tube. The work included first a test and calibration of the electrodes in various standard solutions. The performance of the electrodes was subsequently studied in compacted MX-80 in squeezing cell experiments. The squeezing cell initially contained MX-80 mixed with different solutions at a dry density of 0.8-0.9 Mg/m 3. The pore water was then slowly squeezed out from the clay until the final density of 1.5 Mg/m 3 was reached. The measurement electrodes were then placed in the clay and the potential measurements were started. At the end of the experiments the electrodes were removed from bentonite and recalibrated. The pH and Eh in the squeezed pore waters were determined for comparison. The results obtained so far have led to the conclusion that it is possible to perform pH measurements in compacted bentonite by using IrO x electrodes. The electrode can survive the swelling pressure inside compacted water-saturated clay without losing its ability to function as a pH electrode. It is also possible to perform Eh measurements in compacted clay by using Au and Pt electrodes.

  16. Conditional Toxicity Value (CTV) Predictor for Generating Toxicity Values for Data Sparse Chemicals (Poster)

    EPA Science Inventory

    Various stakeholders and expert groups, including the National Research Council in Science and Decisions, call for “default approaches to support risk estimation for chemicals lacking chemical-specific information.” This project aims to address this challenge through ...

  17. Massive star evolution in close binaries. Conditions for homogeneous chemical evolution

    NASA Astrophysics Data System (ADS)

    Song, H. F.; Meynet, G.; Maeder, A.; Ekström, S.; Eggenberger, P.

    2016-01-01

    Aims: We investigate the impact of tidal interactions, before any mass transfer, on various properties of the stellar models. We study the conditions for obtaining homogeneous evolution triggered by tidal interactions, and for avoiding any Roche lobe overflow (RLOF) during the main-sequence phase. By homogeneous evolution, we mean stars evolving with a nearly uniform chemical composition from the centre to the surface. Methods: We consider the case of rotating stars computed with a strong core-envelope coupling mediated by an interior magnetic field. Models with initial masses between 15 and 60 M⊙, for metallicities between 0.002 and 0.014 and with initial rotation equal to 30% and 66% the critical rotation on the zero age main sequence, are computed for single stars and for stars in close binary systems. We consider close binary systems with initial orbital periods equal to 1.4, 1.6, and 1.8 days and a mass ratio equal to 3/2. Results: In models without any tidal interaction (single stars and wide binaries), homogeneous evolution in solid body rotating models is obtained when two conditions are realised: the initial rotation must be high enough, and the loss of angular momentum by stellar winds should be modest. This last point favours metal-poor fast rotating stars. In models with tidal interactions, homogeneous evolution is obtained when rotation imposed by synchronisation is high enough (typically a time-averaged surface velocities during the main-sequence phase above 250 km s-1), whatever the mass losses. We present plots that indicate for which masses of the primary and for which initial periods the conditions for the homogenous evolution and avoidance of the RLOF are met, for various initial metallicities and rotations. In close binaries, mixing is stronger at higher than at lower metallicities. Homogeneous evolution is thus favoured at higher metallicities. RLOF avoidance is favoured at lower metallicities because stars with less metals remain more compact. We also study the impact of different processes for the angular momentum transport on the surface abundances and velocities in single and close binaries. In models where strong internal coupling is assumed, strong surface enrichments are always associated with high surface velocities in binary or single star models. In contrast, models computed with mild coupling may produce strong surface enrichments associated with low surface velocities. This observable difference can be used to probe different models for the transport of the angular momentum in stars. Homogeneous evolution is more easily obtained in models (with or without tidal interactions) with solid body rotation. Conclusions: Close binary models help us to understand homogeneous massive stars, fast rotating Wolf-Rayet stars, and progenitors of long soft gamma-ray bursts, even at high metallicities.

  18. The Effect of Cooperative Learning Approach Based on Conceptual Change Condition on Students' Understanding of Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Bilgin, Ibrahim; Geban, Omer

    2006-01-01

    The purpose of this study is to investigate the effects of the cooperative learning approach based on conceptual change conditions over traditional instruction on 10th grade students' conceptual understanding and achievement of computational problems related to chemical equilibrium concepts. The subjects of this study consisted of 87 tenth grade…

  19. Effects of different extrusion conditions on the chemical and toxicological fate of fumonisin B1 in maize: a review

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A series of experiments to investigate the chemical and toxicological fate of fumonisin B1 (FB1) under different extrusion conditions using both single- and twin-screw extruders is described. Maize grits were contaminated with FB1 at different concentrations by fermentation with Fusarium verticilli...

  20. Transport and Fate of Bacteria in Porous Media: Coupled Effects of Chemical Conditions and Pore Space Geometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experimental and theoretical studies were undertaken to explore the coupling effects of chemical conditions and pore space geometry on bacteria transport in porous media. The retention of Escherichia coli D21g was investigated in a series of batch and column experiments with solutions of different i...

  1. Metabolic profiling of Lolium perenne shows functional integration of metabolic responses to diverse subtoxic conditions of chemical stress

    PubMed Central

    Serra, Anne-Antonella; Couée, Ivan; Renault, David; Gouesbet, Gwenola; Sulmon, Cécile

    2015-01-01

    Plant communities are confronted with a great variety of environmental chemical stresses. Characterization of chemical stress in higher plants has often been focused on single or closely related stressors under acute exposure, or restricted to a selective number of molecular targets. In order to understand plant functioning under chemical stress conditions close to environmental pollution conditions, the C3 grass Lolium perenne was subjected to a panel of different chemical stressors (pesticide, pesticide degradation compound, polycyclic aromatic hydrocarbon, and heavy metal) under conditions of seed-level or root-level subtoxic exposure. Physiological and metabolic profiling analysis on roots and shoots revealed that all of these subtoxic chemical stresses resulted in discrete physiological perturbations and complex metabolic shifts. These metabolic shifts involved stressor-specific effects, indicating multilevel mechanisms of action, such as the effects of glyphosate and its degradation product aminomethylphosphonic acid on quinate levels. They also involved major generic effects that linked all of the subtoxic chemical stresses with major modifications of nitrogen metabolism, especially affecting asparagine, and of photorespiration, especially affecting alanine and glycerate. Stress-related physiological effects and metabolic adjustments were shown to be integrated through a complex network of metabolic correlations converging on Asn, Leu, Ser, and glucose-6-phosphate, which could potentially be modulated by differential dynamics and interconversion of soluble sugars (sucrose, trehalose, fructose, and glucose). Underlying metabolic, regulatory, and signalling mechanisms linking these subtoxic chemical stresses with a generic impact on nitrogen metabolism and photorespiration are discussed in relation to carbohydrate and low-energy sensing. PMID:25618145

  2. Metabolic profiling of Lolium perenne shows functional integration of metabolic responses to diverse subtoxic conditions of chemical stress.

    PubMed

    Serra, Anne-Antonella; Couée, Ivan; Renault, David; Gouesbet, Gwenola; Sulmon, Cécile

    2015-04-01

    Plant communities are confronted with a great variety of environmental chemical stresses. Characterization of chemical stress in higher plants has often been focused on single or closely related stressors under acute exposure, or restricted to a selective number of molecular targets. In order to understand plant functioning under chemical stress conditions close to environmental pollution conditions, the C3 grass Lolium perenne was subjected to a panel of different chemical stressors (pesticide, pesticide degradation compound, polycyclic aromatic hydrocarbon, and heavy metal) under conditions of seed-level or root-level subtoxic exposure. Physiological and metabolic profiling analysis on roots and shoots revealed that all of these subtoxic chemical stresses resulted in discrete physiological perturbations and complex metabolic shifts. These metabolic shifts involved stressor-specific effects, indicating multilevel mechanisms of action, such as the effects of glyphosate and its degradation product aminomethylphosphonic acid on quinate levels. They also involved major generic effects that linked all of the subtoxic chemical stresses with major modifications of nitrogen metabolism, especially affecting asparagine, and of photorespiration, especially affecting alanine and glycerate. Stress-related physiological effects and metabolic adjustments were shown to be integrated through a complex network of metabolic correlations converging on Asn, Leu, Ser, and glucose-6-phosphate, which could potentially be modulated by differential dynamics and interconversion of soluble sugars (sucrose, trehalose, fructose, and glucose). Underlying metabolic, regulatory, and signalling mechanisms linking these subtoxic chemical stresses with a generic impact on nitrogen metabolism and photorespiration are discussed in relation to carbohydrate and low-energy sensing. PMID:25618145

  3. Greener Syntheses and Chemical Transformations: Sustainable Alternative Methods and Applications of Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a var...

  4. Greener Syntheses and Chemical Transformations Using SustainableAlternative Methods and Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, namely greener reaction medium in aqueous or solventfree conditions and using alternative activation via microwave or photocatalytic activation. Eco-friendly synthesis of nanoma...

  5. Sustainable 'Greener' Methods for Chemical Transformations and Applications of Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 Synthesis of heterocyclic compounds, coupling reactions, and name reac...

  6. Greener Syntheses and Chemical Transformations: Sustainable Alternative Methods and Applications of Nano-Catalysts. (Florence, Italy)

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions. The synthesis of heterocyclic compounds, coupling reactions, and a vari...

  7. Greener Synthesis and Chemical transformations Using Sustainable Alternative Methods and Applications of Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, namely greener reaction medium in aqueous or solventfree conditions and using alternative activation via microwave or photocatalytic activation. Eco-friendly synthesis of nanoma...

  8. Study of Chemical Surface Structure of Natural Sorbents Used for Removing of Pb2+ Ions from Model Aqueous Solutions (part Ii)

    NASA Astrophysics Data System (ADS)

    Bożęcka, Agnieszka; Bożęcki, Piotr; Sanak-Rydlewska, Stanisława

    2014-03-01

    This article presents the results of the chemical structure research of organic sorbent surface such as walnut shells, plums stones and sunflower hulls with using such methods as infrared spectrometry (FTIR) and elemental analysis. Based on the IR spectra identification of functional groups present on the surface of studied materials has been done as well as determination of their effect on the sorption mechanism of Pb2+ ions from aqueous model solutions W artykule przedstawiono wyniki badań chemicznej struktury powierzchni sorbentów organicznych takich jak: łupiny orzecha włoskiego, pestki śliwek oraz łuski słonecznika z wykorzystaniem metody spektrometrii w podczerwieni (FTIR) oraz analizy elementarnej. W oparciu o uzyskane widma IR dokonano identyfikacji grup funkcyjnych obecnych na powierzchni tych materiałów i określono ich wpływ na mechanizm sorpcji jonów Pb2+ z modelowych roztworów wodnych. Analiza elementarna wykazała, że spośród badanych sorbentów, największą zawartość węgla (49,91%) i wodoru (5,93%) mają pestki śliwek. Najwięcej azotu (1,59%) zawierają łuszczyny słonecznika (tabela 1). Zawartość siarki we wszystkich badanych materiałach jest znikoma, dlatego nie udało się jej oznaczyć tą metodą. Obecność pozostałych pierwiastków może świadczyć o istnieniu zarówno alifatycznych jak i aromatycznych połączeń organicznych. Potwierdzeniem tego są również zarejestrowane widma IR (rysunki 1-3). W oparciu o uzyskane wyniki można przypuszczać także, iż udział procesu wymiany jonowej w sorpcji ołowiu z roztworów wodnych jest znaczący. Świadczą o tym m.in. intensywności pasm na widmach IR dla próbek badanych materiałów po ich kontakcie z roztworami jonów Pb2+ (rysunki 4-6).

  9. One-electron reduction of tris(2,2 prime -bipyrimidine)ruthenium(2+) ion in aqueous solution. A photochemical, radiation chemical, and electrochemical study

    SciTech Connect

    Neshvad, G.; Hoffman, M.Z. ); Mulazzani, Q.G.; Ciano, M.; D'Angelantonio, M. ); Venturi, M. Univ. di Bologna )

    1989-08-10

    The reduction of Ru(bpm){sub 3}{sup 2+} in aqueous solution has been investigated by use of photochemical, radiation chemical, and electrochemical techniques. The luminescent excited state of the substrate, *Ru(bpm){sub 3}{sup 2+}, has a lifetime ({tau}{sub 0}) of 0.081 {mu}s and a standard reduction potential of {approximately} 1.2 V; it is quenched by electron donors (D) such as ethylenediaminetetraacetic acid (EDTA), triethanolamine (TEOA), ascorbate ion, deprotonated cysteine, and reduced glutathione with values of k{sub q} that depend on the pH of the solution and the reducing ability of the quencher. The one-electron-reduced species, Ru(bpm){sub 3}{sup +}, is formed in the quenching reaction; it is also produced electrochemically and from the reaction of radiolytically generated CO{sub 2}{sup {center dot}{minus}} with Ru(bpm){sub 3}{sup 2+} (k = 6.7 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}). Ru(bpm){sub 3}{sup +} is a good reducing agent (E{sub ox}{sup 0} = 0.73 V) and reduces MV{sup 2+} (methylviologen) to MV{sup {center dot}+} (k = 1.0 {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}). Ru(bpm){sub 3}{sup +} also undergoes protonation; its acidic form (pK{sub a} 6.3) is a milder reducing agent (E{sub ox}{sup 0} = 0.50 V) but is still capable of reducing MV{sup 2+} (k = 1.0 {times} 10{sup 6} M{sup {minus}1} s{sup {minus}1}). Both forms of Ru(bpm){sub 3}{sup +} are unstable with respect to long-term storage; it is likely they engage in disproportionation and/or reaction with the solvent. The continuous photolysis of a solution containing Ru(bpm){sub 3}{sup 2+}, MV{sup 2+}, and a sacrificial reductive quencher (EDTA, TEOA) generates MV{sup {center dot}+}. Values of {eta}{sub ce} of 0.64 and {approximately}0.7 for TEOA and EDTA, respectively, in alkaline solution have been obtained.

  10. Maximizing productivity of CHO cell-based fed-batch culture using chemically defined media conditions and typical manufacturing equipment.

    PubMed

    Huang, Yao-Ming; Hu, WeiWei; Rustandi, Eddie; Chang, Kevin; Yusuf-Makagiansar, Helena; Ryll, Thomas

    2010-01-01

    A highly productive chemically defined fed-batch process was developed to maximize titer and volumetric productivity for Chinese hamster ovary cell-based recombinant protein manufacturing. Two cell lines producing a recombinant antibody (cell line A) and an Fc-fusion protein (cell line B) were used for development. Both processes achieved product titers of 10 g/L on day 18 under chemically defined conditions. For cell line B, the use of plant derived hydrolysates combined with the optimized chemically defined medium increased the titer to 13 g/L. Volumetric productivities were increased from a base line of about 200 mg/L/d to about 500 mg/L/d under chemically defined conditions and as high as 700 mg/L/d with cell line B using plant derived hydrolysates. Peak cell densities reached greater than 20E6 vc/mL, and cell viabilities were maintained above 80% on day 18 without the use of antiapoptotic genes or temperature shift. A rapid compound screening method was developed to effectively test positive factors within 72 h. Peak volumetric oxygen uptake rates (OUR) more than tripled from the baseline condition. Oxygen demand continued to increase after maximum cell density was reached with a maximal OUR of 3.7 mmol/L/h. The new process format was scaled up and verified at 100 L pilot scale using reactor equipment of similar configuration as used at manufacturing scale. PMID:20945494

  11. Exact Solutions for the Magnetohydrodynamic Flow of a Jeffrey Fluid with Convective Boundary Conditions and Chemical Reaction

    NASA Astrophysics Data System (ADS)

    Alsaedi, Ahmed; Iqbal, Zahid; Mustafa, Meraj; Hayat, Tasawar

    2012-09-01

    The two-dimensional magnetohydrodynamic (MHD) flow of a Jeffrey fluid is investigated in this paper. The characteristics of heat and mass transfer with chemical reaction have also been analyzed. Convective boundary conditions have been invoked for the thermal boundary layer problem. Exact similarity solutions for flow, temperature, and concentration are derived. Interpretation to the embedded parameters is assigned through graphical results for dimensionless velocity, temperature, concentration, skin friction coefficient, and surface heat and mass transfer. The results indicate an increase in the velocity and the boundary layer thickness by increasing the rheological parameter of the Jeffrey fluid. An intensification in the chemical reaction leads to a thinner concentration boundary layer.

  12. Waste treatment process for removal of contaminants from aqueous, mixed-waste solutions using sequential chemical treatment and crossflow microfiltration, followed by dewatering

    SciTech Connect

    Vijayan, S.; Wong, Chi Fun; Buckley, L.P.

    1992-12-31

    It is an object of the claimed invention to combine chemical treatment with microfiltration process to treat groundwater, leachate from contaminated soil washing, surface and run-off waters contaminated with toxic metals, radionuclides and trace amounts of organics from variety of sources. The process can also be used to treat effluents from industrial processes such as discharges associated with smelting, mining and refining operations. Influent contaminants amenable to treatment are from a few mg/L to hundreds of mg/L. By selecting appropriate precipitation, ion exchange and adsorption agents and conditions, efficiencies greater than 99.9 percent can be achieved for removal of contaminants. The filtered water for discharge can be targeted with either an order of magnitude greater or lower than contaminant levels for drinking water.

  13. Laboratory conditions and safety in a chemical warfare agent analysis and research laboratory.

    PubMed

    Kenar, Levent; Karayilanoğlu, Turan; Kose, Songul

    2002-08-01

    Toxic chemicals have been used as weapons of war and also as means of terrorist attacks on civilian populations. Research focusing on chemical warfare agents (CWAs) may be associated with an increased risk of exposure to and contamination by these agents. This article summarizes some of the regulations concerning designation and safety in a CWA analysis and research laboratory and medical countermeasures in case of an accidental exposure. The design of such a laboratory, coupled with a set of safety guidelines, provides for the safe conduct of research and studies involving CWAs. Thus, a discussion of decontamination and protection means against CWAs is also presented. PMID:12188231

  14. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    NASA Astrophysics Data System (ADS)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)

  15. Low-thrust chemical propulsion system propellant expulsion and thermal conditioning study. Executive summary

    NASA Technical Reports Server (NTRS)

    Merino, F.; Wakabayashi, I.; Pleasant, R. L.; Hill, M.

    1982-01-01

    Preferred techniques for providing abort pressurization and engine feed system net positive suction pressure (NPSP) for low thrust chemical propulsion systems (LTPS) were determined. A representative LTPS vehicle configuration is presented. Analysis tasks include: propellant heating analysis; pressurant requirements for abort propellant dump; and comparative analysis of pressurization techniques and thermal subcoolers.

  16. Numerical simulation of the middle atmosphere chemical composition and temperature under changing solar conditions

    NASA Technical Reports Server (NTRS)

    Zadorozhny, A. M.; Dyominov, I. G.; Tuchkov, G. A.

    1989-01-01

    There are given results of the numerical experiments on modelling the influence of solar activity on chemical composition and temperature of the middle atmosphere. The consideration is made for peculiarities of solar activity impact under different values of antropogenic pollution of the atmosphere with chlorofluorocarbons and other stuff.

  17. THE INSTABILITY OF ESTROGENIC CHEMICALS DURING LABORATORY STATIC EXPOSURE CONDITIONS WITH MALE FATHEAD MINNOWS

    EPA Science Inventory

    Endocrine disrupting chemicals (EDCs) such as Para-nonylphenol (NP), estradiol (E2), estrone (E1), estriol (E3) and ethynylestradiol (EE2) are shown to be ubiquitous in surface waters, sediments and sludge. These EDCs are known to induce vitellogenin gene (Vg) expression in male...

  18. Chemical conversion of cisplatin and carboplatin with histidine in a model protein crystallized under sodium iodide conditions

    PubMed Central

    Tanley, Simon W. M.; Helliwell, John R.

    2014-01-01

    Cisplatin and carboplatin are platinum anticancer agents that are used to treat a variety of cancers. Previous X-ray crystallographic studies of carboplatin binding to histidine in hen egg-white lysozyme (HEWL) showed a partial chemical conversion of carboplatin to cisplatin owing to the high sodium chloride concentration used in the crystallization conditions. Also, the co-crystallization of HEWL with carboplatin in sodium bromide conditions resulted in the partial conversion of carboplatin to the transbromoplatin form, with a portion of the cyclobutanedicarboxylate (CBDC) moiety still present. The results of the co-crystallization of HEWL with cisplatin or carboplatin in sodium iodide conditions are now reported in order to determine whether the cisplatin and carboplatin converted to the iodo form, and whether this took place in a similar way to the partial conversion of carboplatin to cisplatin in NaCl conditions or to transbromoplatin in NaBr conditions as seen previously. It is reported here that a partial chemical transformation has taken place to a transplatin form for both ligands. The NaI-grown crystals belonged to the monoclinic space group P21 with two molecules in the asymmetric unit. The chemically transformed cisplatin and carboplatin bind to both His15 residues, i.e. in each asymmetric unit. The binding is only at the Nδ atom of His15. A third platinum species is also seen in both conditions bound in a crevice between symmetry-related molecules. Here, the platinum is bound to three I atoms identified based on their anomalous difference electron densities and their refined occupancies, with the fourth bound atom being a Cl atom (in the cisplatin case) or a portion of the CBDC moiety (in the carboplatin case). PMID:25195879

  19. Boundary conditions for the paleoenvironment: Chemical and Physical Processes in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Schloerb, F. P.; Ziurys, L. M.

    1986-01-01

    The present research includes searches for important new interstellar constituents; observations relevant to differentiating between different models for the chemical processes that are important in the interstellar environment; and coordinated studies of the chemistry, physics, and dynamics of molecular clouds which are the sites or possible future sites of star formation. Recent research has included the detection and study of four new interstellar molecules; searches which have placed upper limits on the abundance of several other potential constituents of interstellar clouds; quantitative studies of comparative molecular abundances in different types of interstellar clouds; investigation of reaction pathways for astrochemistry from a comparison of theory and the observed abundance of related species such as isomers and isotopic variants; studies of possible tracers of energenic events related to star formation, including silicon and sulfur containing molecules; and mapping of physical, chemical, and dynamical properties over extended regions of nearby cold molecular clouds.

  20. Monte Carlo simulation study on the flow conditions of a vacuum chemical epitaxy system

    NASA Astrophysics Data System (ADS)

    Cotta, M. A.; de Carvalho, M. M. G.

    1992-07-01

    This work presents a numerical simulation, using Monte Carlo method, of the gas phase behavior in a vacuum chemical epitaxy (VCE) system, without hydride cracker. From this simulation, it is shown that the growth rate depends on the gas - mainly hydride —pressure in the growth chamber. This dependence is stronger for pressures above 10 -3 Torr, where the growth rate decreases almost linearly with increasing pressure. The slope of this curve decreases with the sticking coefficient of the organometallic molecules, that is, when growth temperature increases. Experimental results agree well with the predicted results which can, qualitatively, explain the growth rate behavior with the hydride flows used in VCE, and show that gas phase collisions should not be neglected even in chemical beam epitaxy (CBE) systems.

  1. Sensitivity of the invasive bivalve Corbicula fluminea to candidate control chemicals: The role of dissolved oxygen conditions.

    PubMed

    Rosa, Inês C; Garrido, Rita; Ré, Ana; Gomes, João; Pereira, Joana L; Gonçalves, Fernando; Costa, Raquel

    2015-12-01

    The freshwater Corbicula fluminea is a major aquatic nuisance worldwide. Current pest control methods raise cost-effectiveness and environmental concerns, which motivate research into improved mitigation approaches. In this context, the susceptibility of the clams to chemicals under reduced oxygen conditions was examined. Biocides with different mechanisms of toxicity (niclosamide, polyDADMAC, ammonium nitrate, potassium chloride and dimethoate) were tested under normoxic (>7 mg L(-1) dissolved O2) and hypoxic (<2 mg L(-1) dissolved O2) conditions. Hypoxia was observed to potentiate chemical treatment, particularly when combined with non-overwhelming doses that would produce only intermediate responses by themselves. For niclosamide, ammonium nitrate and dimethoate, clam mortality enhancements up to 400% were observed under hypoxia as compared to dosing upon normal dissolved oxygen conditions. For polyDADMAC and potassium chloride, substantially lower mortality enhancements were found. The differences in the clams' sensitivity to the chemicals under hypoxia could be linked to the expected mechanisms of action. This suggests that judicious selection of the biocide is essential if optimized combined control treatments are to be designed and provides an insight into the interference of frequent hypoxia events in the response of natural clam populations to contaminant loads. PMID:26254082

  2. Dependence of electro-optical properties on the deposition conditions of chemical bath deposited CdS thin films

    SciTech Connect

    Dona, J.M.; Herrero, J.

    1997-11-01

    Lately, there has been a sharp increase in the publication of papers on chemical bath deposition of CdS thin films and related materials due to successful results obtained using this method to fabricate CdS thin-film buffer layers for CuInSe{sub 2}- and CdTe-based polycrystalline thin-film solar cells. Generally, these papers focus on previously proposed methods of studying film characteristics without a systematic study of the influence of deposition conditions on film characteristics. In this paper the authors present an exhaustive study of the chemical bath-deposited CdS thin films electro-optical properties dependence on deposition variables. The authors propose not only a set of conditions for obtaining CdS thin films by this method but additionally, suitable deposition process conditions for certain application requirements, such as buffer layers for thin-film solar cells. The observed electro-optical characteristics dependence on the deposition variables corroborates the chemical mechanism that they proposed previously for this process.

  3. Physical and Chemical Conditions in the Dust Formation Zone of IRC+10216

    NASA Astrophysics Data System (ADS)

    Fonfría Expósito, J. P.; Cernicharo, J.; Richter, M. J.; Lacy, J.

    A mid-infrared high-resolution spectral survey of the source IRC+10216 (CW Leo) has been carried out in the range 11 to 14 μm. A large numer of lines of C2H2 and HCN, among their most abundant isotopologues, have been identified. Many lines belong to hot bands involving high-energy ro-vibrational levels which allows the accurate determination of the physical and chemical conditions in the inner envelope. For this purpose, we have developed a radiative transfer model which can deal with almost all the detected lines, fitting them satisfactorily. We have fitted the continuum with the aid of the ISO avaliable data, and more than 200 different rovibrational lines to get the kinetic, vibrational and rotational temperatures and the abundances of the C2H2 and HCN between 1 and 250 R*. 1. Introduction IRC+10216 is a C-rich AGB star with an large circumstellar envelope (CSE) at ~ 180 pc from the Earth. The stellar temperature is ~ 2300 K. The derived mass-loss rate is set to be 2 × 10-5 Msol yr-1 approximately (Keady et al. 1988, Cernicharo et al. 1999). By now, 60 different molecular species have been detected besides a large number of their isotopologues. The dust grains, which are assumed to be formed by amorphous graphite and refractary species such as SiC, condense in two different shells: the first one over 5 R* and the second over 15 R* (Keady et al. 1988). The acceleration produced by the interaction between the dust and the photons emitted by the star and other phenomena, establish a complex velocity profile with velocities of 1 - 3 km s-1 (1 ≤ r/R* ≤ 5), 11 km s-1 (5 ≤ r/R* ≤ 15) and 14 km s-1 (15 ≤ r/R*) (Keady et al. 1988, Ridgway et al. 1988). The most abundant species is CO with 8 × 10-4, followed by C2H2 with 8 × 10-5 and HCN with 4 × 10-5 (Keady et al. 1993, Cernicharo et al. 1996). 2. Observations, detections and results The observations were obtained in December of 2002 with the TEXES spectrometer (Lacy et al. 2001), working between 5 and 25 μm, and the 3 m optimized infrared telescope IRTF in Hawaii. The data were corrected for atmospheric effects using the difference of a black body and the atmospheric emission. In addition, the baseline have been removed using a four degree polynomial. In the forest of lines detected in the observed spectrum we have identified corresponding to the R and Q branches of rovibrational transitions ν5, ν4+ν5-ν4, 2ν5-ν5, 2ν4+ν5-2ν4, ν4+2ν5-ν4+ν5 and 3ν5-2ν5 for C2H2, some of them for H13CCH and ν2 and 2ν2-ν2 for HCN. Several lines of SiS have been identified and many lines remain still unidentified. The Figure 1 shows part of the whole spectrum. The main results derived through the fittings of the lines show that the abundances of C2H2 and HCN have their maximums in the middle region (between the two dust formation shells) as the LTE models predict, being compatible with the values obtained from observations for the outer envelope. The vibrational temperature behavior depends on the energy of the level and seems to support the existence of radiative pumping mechanisms that deviates the populations of the vibrational levels from LTE (Cernicharo et al. 1999). These deviations depend on the molecule, being very different for C2H2 than HCN because of their radiative selection rules (e.g., ν4 (πg) of C2H2 is not connected with the G.S.). While most of the vibrational levels of C2H2 are in LTE in the innermost envelope, deviating from it in the rest of the CSE, the vibrational levels of HCN present an important radiative pumping even near the star. The rotational levels seem to be in LTE until J = 15 for all the studied vibrational levels.

  4. Chemical conversion of cisplatin and carboplatin with histidine in a model protein crystallized under sodium iodide conditions

    SciTech Connect

    Tanley, Simon W. M.; Helliwell, John R.

    2014-08-29

    Crystals of HEWL with cisplatin and HEWL with carboplatin grown in sodium iodide conditions both show a partial chemical transformation of cisplatin or carboplatin to a transiodoplatin (PtI{sub 2}X{sub 2}) form. The binding is only at the N{sup δ} atom of His15. A further Pt species (PtI{sub 3}X) is also seen, in both cases bound in a crevice between symmetry-related protein molecules. Cisplatin and carboplatin are platinum anticancer agents that are used to treat a variety of cancers. Previous X-ray crystallographic studies of carboplatin binding to histidine in hen egg-white lysozyme (HEWL) showed a partial chemical conversion of carboplatin to cisplatin owing to the high sodium chloride concentration used in the crystallization conditions. Also, the co-crystallization of HEWL with carboplatin in sodium bromide conditions resulted in the partial conversion of carboplatin to the transbromoplatin form, with a portion of the cyclobutanedicarboxylate (CBDC) moiety still present. The results of the co-crystallization of HEWL with cisplatin or carboplatin in sodium iodide conditions are now reported in order to determine whether the cisplatin and carboplatin converted to the iodo form, and whether this took place in a similar way to the partial conversion of carboplatin to cisplatin in NaCl conditions or to transbromoplatin in NaBr conditions as seen previously. It is reported here that a partial chemical transformation has taken place to a transplatin form for both ligands. The NaI-grown crystals belonged to the monoclinic space group P2{sub 1} with two molecules in the asymmetric unit. The chemically transformed cisplatin and carboplatin bind to both His15 residues, i.e. in each asymmetric unit. The binding is only at the N{sup δ} atom of His15. A third platinum species is also seen in both conditions bound in a crevice between symmetry-related molecules. Here, the platinum is bound to three I atoms identified based on their anomalous difference electron densities and their refined occupancies, with the fourth bound atom being a Cl atom (in the cisplatin case) or a portion of the CBDC moiety (in the carboplatin case)

  5. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

    PubMed Central

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J

    2015-01-01

    Summary Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  6. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions.

    PubMed

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J; Schanz, Hans-Jörg

    2015-01-01

    Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2',6'-dimethyl-4'-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  7. The effect of chemical composition and austenite conditioning on the transformation behavior of microalloyed steels

    SciTech Connect

    Mousavi Anijdan, S.H.; Rezaeian, Ahmad; Yue, Steve

    2012-01-15

    In this investigation, by using continuous cooling torsion (CCT) testing, the transformation behavior of four microalloyed steels under two circumstances of austenite conditioning and non-conditioning was studied. A full scale hot-rolling schedule containing a 13-pass deformation was employed for the conditioning of the austenite. The CCT tests were then employed till temperature of {approx} 540 Degree-Sign C and the flow curves obtained from this process were analyzed. The initial and final microstructures of the steels were studied by optical and electron microscopes. Results show that alloying elements would decrease the transformation temperature. This effect intensifies with the gradual increase of Mo, Nb and Cu as alloying elements added to the microalloyed steels. As well, austenite conditioning increased the transformation start temperature due mainly to the promotion of polygonal ferrite formation that resulted from a pancaked austenite. The final microstructures also show that CCT alone would decrease the amount of bainite by inducing ferrite transformation in the two phase region. In addition, after the transformation begins, the deformation might result in the occurrence of dynamic recrystallization in the ferrite region. This could lead to two different ferrite grain sizes at the end of the CCT. Moreover, the Nb bearing steels show no sign of decreasing the strength level after the transformation begins in the non-conditioned situation and their microstructure is a mix of polygonal ferrite and bainite indicating an absence of probable dynamic recrystallization in this condition. In the conditioned cases, however, these steels show a rapid decrease of the strength level and their final microstructures insinuate that ferrite could have undergone a dynamic recrystallization due to deformation. Consequently, no bainite was seen in the austenite conditioned Nb bearing steels. The pancaking of austenite in the latest cases produced fully polygonal ferrite structures. - Highlights: Black-Right-Pointing-Pointer Adding alloying elements would decrease the transformation temperatures. Black-Right-Pointing-Pointer Austenite conditioning increases the transformation start temperature. Black-Right-Pointing-Pointer Deformation could induce the occurrence of dynamic recrystallization in ferrite region.

  8. Growth process conditions of vertically aligned carbon nanotubes using plasma enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Chhowalla, M.; Teo, K. B. K.; Ducati, C.; Rupesinghe, N. L.; Amaratunga, G. A. J.; Ferrari, A. C.; Roy, D.; Robertson, J.; Milne, W. I.

    2001-11-01

    The growth of vertically aligned carbon nanotubes using a direct current plasma enhanced chemical vapor deposition system is reported. The growth properties are studied as a function of the Ni catalyst layer thickness, bias voltage, deposition temperature, C2H2:NH3 ratio, and pressure. It was found that the diameter, growth rate, and areal density of the nanotubes are controlled by the initial thickness of the catalyst layer. The alignment of the nanotubes depends on the electric field. Our results indicate that the growth occurs by diffusion of carbon through the Ni catalyst particle, which rides on the top of the growing tube.

  9. Sustainable Applications of Nano-Catalysts and Alternative Methods in the Greener Synthesis and Transformations of Chemical

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a var...

  10. Inactivation of the novel avian influenza A (H7N9) virus under physical conditions or chemical agents treatment

    PubMed Central

    2013-01-01

    Background In the spring of 2013, a novel avian-origin influenza A (H7N9) virus in Eastern China emerged causing human infections. Concerns that a new influenza pandemic could occur were raised. The potential effect of chemical agents and physical conditions on inactivation of the novel avian influenza H7N9 virus had not been assessed. Methods To determine the inactivation effectiveness of the novel avian influenza A (H7N9) virus under various physical conditions and chemical treatments, two H7N9 viruses A/Anhui/1/2013 and A/Shanghai/1/2013 were treated by varied temperatures, ultraviolet light, varied pHs and different disinfectants. The viruses with107.7 EID50 were exposed to physical conditions (temperature, ultraviolet light and pH) or treated with commercial chemical agents (Sodium Hypochlorite, Virkon-S, and Ethanol) respectively. After these treatments, the viruses were inoculated in SPF embryonated chicken eggs, the allantoic fluid was collected after 7296 hours culture at 35C and tested by haemagglutination assay. Results Both of the tested viruses could tolerate conditions under 56C for 15 minutes or 60C for 5 minutes, but their infectivity was completely lost under 56C for 30 minutes, 65C for 10 minutes, 70C, 75C and 100C for 1 minute. It was also observed that the H7N9 viruses lost their infectivity totally after exposure of ultraviolet light irradiation for 30 minutes or longer time. Additionally, the viruses were completely inactivated at pH less than 2 for 0.5 hour or pH 3 for 24 hours, however, viruses remained infectious under pH treatment of 412 for 24 hours. The viruses were totally disinfected when treated with Sodium Hypochlorite, Virkon-S and Ethanol at recommended concentrations after only 5 minutes. Conclusions The novel avian influenza A (H7N9) virus can be inactivated under some physical conditions or with chemical treatments, but they present high tolerance to moderately acidic or higher alkali conditions. The results provided the essential information for public health intervention of novel H7N9 avian influenza outbreak. PMID:24034697

  11. Studying of boiling of aqueous solutions under elevated pressures and evaluating the circulation conditions in boiling-type evaporators at supercritical mineralization

    NASA Astrophysics Data System (ADS)

    Lavrikov, A. V.; Kuzma-Kichta, Yu. A.

    2009-03-01

    This publication concerns the analysis of an interaction between steam bubbles in highly mineralized aqueous solutions flowing in the natural-circulation loop of a flash evaporator. Data are given on the distribution of steam bubbles with respect to their diameters and their floating velocities; an expression is also given for the interaction factor making it possible to improve the technique of hydrodynamics calculations for the apparatuses under discussion.

  12. Guidelines for measuring the physical, chemical, and biological condition of wilderness ecosystems. General technical report (Final)

    SciTech Connect

    Fox, D.G.; Bernabo, J.C.; Hood, B.

    1987-11-01

    Guidelines include a large number of specific measures to characterize the existing condition of wilderness resources. Measures involve the atmospheric environment, water chemistry and biology, geology and soils, and flora. Where possible, measures are coordinated with existing long-term monitoring programs. Application of the measures will allow more effective evaluation of proposed new air-pollution sources.

  13. Adsorption kinetics of magnetic biochar derived from peanut hull on removal of Cr (VI) from aqueous solution: Effects of production conditions and particle size.

    PubMed

    Han, Yitong; Cao, Xi; Ouyang, Xin; Sohi, Saran P; Chen, Jiawei

    2016-02-01

    Magnetic biochar was made from peanut hull biomass using iron chloride in a simplified aqueous phase approach and pyrolysis at alternative peak temperatures (450-650 °C). Magnetic biochar showed an extreme capacity for adsorption of hexavalent chromium Cr (VI) from aqueous solution, which was 1-2 orders of magnitude higher compared to standard (non-magnetic) biochar from the same feedstock. Adsorption increased with pyrolysis temperature peaking at 77,542 mg kg(-1) in the sample pyrolysed at 650 °C. In contrast to magnetic biochar, the low adsorption capacity of standard biochar decreased with increasing pyrolysis temperature. The fine particle size of magnetic biochar and low aqueous pH were also important for adsorption. Surfaces of products from batch adsorption experiments were characterized by scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, X-ray photoelectron spectroscopy and vibrating sample magnetometer. This revealed that γ-Fe2O3 was crucial to the properties (adsorbance and magnetism) of magnetic biochar. The removal mechanism was the Cr (VI) electrostatic attracted on protonated -OH on γ-Fe2O3 surface and it could be desorbed by alkaline solution. Findings suggest that pyrolysis has potential to create effective, magnetically recoverable adsorbents relevant to environmental application. PMID:26692510

  14. Chemically defined conditions for human iPS cell derivation and culture

    PubMed Central

    Chen, Guokai; Gulbranson, Daniel R.; Hou, Zhonggang; Bolin, Jennifer M.; Ruotti, Victor; Probasco, Mitchell D.; Smuga-Otto, Kimberly; Howden, Sara E.; Diol, Nicole R.; Propson, Nicholas E.; Wagner, Ryan; Lee, Garrett O.; Antosiewicz-Bourget, Jessica; Teng, Joyce M. C.; Thomson, James A.

    2011-01-01

    We reexamine the individual components for human ES and iPS cell culture, and formulate a cell culture system in which all protein reagents for liquid media, attachment surfaces, and splitting are chemically defined. A major improvement is the lack of a serum albumin component, as variations in either animal or human sourced albumin batches have previously plagued human ES and iPS cell culture with inconsistencies. Using this new medium (E8) and vitronectin-coated surfaces, we demonstrate improved derivation efficiencies of vector-free human iPS cells with an episomal approach. This simplified E8 medium should facilitate both the research use and clinical applications of human ES and iPS cells and their derivatives, and should be applicable to other reprogramming methods. PMID:21478862

  15. Solving Heat Conduction Problems in Movable Boundary Domains under Intensive Physical-Chemical Transformation Conditions

    NASA Astrophysics Data System (ADS)

    Garashchenko, A. N.; Rudzinsky, V. P.; Garashchenko, N. A.

    2016-02-01

    Results of solving problems of simulating temperature fields in domains with movable boundaries of characteristic zones of intensive physical-chemical and thermomechanical transformations to be realized in materials upon high-temperature heating have been presented. Intumescent fire-protective coatings based on organic and mineral materials are the object of study. Features of numerical realization of input equation systems taking into account, in particular, a dynamics of considerable increase and subsequent decrease of the intumescent layer thickness have been considered. Example calculations for structures of metal and wood protected with various coatings are given. Results of calculating two-dimensional temperature fields in polymer composite square-shaped structures with internal cruciform load-bearing elements have been presented. The intumescent coating is arranged on the external surface of a structure. The solution of the above-listed problems is of important significance to provide fire protection of different-purpose structures and products.

  16. Effect of preparation conditions on physic-chemical properties of tin-doped nanocrystalline indium oxide

    NASA Astrophysics Data System (ADS)

    Malinovskaya, T. D.; Sachkov, V. I.; Zhek, V. V.; Nefedov, R. A.

    2016-01-01

    In this paper the results of investigation of phase formation and change of concentration of free electrons (Ne) in indium tin oxide system during heat treatment of coprecipitated hydroxides of indium and tin from nitric and hydrochloric solutions and also, for comparison melts of salts nitrates by an alkaline reactant (NH4OH) are considered.The performed investigation allowed to set the optimal condition of preparation of polycrystalline tin-doped indium oxide with maximal electron concentration.

  17. Evaluation of the migration of chemicals from baby bottles under standardised and duration testing conditions.

    PubMed

    Onghena, Matthias; Van Hoeck, Els; Negreira, Noelia; Quirynen, Laurent; Van Loco, Joris; Covaci, Adrian

    2016-05-01

    After the prohibition of bisphenol-A-containing polycarbonate baby bottles in the European Union (EU), alternative materials, such as polypropylene, polyethersulphone, Tritan™ copolyester, etc., have appeared on the market. Based on an initial screening and in vitro toxicity assessment, the most toxic migrating compounds were selected to be monitored and quantified using validated GC- and LC-QqQ-MS methods. The effect of several 'real-life-use conditions', such as microwave, sterilisation and dishwasher, on the migration of different contaminants was evaluated by means of duration tests. These results were compared with a reference treatment (filling five times with pre-heated simulant at 40°C) and with the legal EU 'repetitive-use conditions' (three migrations, 2 h at 70°C). Analysis of the third migration step of the EU repetitive-use conditions (which has to comply with the EU legislative migration limits) showed that several non-authorised compounds were observed in some baby bottles exceeding 10 µg kg(-1). However, all authorised compounds were detected well below their respective specific migration limits (SMLs). The reference experiment confirmed the migration of some of the compounds previously detected in the EU repetitive-use experiment, though at lower concentrations. Analysis of extracts from the microwave and dishwasher experiments showed a reduction in the migration during the duration tests. In general, the concentrations found were low and comparable with the reference experiment. Similar observations were made for the two sterilisation types: steam and cooking sterilisation. However, steam sterilisation seems to be more recommended for daily use of baby bottles, since it resulted in a lower release of substances afterwards. Repeated use of baby bottles under 'real-life' conditions showed no increase in the migration of investigated compounds and, after some time, the migration of these compounds even became negligible. PMID:27043734

  18. An evaluation of a river health using the index of biological integrity along with relations to chemical and habitat conditions.

    PubMed

    An, Kwang-Guk; Park, Seok Soon; Shin, Joung-Yi

    2002-11-01

    We evaluated the health condition of a temperate river during June-November 1999 through applications of the index of biological integrity (IBI) using fish assemblages and qualitative habitat evaluation index (QHEI) as well as chemical analyses. Overall IBI values ranged from 13 to 37 and averaged 23 (n = 25, standard error = 1.16), indicating a "poor" or "very poor" condition according to the criteria of modified Karr [Fisheries 6 (1981) 21]. The values of mean IBI declined at a rate of 0.22 km(-1) (R2 = 0.91, p < 0.05) along the longitudinal distance from the headwaters to the downstream sites. Reduced IBI values at downstream sites reflected low forest cover, high population density and high nutrient enrichments. Ecotoxicity tests using the river water also showed that toxic impacts were evident in the downriver sites. These factors resulted in decreases of riffle benthic species and insectivores and increases of tolerant species, anormalies and exotic species in the river. Spatial pattern in IBI agreed with QHEI values, which showed a linear relation (R2 = 0.998, p < 0.001) with species richness. Field measurements of conductivity and pH, an indicators for variation of conservative ions, showed that the river water was diluted by 40% fold by summer monsoon rain and surface run-off from the watershed, resulting in a physical and chemical instability during the monsoon. For these reasons, average IBI values during the monsoon and postmonsoon decreased >20% compared to the premonsoon, indicating that IBI values were also affected by flow regime. Based on the overall physico-chemical data and IBI values, the river health is rapidly degrading due to the combined effect of chemical contaminations and habitat modifications. PMID:12437291

  19. All-aqueous multiphase microfluidics

    PubMed Central

    Song, Yang; Sauret, Alban; Cheung Shum, Ho

    2013-01-01

    Immiscible aqueous phases, formed by dissolving incompatible solutes in water, have been used in green chemical synthesis, molecular extraction and mimicking of cellular cytoplasm. Recently, a microfluidic approach has been introduced to generate all-aqueous emulsions and jets based on these immiscible aqueous phases; due to their biocompatibility, these all-aqueous structures have shown great promises as templates for fabricating biomaterials. The physico-chemical nature of interfaces between two immiscible aqueous phases leads to unique interfacial properties, such as an ultra-low interfacial tension. Strategies to manipulate components and direct their assembly at these interfaces needs to be explored. In this paper, we review progress on the topic over the past few years, with a focus on the fabrication and stabilization of all-aqueous structures in a multiphase microfluidic platform. We also discuss future efforts needed from the perspectives of fluidic physics, materials engineering, and biology for fulfilling potential applications ranging from materials fabrication to biomedical engineering. PMID:24454609

  20. Low-thrust chemical propulsion system propellant expulsion and thermal conditioning study

    NASA Technical Reports Server (NTRS)

    Merino, F.; Wakabayashi, I.; Pleasant, R. L.; Hill, M.

    1982-01-01

    Thermal conditioning systems for satisfying engine net positive suction pressure (NPSP) requirements, and propellant expulsion systems for achieving propellant dump during a return-to-launch site (RTLS) abort were studied for LH2/LO2 and LCH4/LO2 upper stage propellant combinations. A state-of-the-art thermal conditioning system employing helium injection beneath the liquid surface shows the lowest weight penalty for LO2 and LCH4. A technology system incorporating a thermal subcooler (heat exchanger) for engine NPSP results in the lowest weight penalty for the LH2 tank. A preliminary design of two state-of-the-art and two new technology systems indicates a weight penalty difference too small to warrant development of a LH2 thermal subcooler. Analysis results showed that the LH2/LO2 propellant expulsion system is optimized for maximum dump line diameters, whereas the LCH4/LO2 system is optimized for minimum dump line diameter (LCH4) and maximum dump line diameter (LO2). The primary uncertainty is the accurate determination of two-phase flow rates through the dump system; experimentation is not recommended because this uncertainty is not considered significant.

  1. Meteorites and the physico-chemical conditions in the early solar nebula

    NASA Astrophysics Data System (ADS)

    Aléon, J.

    2010-01-01

    Chondritic meteorites constitute the most ancient rock record available in the laboratory to study the formation of the solar system and its planets. Detailed investigations of their mineralogy, petrography, chemistry and isotopic composition and comparison with other primitive solar system samples such as cometary dust particles have allowed through the years to decipher the conditions of formation of their individual components thought to have once been free-floating pieces of dust and rocks in the early solar nebula. When put in the context of astrophysical models of young stellar objects, chondritic meteorites and cometary dust bring essential insights on the astrophysical conditions prevailing in the very first stages of the solar system. Several exemples are shown in this chapter, which include (1) high temperature processes and the formation of chondrules and refractory inclusions, (2) oxygen isotopes and their bearing on photochemistry and large scale geochemical reservoirs in the nebula, (3) organosynthesis and cold cloud chemistry recorded by organic matter and hydrogen isotopes, (4) irradiation of solids by flares from the young Sun and finally (5) large scale transport and mixing of material evidenced in chondritic interplanetary dust particles and samples returned from comet Wild2 by the Stardust mission.

  2. Physico­chemical Properties of Secondary Organic Aerosol (soa) Particles Generated Under Laboratory Photooxidation Conditions

    NASA Astrophysics Data System (ADS)

    Demirdjian, B.; Rossi, M. J.

    The goal of this experiment is to investigate the chemical reactivity of secondary or- ganic aerosol particles (SOA) in the presence of NOx. of special interest is the ques- tion whether or not SOA enables the reduction of NO2 to HONO, an important photochemical OH precursor. We report the controlled production of SOA particles using 5ppm of toluene (C7H8) or limonene (C10H16) in the presence of O3 or NO2 at 60% r.h. at 1 atmosphere of air using a (filtered) 150W high­pressure Xe arc lamp as a photon source. The particle production is taking place in an atmospheric pressure flow cell whose gas phase residence time was chosen to lie in the range of one to several seconds. The gas phase is monitored using a differentially pumped quadrupole mass spectrometer whereas the condensed phase has been characterized both by its total particle count using a Condensation Nucleation Counter (CNC) or a downstream Differential Mobility Analyzer (DMA) coupled to an additional CNC. Particle counts of several 105 particles cm-3 were routinely achieved. Both O3 and NO2 are removed immediately after the flow reactor using a diffusion denuder coated with either KI or NDA. The flow has been directed across a glass fiber filter during one to two hours at constant throughput. Subsequently the SOA particles supported on the glass fiber fil- ter, typically a few mg, have been investigated in a low-pressure Knudsen flow reactor using NO2 and H2O.

  3. Determination of formal kinetic constants of thermal decomposition of aqueous hydrogen peroxide solution in a mixture of magnetic powder, based on experimental thermogram, obtained in adiabatic conditions

    NASA Astrophysics Data System (ADS)

    Zaripov, Jamshed; Borisov, Boris; Bondarchuk, Sergey

    2014-08-01

    Process of thermal decomposition of hydrogen peroxide aqueous solution with the addition of magnetic powder in the form of toner for printers and lanthanum manganite were considered. Obtained resulting from an experiment in the Dewar container conducted thermogram analyzed using mass balance equations and heat. Formal kinetic parameters determined, and conclude that the magnetic powder in the mixture does not have catalytic properties. The described technique is recommended as a rapid analysis of the kinetics of the various reactions to substances having predefined thermal and thermodynamic properties.

  4. Experimental studies of a single-effect absorption refrigerator using aqueous lithium-bromide: Effect of operating condition to system performance

    SciTech Connect

    Aphornratana, Satha; Sriveerakul, Thanarath

    2007-11-15

    This paper describes an experimental investigation of a single-effect absorption using aqueous lithium-bromide as working fluid. A 2 kW cooling capacity experimental refrigerator was tested with various operating temperatures. It was found that the solution circulation ratio (SCR) has a strong effect on the system performance. The measured SCR was 2-5 times greater than the theoretical prediction. This was due to the low performance of the absorber. The use of solution heat exchanger could increase the COP by up to 60%. (author)

  5. Chemical and physical studies of type 3 chondrites. IX. Thermoluminescence and hydrothermal annealing experiments and their relationship to metamorphism and aqueous alteration in type < 3. 3 ordinary chondrites

    SciTech Connect

    Guimon, R.K.; Lofgren, G.E.; Sears, D.W.G.

    1988-01-01

    Samples of four type 3 chondrites have been annealed at 400-850/sup 0/C and 0.77-1 kbar for 10-500 h in the presence of various amounts of water (0-10 wt.%) and sodium disilicate (0-2 molal) and their thermoluminescence properties measured. After annealing for > 20 h at temperatures > 600/sup 0/C, the TL sensitivity of the samples increased by factors of up to 40. After annealing at < 600/sup 0/C for 10-500 h, or relatively short periods at high temperatures (e.g., less than or equal to 20 h at 850/sup 0/C), the TL sensitivity of the samples decreased by up to 2 orders of magnitude (depending on the original value). The TL peak temperatures observed in the present experiments are consistent with a low form of feldspar (the TL phosphor) being produced at < 800/sup 0/C and a high form being produced at > 800/sup 0/C. When both high and low forms were present originally, the low-form was destroyed preferentially. The authors suggest that these data are consistent with the TL-metamorphism trends observed in type > 3.2 chondrites, being due to the formation of feldspar by the devitrification of chondrule glass during metamorphism. For types < 3.2, the TL data are equally consistent with these types experiencing lower levels of metamorphism than the higher types, or with type 3.0 being produced from higher types by aqueous alteration. The presence of water with non-terrestrial D/H ratios, and petrographic evidence for aqueous alteration in Semarkona, lead to favoring the aqueous alteration hypothesis.

  6. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-19

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified,more » including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  7. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-23

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenatedmore » molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  8. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-08-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (\\centerdot OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than \\centerdot OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  9. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Laskin, A.; Anastasio, C.; Laskin, J.; Zhang, Q.

    2014-12-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants - the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  10. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    SciTech Connect

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  11. Chemical hydrogen charging conditions for martensite transformation and surface cracking in type 304 stainless steel

    SciTech Connect

    Yang, Q.; Qiao, L.J.; Luo, J.L.; Chiovelli, S.

    1999-05-07

    It is well known that the presence of hydrogen in 304 stainless steel can induce martensite transformation and surface cracking in austenitic stainless steels. The change in microstructure would affect the corrosion behavior. Martensite could be preferentially dissolved, which results in an increase in anodic dissolution and facilitates the formation of active paths for stress corrosion cracking. Hydrogen-induced martensite has some effects on pitting corrosion and is also found to be related to hydrogen embrittlement. In previous reports, almost all the results were obtained by charging the specimens at very high cathodic current densities ({ge}50mA/cm{sup 2}). The objective of this work is to investigate the critical charging conditions for hydrogen-induced martensitic transformation and surface cracking of 304 stainless steel.

  12. The use of the magnetic field effect for studying a chemiluminescent chemical reaction in aqueous solution. Reaction rate constants and lifetimes of intermediate molecules

    NASA Astrophysics Data System (ADS)

    Triebel, Michael M.; Totrov, Maxim M.; Zorinyants, George E.; Frankevich, Eugene L.

    1993-11-01

    The phase shift magnetic field effect technique is applied for investigation of the chemiluminescent (ChL) reaction of luminol oxidation by potassium ferricyanide in aqueous alkali solution. The external modulated magnetic field changed the rate constant of recombination of luminol radicals. Rate constants of intermediate stages of the reaction are obtained: 10 8 M -1 s -1 for diazaquinone reaction with hydrogen peroxide, 2 X 10 6 M -1 s -1 for diazaquinone hydrolysis and 2 X 10 5 s -1 for the decomposition of hydroperoxide, which is a precursor of the light emitter.

  13. Emergence of Photoautotrophic Minimal Protocell-Like Supramolecular Assemblies, "Jeewanu" Synthesied Photo Chemically in an Irradiated Sterilised Aqueous Mixture of Some Inorganic and Organic Substances

    NASA Astrophysics Data System (ADS)

    Gupta, Vinod Kumar

    2014-12-01

    Sunlight exposed sterilised aqueous mixture of ammonium molybdate, diammonium hydrogen phosphate, biological minerals and formaldehyde showed photochemical formation of self-sustaining biomimetic protocell-like supramolecular assemblies "Jeewanu" (Bahadur and Ranganayaki J Brit Interplanet Soc 23:813-829 1970). The structural and functional characteristics of Jeewanu suggests that in possible prebiotic atmosphere photosy nergistic collaboration of non-linear processes at mesoscopic level established autocatalytic pathways on mineral surfaces by selforganisation and self recognition and led to emergence of similar earliest energy transducing supramolecular assemblies which might have given rise to common universal ancestor on the earth or elsewhere.

  14. Chemical profiling of Jatropha tissues under different torrefaction conditions: application to biomass waste recovery.

    PubMed

    Watanabe, Taiji; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

    2014-01-01

    Gradual depletion of the world petroleum reserves and the impact of environmental pollution highlight the importance of developing alternative energy resources such as plant biomass. To address these issues, intensive research has focused on the plant Jatropha curcas, which serves as a rich source of biodiesel because of its high seed oil content. However, producing biodiesel from Jatropha generates large amounts of biomass waste that are difficult to use. Therefore, the objective of our research was to analyze the effects of different conditions of torrefaction on Jatropha biomass. Six different types of Jatropha tissues (seed coat, kernel, stem, xylem, bark, and leaf) were torrefied at four different temperature conditions (200°C, 250°C, 300°C, and 350°C), and changes in the metabolite composition of the torrefied products were determined by Fourier transform-infrared spectroscopy and nuclear magnetic resonance analyses. Cellulose was gradually converted to oligosaccharides in the temperature range of 200°C-300°C and completely degraded at 350°C. Hemicellulose residues showed different degradation patterns depending on the tissue, whereas glucuronoxylan efficiently decomposed between 300°C and 350°C. Heat-induced depolymerization of starch to maltodextrin started between 200°C and 250°C, and oligomer sugar structure degradation occurred at higher temperatures. Lignin degraded at each temperature, e.g., syringyl (S) degraded at lower temperatures than guaiacyl (G). Finally, the toxic compound phorbol ester degraded gradually starting at 235°C and efficiently just below 300°C. These results suggest that torrefaction is a feasible treatment for further processing of residual biomass to biorefinery stock or fertilizer. PMID:25191879

  15. Chemical Profiling of Jatropha Tissues under Different Torrefaction Conditions: Application to Biomass Waste Recovery

    PubMed Central

    Watanabe, Taiji; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

    2014-01-01

    Gradual depletion of the world petroleum reserves and the impact of environmental pollution highlight the importance of developing alternative energy resources such as plant biomass. To address these issues, intensive research has focused on the plant Jatropha curcas, which serves as a rich source of biodiesel because of its high seed oil content. However, producing biodiesel from Jatropha generates large amounts of biomass waste that are difficult to use. Therefore, the objective of our research was to analyze the effects of different conditions of torrefaction on Jatropha biomass. Six different types of Jatropha tissues (seed coat, kernel, stem, xylem, bark, and leaf) were torrefied at four different temperature conditions (200°C, 250°C, 300°C, and 350°C), and changes in the metabolite composition of the torrefied products were determined by Fourier transform-infrared spectroscopy and nuclear magnetic resonance analyses. Cellulose was gradually converted to oligosaccharides in the temperature range of 200°C–300°C and completely degraded at 350°C. Hemicellulose residues showed different degradation patterns depending on the tissue, whereas glucuronoxylan efficiently decomposed between 300°C and 350°C. Heat-induced depolymerization of starch to maltodextrin started between 200°C and 250°C, and oligomer sugar structure degradation occurred at higher temperatures. Lignin degraded at each temperature, e.g., syringyl (S) degraded at lower temperatures than guaiacyl (G). Finally, the toxic compound phorbol ester degraded gradually starting at 235°C and efficiently just below 300°C. These results suggest that torrefaction is a feasible treatment for further processing of residual biomass to biorefinery stock or fertilizer. PMID:25191879

  16. Direct density measurements under mantle and core conditions and chemical characterization of high-PT samples (Invited)

    NASA Astrophysics Data System (ADS)

    Fei, Y.

    2009-12-01

    We simulate the physical conditions of Earth’s interior in multi-anvil apparatus and diamond-anvil cell (DAC) that can routinely generate pressure(P)-temperature(T) conditions corresponding to the top of the lower mantle and the outer core, respectively. The challenges have been to obtain precious measurements of physical properties of mantle and core material under well-controlled simultaneous high P-T conditions and to obtain chemical information of the recovered high P-T diamond-anvil cell samples. We have developed a range of complementary high-PT devices to optimize sample environment and P-T stability. They include large-volume multi-anvil apparatus, externally heated DAC, internal-heating DAC, laser-heating DAC, combination of internal- and laser-heating DAC, and combination of externally heated and laser-heating DAC. The externally heated and laser-heating DACs are complementary in P-T range and heating stability, whereas the combination of externally heated and laser-heating DAC shows great promises to achieve stable simultaneous high P-T conditions. We have take the internal resistance heating of metallic sample in the diamond-anvil cell into a new level, generating stable heating up to 2100 K at 70 GPa with iron foil. Higher, stable temperatures were achieved by combination of internal- and laser-heating, a promise technique for studying conductive samples at high pressure and temperature. The combination of improved high-PT technique and advancement in synchrotron X-ray diffraction has significantly expanded our capability to investigate the physical properties of the Earth’s mantle and core. We have determined the densities of (Al,Fe)-bearing mantle perovskite and (Mg,Fe)O solid solutions, with high precision, up to 135 GPa and 2700 K, covering the entire lower mantle P-T conditions. I will also show density measurements of iron alloys at simultaneous high P-T, using internal- and laser-heating DACs and combination of internal- and laser-heating. Stable temperature generation in the DAC is a key to obtaining reproducible, reliable chemical information of the laser-heated samples. Use of micro- and nano-analytical tools such as FIB and FE-SEM to recover and analyze recovered DAC samples will be demonstrated. The complete characterization of chemical and physical properties of the mantle and core materials at high pressure and temperature will further advance our understanding of the Earth’s interior.

  17. Chemical and Physical Environmental Conditions Underneath Mat- and Canopy-Forming Macroalgae, and Their Effects on Understorey Corals

    PubMed Central

    Hauri, Claudine; Fabricius, Katharina E.; Schaffelke, Britta; Humphrey, Craig

    2010-01-01

    Disturbed coral reefs are often dominated by dense mat- or canopy-forming assemblages of macroalgae. This study investigated how such dense macroalgal assemblages change the chemical and physical microenvironment for understorey corals, and how the altered environmental conditions affect the physiological performance of corals. Field measurements were conducted on macroalgal-dominated inshore reefs in the Great Barrier Reef in quadrats with macroalgal biomass ranging from 235 to 1029 g DW m−2 dry weight. Underneath mat-forming assemblages, the mean concentration of dissolved oxygen was reduced by 26% and irradiance by 96% compared with conditions above the mat, while concentrations of dissolved organic carbon and soluble reactive phosphorous increased by 26% and 267%, respectively. The difference was significant but less pronounced under canopy-forming assemblages. Dissolved oxygen declined and dissolved inorganic carbon and alkalinity increased with increasing algal biomass underneath mat-forming but not under canopy-forming assemblages. The responses of corals to conditions similar to those found underneath algal assemblages were investigated in an aquarium experiment. Coral nubbins of the species Acropora millepora showed reduced photosynthetic yields and increased RNA/DNA ratios when exposed to conditions simulating those underneath assemblages (pre-incubating seawater with macroalgae, and shading). The magnitude of these stress responses increased with increasing proportion of pre-incubated algal water. Our study shows that mat-forming and, to a lesser extent, canopy-forming macroalgal assemblages alter the physical and chemical microenvironment sufficiently to directly and detrimentally affect the metabolism of corals, potentially impeding reef recovery from algal to coral-dominated states after disturbance. Macroalgal dominance on coral reefs therefore simultaneously represents a consequence and cause of coral reef degradation. PMID:20856882

  18. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions

    PubMed Central

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-01-01

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto the GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. Our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/electrode interface in a photoelectrochemical solar cell. PMID:27108711

  19. Electronic and chemical structure of the H2O/GaN(0001) interface under ambient conditions.

    PubMed

    Zhang, Xueqiang; Ptasinska, Sylwia

    2016-01-01

    We employed ambient pressure X-ray photoelectron spectroscopy to investigate the electronic and chemical properties of the H2O/GaN(0001) interface under elevated pressures and/or temperatures. A pristine GaN(0001) surface exhibited upward band bending, which was partially flattened when exposed to H2O at room temperature. However, the GaN surface work function was slightly reduced due to the adsorption of molecular H2O and its dissociation products. At elevated temperatures, a negative charge generated on the surface by a vigorous H2O/GaN interfacial chemistry induced an increase in both the surface work function and upward band bending. We tracked the dissociative adsorption of H2O onto the GaN(0001) surface by recording the core-level photoemission spectra and obtained the electronic and chemical properties at the H2O/GaN interface under operando conditions. Our results suggest a strong correlation between the electronic and chemical properties of the material surface, and we expect that their evolutions lead to significantly different properties at the electrolyte/electrode interface in a photoelectrochemical solar cell. PMID:27108711

  20. Control of transport and magnetism in ferromagnetic semiconducting superlattices through growth conditions and chemical surface effects

    NASA Astrophysics Data System (ADS)

    Kreutz, Theodore Carlton

    2003-10-01

    Within the emerging area of spintronics, magnetic semiconductors have been the subject of many recent studies. Advances in magnetizing traditional semiconductors like GaAs, through the introduction of Mn, have been the focus of many experiments. Recently, studies have focused on ferromagnetic semiconducting superlattices, where half-monolayer MnAs planes are separated by GaAs spacers. These structures have only recently been grown, and it is of particular interest to discover the properties of this material, and if it can be used in future spintronic devices. We have studied changes in the magnetic and transport properties of ferromagnetic semiconducting superlattices as a function of temperature, superlattice period and substrate growth temperature. We have measured the resistance, Hall resistance and magnetoresistance over a wide range of temperatures. We see that as the period of the superlattice increases, the per-layer resistance and the Curie temperature reach saturation values at approximately the same value. We also find that electrical transport is predominantly through hopping conduction. The anomalous Hall effect dominates the Hall resistance. With the period fixed, we vary the substrate temperature during growth and observe that higher substrate temperatures lead to less resistive samples. Also, for samples with high substrate temperatures, we find that the anomalous Hall coefficient can flip in sign. We also observe changes in the magnetic anisotropy as we vary the period of the superlattice and the substrate temperature. We observe this change with planar Hall effect as well as SQUID magnetometry measurements. Samples with short periods show cubic magnetic anisotropy whereas samples with larger period show uniaxial anisotropy. We then determine the anisotropy constants for this material. We also see that the switching is dominated by domain pinning processes. Finally, we are able to change the Curie temperature of ½ ML MnAs planes in GaAs through the addition of chemical adsorbates. We find that we can reduce the Curie temperature by over 50 K. The reduction is linked to how well ordered the adsorbate is.

  1. Influence of Aqueous-Salt Conditions on the Structure and Dynamics of the Monomeric and Novel Dimeric forms of the Alzheimer s ABeta21-30 protein fragment

    NASA Astrophysics Data System (ADS)

    Smith, Micholas Dean

    The behavior of the Alzheimer's related peptide Abeta is the subject of much study. In typical computational studies the environment local to the peptide is assumed to be pure water; however, in vivo the peptide is found in the extracellular space near the plasma membrane which is rich in ionic species. In this thesis, the hypothesis that the presence of group I/IIA salts will result in increased sampling of disordered structures as well as modify the dynamics of meta-stable structural motifs in the small folding nucleus of the Abeta peptide (Abeta21-30) is examined under a variety of ionic environments and was shown that of the tested salts, CaCl2 (and MgCl2, to a much lesser degree) did increase the propensity for disordered states; while, the group IA salts, KCl and NaCl, had little effect on the secondary structure of the peptide. Further, study of three familial mutations of this peptide region is also performed under aqueous salt-environments to elucidate further mechanistic details of how aqueous salts modify the region's behavior. Finally, as experimental results have highlighted that aggregation rates of the full-length peptide are modified by the presence of CaCl2, this work examines novel dimers states of Abeta21-30 and their stabilities when exposed to CaCl2.

  2. Tenascin C Promotes Hematoendothelial Development and T Lymphoid Commitment from Human Pluripotent Stem Cells in Chemically Defined Conditions

    PubMed Central

    Uenishi, Gene; Theisen, Derek; Lee, Jeong-Hee; Kumar, Akhilesh; Raymond, Matt; Vodyanik, Maxim; Swanson, Scott; Stewart, Ron; Thomson, James; Slukvin, Igor

    2014-01-01

    Summary The recent identification of hemogenic endothelium (HE) in human pluripotent stem cell (hPSC) cultures presents opportunities to investigate signaling pathways that are essential for blood development from endothelium and provides an exploratory platform for de novo generation of hematopoietic stem cells (HSCs). However, the use of poorly defined human or animal components limits the utility of the current differentiation systems for studying specific growth factors required for HE induction and manufacturing clinical-grade therapeutic blood cells. Here, we identified chemically defined conditions required to produce HE from hPSCs growing in Essential 8 (E8) medium and showed that Tenascin C (TenC), an extracellular matrix protein associated with HSC niches, strongly promotes HE and definitive hematopoiesis in this system. hPSCs differentiated in chemically defined conditions undergo stages of development similar to those previously described in hPSCs cocultured on OP9 feeders, including the formation of VE-Cadherin+CD73−CD235a/CD43− HE and hematopoietic progenitors with myeloid and T lymphoid potential. PMID:25448067

  3. Effects of spray-drying conditions on the chemical, physical, and sensory properties of cheese powder.

    PubMed

    Koca, Nurcan; Erbay, Zafer; Kaymak-Ertekin, Figen

    2015-05-01

    Dairy powders are produced to increase the shelf life of fresh dairy products and for use as flavoring agents. In this study, 24 cheese powders produced under 7 different conditions were used to investigate the effects of spray-drying parameters (e.g., inlet air temperature, atomization pressure, and outlet air temperature) on the quality of white cheese powder. Composition, color, physical properties, reconstitution, and sensory characteristics of white cheese powders were determined. The results revealed that the white cheese powders produced in this study had low moisture content ratios and water activity values. High outlet air temperatures caused browning and enhanced Maillard reactions. Additionally, high outlet air temperatures increased wettability and dispersibility and decreased the solubility of white cheese powders. Free fat content was positively correlated with inlet air temperature and negatively correlated with outlet air temperature and atomization pressure. Sensory analyses revealed that white cheese powder samples had acceptable sensory characteristics with the exception of the sample produced at an outlet air temperature of 100°C, which had high scores for scorched flavor and color and low scores for cheese flavor. PMID:25771045

  4. Conditioned Place Avoidance of Zebrafish (Danio rerio) to Three Chemicals Used for Euthanasia and Anaesthesia

    PubMed Central

    Wong, Devina; von Keyserlingk, Marina A. G.; Richards, Jeffrey G.; Weary, Daniel M.

    2014-01-01

    Zebrafish are becoming one of the most used vertebrates in developmental and biomedical research. Fish are commonly killed at the end of an experiment with an overdose of tricaine methanesulfonate (TMS, also known as MS-222), but to date little research has assessed if exposure to this or other agents qualifies as euthanasia (i.e. a “good death”). Alternative agents include metomidate hydrochloride and clove oil. We use a conditioned place avoidance paradigm to compare aversion to TMS, clove oil, and metomidate hydrochloride. Zebrafish (n = 51) were exposed to the different anaesthetics in the initially preferred side of a light/dark box. After exposure to TMS zebrafish spent less time in their previously preferred side; aversion was less pronounced following exposure to metomidate hydrochloride and clove oil. Nine of 17 fish exposed to TMS chose not to re-enter the previously preferred side, versus 2 of 18 and 3 of 16 refusals for metomidate hydrochloride and clove oil, respectively. We conclude that metomidate hydrochloride and clove oil are less aversive than TMS and that these agents be used as humane alternatives to TMS for killing zebrafish. PMID:24505365

  5. Conditioned place avoidance of zebrafish (Danio rerio) to three chemicals used for euthanasia and anaesthesia.

    PubMed

    Wong, Devina; von Keyserlingk, Marina A G; Richards, Jeffrey G; Weary, Daniel M

    2014-01-01

    Zebrafish are becoming one of the most used vertebrates in developmental and biomedical research. Fish are commonly killed at the end of an experiment with an overdose of tricaine methanesulfonate (TMS, also known as MS-222), but to date little research has assessed if exposure to this or other agents qualifies as euthanasia (i.e. a "good death"). Alternative agents include metomidate hydrochloride and clove oil. We use a conditioned place avoidance paradigm to compare aversion to TMS, clove oil, and metomidate hydrochloride. Zebrafish (n = 51) were exposed to the different anaesthetics in the initially preferred side of a light/dark box. After exposure to TMS zebrafish spent less time in their previously preferred side; aversion was less pronounced following exposure to metomidate hydrochloride and clove oil. Nine of 17 fish exposed to TMS chose not to re-enter the previously preferred side, versus 2 of 18 and 3 of 16 refusals for metomidate hydrochloride and clove oil, respectively. We conclude that metomidate hydrochloride and clove oil are less aversive than TMS and that these agents be used as humane alternatives to TMS for killing zebrafish. PMID:24505365

  6. Chemical and structural modifications of laser treated WTi surfaces at different ambient conditions

    NASA Astrophysics Data System (ADS)

    Petrović, S.; Peruško, D.; Milovanović, D.; Siketić, Z.; Jakšić, M.; Kovač, J.; Gaković, B.; Milosavljević, M.; Trtica, M.

    2011-11-01

    In this work we have studied the influence of laser modification on the composition and structure of tungsten titanium (WTi) thin films, deposited on n-type (100) silicon wafers. After deposition, the samples were multi-pulse laser irradiated in a nitrogen, oxygen, and helium ambient. The composition of the WTi/Si sample was determined by Elastic Recoil Detection Analysis (ERDA). Surface morphology was monitored by Atomic Force Microscopy (AFM). In the experiment, typical laser output parameters were: wavelength 1064 nm, pulse duration 150 ps, and laser pulse energy 30 mJ. Surface concentrations of W and Ti, as well as the concentration of gas components nitrogen and oxygen were determinated before and after the action of laser radiation in different ambient conditions. The contents of W and Ti decreased after irradiation due to adsorbed gases from the surrounding atmosphere. After surface irradiation in the inert ambient (He), the concentrations of the components were not significantly changed. In other cases, oxygen was the dominant component at the surface, probably due to the high affinity of thin film components. Also, the morphological changes occurred at the surface of WTi, as an increase in the surface roughness and formation of the granular structures are a result of laser-induced surface oxidation and recrystallization.

  7. In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: A new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions

    USGS Publications Warehouse

    Lu, W.J.; Chou, I.-Ming; Burruss, R.C.; Yang, M.Z.

    2006-01-01

    A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition. ?? 2006 Society for Applied Spectroscopy.

  8. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  9. Dynamics-based selective 2D (1)H/(1)H chemical shift correlation spectroscopy under ultrafast MAS conditions.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of (1)H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of (1)H/(1)H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  10. Collisions of small ice particles under microgravity conditions. II. Does the chemical composition of the ice change the collisional properties?

    NASA Astrophysics Data System (ADS)

    Hill, C. R.; Heißelmann, D.; Blum, J.; Fraser, H. J.

    2015-03-01

    Context. Understanding the collisional properties of ice is important for understanding both the early stages of planet formation and the evolution of planetary ring systems. Simple chemicals such as methanol and formic acid are known to be present in cold protostellar regions alongside the dominant water ice; they are also likely to be incorporated into planets which form in protoplanetary disks, and planetary ring systems. However, the effect of the chemical composition of the ice on its collisional properties has not yet been studied. Aims: Collisions of 1.5 cm ice spheres composed of pure crystalline water ice, water with 5% methanol, and water with 5% formic acid were investigated to determine the effect of the ice composition on the collisional outcomes. Methods: The collisions were conducted in a dedicated experimental instrument, operated under microgravity conditions, at relative particle impact velocities between 0.01 and 0.19 ms-1, temperatures between 131 and 160 K and a pressure of around 10-5 mbar. Results: A range of coefficients of restitution were found, with no correlation between this and the chemical composition, relative impact velocity, or temperature. Conclusions: We conclude that the chemical composition of the ice (at the level of 95% water ice and 5% methanol or formic acid) does not affect the collisional properties at these temperatures and pressures due to the inability of surface wetting to take place. At a level of 5% methanol or formic acid, the structure is likely to be dominated by crystalline water ice, leading to no change in collisional properties. The surface roughness of the particles is the dominant factor in explaining the range of coefficients of restitution.

  11. Effects of Atmospheric Conditions and the Land/Atmospheric Interface on Transport of Chemical Vapors from Subsurface Sources

    NASA Astrophysics Data System (ADS)

    Rice, A. K.; Smits, K. M.; Cihan, A.; Howington, S. E.; Illangasekare, T. H.

    2013-12-01

    Understanding the movement of chemical vapors and gas through variably saturated soil subjected to atmospheric thermal and mass flux boundary conditions at the land/atmospheric interface is important to many applications, including landmine detection, methane leakage during natural gas production from shale and CO2 leakage from deep geologic storage. New, advanced technologies exist to sense chemical signatures and gas leakage at the land/atmosphere interface, but interpretation of sensor signals remains a challenge. Chemical vapors are subject to numerous interactions while migrating through the soil environment, masking source conditions. The process governing movement of gases through porous media is often assumed to be Fickian diffusion through the air phase with minimal quantification of other processes, such as convective gas flow and temporal or spatial variation in soil moisture. Vapor migration is affected by atmospheric conditions (e.g. humidity, temperature, wind velocity), soil thermal and hydraulic properties and contaminant properties, all of which are physically and thermodynamically coupled. The complex coupling of two drastically different flow regimes in the subsurface and atmosphere is commonly ignored in modeling efforts, or simplifying assumptions are made to treat the systems as de-coupled. Experimental data under controlled laboratory settings are lacking to refine the theory for proper coupling and complex treatment of vapor migration through porous media in conversation with atmospheric flow and climate variations. Improving fundamental understanding and accurate quantification of these processes is not feasible in field settings due to lack of controlled initial and boundary conditions and inability to fully characterize the subsurface at all relevant scales. The goal of this work is to understand the influence of changes in atmospheric conditions to transport of vapors through variably saturated soil. We have developed a tank apparatus with a network of soil and atmospheric sensors and a head space for air flow to simulate the atmospheric boundary layer. Experiments were performed under varying temperature values at the soil surface bounded by the atmospheric boundary layer. The model of Smits et al. [2011], accounting for non-equilibrium phase change and coupled heat, water vapor and liquid water flux through soil, was amended to include organic vapor in the gas phase and migration mechanisms often overlooked in models (thermal and Knudsen diffusion, density driven advection). Experimental results show increased vapor mass flux across the soil/atmospheric interface due to heat applied from the atmosphere and coupling of heat and mass transfer in the shallow subsurface for both steady and diurnal temperature patterns. Comparison of model results to experimental data shows dynamic interactions between transport in porous media and boundary conditions. Results demonstrate the value of considering interactions of the atmosphere and subsurface to better understand chemical gas transport through unsaturated soils and the land/atmospheric interface.

  12. A localized tolerance in the substrate specificity of the fluorinase enzyme enables "last-step" 18F fluorination of a RGD peptide under ambient aqueous conditions.

    PubMed

    Thompson, Stephen; Zhang, Qingzhi; Onega, Mayca; McMahon, Stephen; Fleming, Ian; Ashworth, Sharon; Naismith, James H; Passchier, Jan; O'Hagan, David

    2014-08-18

    A strategy for last-step (18)F fluorination of bioconjugated peptides is reported that exploits an "Achilles heel" in the substrate specificity of the fluorinase enzyme. An acetylene functionality at the C-2 position of the adenosine substrate projects from the active site into the solvent. The fluorinase catalyzes a transhalogenation of 5'-chlorodeoxy-2-ethynyladenosine (ClDEA) to 5'-fluorodeoxy-2-ethynyladenosine (FDEA). Extending a polyethylene glycol linker from the terminus of the acetylene allows the presentation of bioconjugation cargo to the enzyme for (18)F labelling. The method uses an aqueous solution (H2(18)O) of [(18)F]fluoride generated by the cyclotron and has the capacity to isotopically label peptides of choice for positron emission tomography (PET). PMID:24989327

  13. Is Vanadate Reduced by Thiols under Biological Conditions?: Changing The Redox Potential of V(V)/V(IV) by Complexation in Aqueous solution

    PubMed Central

    Crans, Debbie C.; Zhang, Boyan; Gaidamauskas, Ernestas; Keramidas, Anastasios D.; Willsky, Gail R.; Roberts, Chris R.

    2010-01-01

    Although dogma states that vanadate is readily reduced by glutathione, cysteine and other thiols, there are several examples documenting that vanadium(V)-sulfur complexes can form and be observed. This conundrum has impacted life scientists for more than two decades. Investigation of this problem requires an understanding of both the complexes that form from vanadium(IV) and (V) and a representative thiol in aqueous solution. The reactions of vanadate and hydrated vanadyl cation with 2-mercaptoethanol have been investigated using multinuclear NMR, EPR and UV-vis spectroscopy. Vanadate forms a stable complex of 2:2 stoichiometry with 2-mercaptoethanol at neutral and alkaline pH. In contrast, vanadate can oxidize 2-mercaptoethanol; this process is favored at low pH and high solute concentrations. The complex that forms between aqueous vanadium(IV) and 2-mercaptoethanol has a 1:2 stoichiometry and can be observed at high pH and high 2-mercaptoethanol concentration. The solution structures have been deduced and speciation diagrams prepared. This work demonstrates that both vanadium(IV) and (V)-thiol complexes form and that redox chemistry also takes place. Whether reduction of vanadate takes place is governed by a combination of parameters: pH, solute- and vanadate-concentrations and the presence of other complexing ligands. Based on these results it is now possible to understand the distribution of vanadium in oxidation states (IV) and (V) in the presence of glutathione, cysteine and other thiols and begin to evaluate the forms of the vanadium compounds that exert a particular biological effect including the insulin-enhancing agents, anti-amoebic agents and interactions with vanadium binding proteins. PMID:20359175

  14. Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study.

    PubMed

    Shah, Bhavna; Mistry, Chirag; Shah, Ajay

    2013-04-01

    Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)-an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer-Emmett-Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions. PMID:22739768

  15. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases.

    PubMed

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases. PMID:24952470

  16. Chemical reaction conditions in a Danish 80 MW{sub th} CFB-boiler co-firing straw and coal

    SciTech Connect

    Hansen, P.F.B.

    1997-12-31

    Future boilers to be constructed in Denmark including boilers intended for energy conversion of biomass (straw and wood chips) will be designed for Ultra Super Critical steam data. The high steam temperatures and subsequently metal temperatures in the superheaters will increase the corrosion hazard significantly. Severe superheater corrosion observed in the convective path and on test tubes inserted into the loop seal of a Danish 80 MW{sub th} Ahlstroem Pyroflow CFB boiler co-firing coal and straw initiated this study on the conditions under which the chemical reactions occur and deposits form. Load changes--caused by variations in public demand for district heating shifts the reaction conditions in the loop seal between predominantly reducing and predominantly oxidizing conditions. Furthermore the external particle circulation rate and the local temperatures are strongly affected. Deposits collected in the loop seal on temperature controlled probes reveals Cl concentrations more than Twenty Thousand times higher than found in the surrounding bed material. The results are discussed and suggestions on how to reduce high temperature corrosion and superheater fouling are presented.

  17. Protective effect of conditioning agents on Afro-ethnic hair chemically treated with thioglycolate-based straightening emulsion.

    PubMed

    Dias, Tania Cristina de Sá; Baby, André Rolim; Kaneko, Telma Mary; Velasco, Maria Valéria Robles

    2008-06-01

    Straightening is a chemical process by which excessively curly hair is straightened in an irreversible way. Generally, products are formulated as emulsions with high pH value (9.0-12.0), which, after applied on hair, cause considerable damage, making it dry and fragile. This research work evaluated the protective effect of lauryl PEG/PPG-18/18 methicone, cyclopentasiloxane (and) PEG-12 dimethicone cross-polymer, jojoba oil, and aqua (and) cystine bis-PG propyl silanetriol, as conditioning agents, on Afro-ethnic hair locks treated with thioglycolate-based straightening emulsions by protein loss, combability, and traction to rupture. Standard Afro-ethnic hair locks were prepared following a protocol for straightening emulsion application. Considering the assays performed, the addition of conditioning agents to the straightening emulsion with ammonium thioglycolate benefited the hair fiber, thus diminishing protein loss, protecting the hair thread, and improving resistance to breakage. Jojoba oil and lauryl PEG/PPG-18/18 methicone were the conditioning agents that presented the best results. Straightening emulsions with ammonium thioglycolate containing aqua (and) cystine bis-PG propyl silanetriol and cyclopentasiloxane (and) PEG-12 dimethicone cross-polymer were the ones that provided higher breakage resistance of the thread. PMID:18482015

  18. Mars aqueous chemistry experiment

    NASA Technical Reports Server (NTRS)

    Clark, Benton C.; Mason, Larry W.

    1994-01-01

    Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

  19. Effect of vacuum conditions and plasma concentration on the chemical composition and adhesion of vacuum-plasma coatings

    NASA Astrophysics Data System (ADS)

    Borisov, D. P.; Kuznetsov, V. M.; Slabodchikov, V. A.

    2015-11-01

    The paper reports on the chemical composition of titanium nitride (TiN) and silicon (Si) coatings deposited with a new technological vacuum plasma setup which comprises magnetron sputtering systems, arc evaporators, and an efficient plasma generator. It is shown that due to highly clean vacuum conditions and highly clean surface treatment in the gas discharge plasma, both the coating-substrate interface and the coatings as such are almost free from oxygen and carbon. It is found that the coating-substrate interface represents a layer of thickness ≥ 60 nm formed through vacuum plasma mixing of the coating and substrate materials. The TiN coatings obtained on the new equipment display a higher adhesion compared to brass coatings deposited by industrial technologies via intermediate titanium oxide layers. It is concluded that the designed vacuum plasma equipment allows efficient surface modification of materials and articles by vacuum plasma immersion processes.

  20. Chemical repair of base lesions, AP-sites, and strand breaks on plasmid DNA in dilute aqueous solution by ascorbic acid

    SciTech Connect

    Hata, Kuniki; Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 ; Urushibara, Ayumi; Yamashita, Shinichi; Shikazono, Naoya; Yokoya, Akinari; Katsumura, Yosuke; Nuclear Professional School, School of Engineering, The University of Tokyo, 2-22 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1188

    2013-05-03

    Highlights: •We report a novel mechanism of radiation protection of DNA by chemical activity of ascorbic acid. •The “chemical repair” of DNA damage was revealed using biochemical assay and chemical kinetics analysis. •We found that ascorbic acid significantly repairs precursors of nucleobase lesions and abasic sites. •However, ascorbic acid seldom repairs precursors of DNA-strand breaks. -- Abstract: We quantified the damage yields produced in plasmid DNA by γ-irradiation in the presence of low concentrations (10–100 μM) of ascorbic acid, which is a major antioxidant in living systems, to clarify whether it chemically repairs radiation damage in DNA. The yield of DNA single strand breaks induced by irradiation was analyzed with agarose gel electrophoresis as conformational changes in closed circular plasmids. Base lesions and abasic sites were also observed as additional conformational changes by treating irradiated samples with glycosylase proteins. By comparing the suppression efficiencies to the induction of each DNA lesion, in addition to scavenging of the OH radicals derived from water radiolysis, it was found that ascorbic acid promotes the chemical repair of precursors of AP-sites and base lesions more effectively than those of single strand breaks. We estimated the efficiency of the chemical repair of each lesion using a kinetic model. Approximately 50–60% of base lesions and AP-sites were repaired by 10 μM ascorbic acid, although strand breaks were largely unrepaired by ascorbic acid at low concentrations. The methods in this study will provide a route to understanding the mechanistic aspects of antioxidant activity in living systems.

  1. Identification of morphological and chemical markers of dry- and wet-season conditions in female Anopheles gambiae mosquitoes

    PubMed Central

    2014-01-01

    Background Increased understanding of the dry-season survival mechanisms of Anopheles gambiae in semi-arid regions could benefit vector control efforts by identifying weak links in the transmission cycle of malaria. In this study, we examined the effect of photoperiod and relative humidity on morphologic and chemical traits known to control water loss in mosquitoes. Methods Anopheles gambiae body size (indexed by wing length), mesothoracic spiracle size, and cuticular hydrocarbon composition (both standardized by body size) were examined in mosquitoes raised from eggs exposed to short photoperiod and low relative humidity, simulating the dry season, or long photoperiod and high relative humidity, simulating the wet-season. Results Mosquitoes exposed to short photoperiod exhibited larger body size and larger mesothoracic spiracle length than mosquitoes exposed to long photoperiod. Mosquitoes exposed to short photoperiod and low relative humidity exhibited greater total cuticular hydrocarbon amount than mosquitoes exposed to long photoperiod and high relative humidity. In addition, total cuticular hydrocarbon amount increased with age and was higher in mated females. Mean n-alkane retention time (a measure of cuticular hydrocarbon chain length) was lower in mosquitoes exposed to short photoperiod and low relative humidity, and increased with age. Individual cuticular hydrocarbon peaks were examined, and several cuticular hydrocarbons were identified as potential biomarkers of dry- and wet-season conditions, age, and insemination status. Conclusions Results from this study indicate that morphological and chemical changes underlie aestivation of Anopheles gambiae and may serve as biomarkers of aestivation. PMID:24970701

  2. Kinetic studies of chemical shrinkage and residual stress formation in thermoset epoxy adhesives under confined curing conditions

    NASA Astrophysics Data System (ADS)

    Schumann, M.; Gei, P. L.

    2015-05-01

    Faultless processing of thermoset polymers in demanding applications requires a profound mastering of the curing kinetics considering both the physico-chemical changes in the transition from the liquid to the solid state and the consolidation of the polymers network in the diffusion controlled curing regime past the gel point. Especially in adhesive joints shrinkage stress occurring at an early state of the curing process under confined conditions is likely to cause defects due to local debonding and thus reduce their strength and durability1. Rheometry is considered the method of choice to investigate the change of elastic and viscous properties in the progress of curing. Drawbacks however relate to experimental challenges in accessing the full range of kinetic parameters of thermoset resins with low initial viscosity from the very beginning of the curing reaction to the post-cure consolidation of the polymer due to the formation of secondary chemical bonds. Therefore the scope of this study was to interrelate rheological data with results from in-situ measurements of the shrinkage stress formation in adhesive joints and with the change of refractive index in the progress of curing. This combination of different methods has shown to be valuable in gaining advanced insight into the kinetics of the curing reaction. The experimental results are based on a multi component thermoset epoxy-amine adhesive.

  3. Studies on the phytoplankton populations and physico-chemical conditions of treated sewage discharged into Lake Manzala in Egypt.

    PubMed

    el-Naggar, M E; Shaaban-Dessouki, S A; Abdel-Hamid, M I; Aly, E M

    1998-04-01

    Over a full year, the phytoplankton populations and physico-chemical conditions of treated sewage discharged into Lake Manzala in Egypt were investigated. Sixty-seven species of algae were identified, 18 Cyanophyta (Cyanobacteria), 19 Chlorophyta, 21 Bacillariophyta, 6 Euglenophyta, 2 Cryptophyta and one species Pyrrhophyta. Nitzschia (6 spp.), Scenedesmus (6 spp.), Navicula (4 spp.), Oscillatoria (4 spp.) and Euglena (4 spp.) were the most common genera. A remarkable seasonal variation in species composition and standing crop of the phytoplankton populations was noted during the study. The total phytoplankton standing crop appeared to be mainly dependent on the growth of certain species viz., Oscillatoria chalybea, O. princepes, O. tenuis, Microcystis aeruginosa, Anabaena constricta (Cyanophyta), Nitzschia obtusa, Bacillaria paradoxa, Cocconeis placentula, Cyclotella meneghiniana (Bacillariophyta), Pandorina morum, Volvox sp. (Chlorophyta) and Phacus curvicauda (Euglenophyta). The continuous presence of Anabaena constricta and Nitzschia palea was recorded in the treated sewage. The least represented algal divisions were Pyrrhophyta and Cryptophyta, both in terms of quality and quantity. The data indicate that the secondary effluents were unstable in their chemical features and grossly polluted. Therefore, the treatment systems must treat the discharged sewage to a tertiary level before discharging into Lake Manzala. PMID:9579343

  4. Distribution of fish, benthic invertebrate, and algal communities in relation to physical and chemical conditions, Yakima River basin, Washington, 1990

    USGS Publications Warehouse

    Cuffney, T.F.; Meador, M.R.; Porter, S.D.; Gurtz, M.E.

    1997-01-01

    Biological investigations were conducted in the Yakima River Basin, Washington, in conjunction with a pilot study for the U.S. Geological Survey's National Water-Quality Assessment Program. Ecological surveys were conducted at 25 sites in 1990 to (1) assess water-quality conditions based on fish, benthic invertebrate, and algal communities; (2) determine the hydrologic, habitat, and chemical factors that affect the distributions of these organisms; and (3) relate physical and chemical conditions to water quality. Results of these investigations showed that land uses and other associated human activities influenced the biological characteristics of streams and rivers and overall water-quality conditions. Fish communities of headwater streams in the Cascades and Eastern Cascades ecoregions of the Yakima River Basin were primarily composed of salmonids and sculpins, with cyprinids dominating in the rest of the basin. The most common of the 33 fish taxa collected were speckled dace, rainbow trout, and Paiute sculpin. The highest number of taxa (193) was found among the inverte- brates. Insects, particularly sensitive forms such as mayflies, stoneflies, and caddisflies (EPT--Ephemeroptera, Plecoptera, and Trichoptera fauna), formed the majority of the invertebrate communities of the Cascades and Eastern Cascades ecoregions. Diatoms dominated algal communities throughout the basin; 134 algal taxa were found on submerged rocks, but other stream microhabitats were not sampled as part of the study. Sensitive red algae and diatoms were predominant in the Cascades and Eastern Cascades ecoregions, whereas the abundance of eutrophic diatoms and green algae was large in the Columbia Basin ecoregion of the Yakima River Basin. Ordination of physical, chemical, and biological site characteristics indicated that elevation was the dominant factor accounting for the distribution of biota in the Yakima River Basin; agricultural intensity and stream size were of secondary importance. Ordination identified three site groups and three community types. Site groups consisted of (1) small streams of the Cascades and Eastern Cascades ecoregions, (2) small streams of the Columbia Basin ecoregions, and (3) large rivers of the Cascades and Columbia Basin ecoregions. The small streams of the Columbia Basin could be further subdivided into two groups--one where agricultural intensity was low and one where agricultural intensity was moderate to high. Dividing the basin into these three groups removed much of the influence of elevation and facilitated the analysis of land-use effects. Community types identified by ordination were (1) high elevation, cold-water communities associated with low agricultural intensity; (2) lower elevation, warm-water communities associated with low agricultural intensity, and (3) lower elevation, warm-water communities associated with moderate to high agricultural intensity. Multimetric community condition indices indicated that sites in the Cascades and Eastern Cascades site group were largely unimpaired. In contrast, all but two sites in the Columbia Basin site group were impaired, some severely. Agriculture (nutrients and pesticides) was the primary factor responsible for this impairment, and all impaired sites were characterized by multiple indicators of impairment. Three sites (Granger Drain, Moxee Drain, and Spring Creek) had high levels of impairment. Sites in the large-river site group were moderately to severely impaired downstream from the city of Yakima. High levels of impairment at large-river sites corresponded with high levels of pesticides in fish tissues and the occurrence of external anomalies. The response exhibited by invertebrates and algae to a gradient of agricultural intensity suggested a threshold response for sites in the Columbia Basin site group. Community condition declined precipitously at agricultural intensities above 50 (non-pesticide agricultural intensity index) and showed little respon

  5. Testing Insecticidal Activity of Novel Chemically Synthesized siRNA against Plutella xylostella under Laboratory and Field Conditions

    PubMed Central

    Gong, Liang; Chen, Yong; Hu, Zhen; Hu, Meiying

    2013-01-01

    Background Over the last 60 years, synthetic chemical pesticides have served as a main tactic in the field of crop protection, but their availability is now declining as a result of the development of insect resistance. Therefore, alternative pest management agents are needed. However, the demonstration of RNAi gene silencing in insects and its successful usage in disrupting the expression of vital genes opened a door to the development of a variety of novel, environmentally sound approaches for insect pest management. Methodology/Principal Findings Six small interfering RNAs (siRNAs) were chemically synthesized and modified according to the cDNA sequence of P. xylostella acetylcholine esterase genes AChE1 and AChE2. All of them were formulated and used in insecticide activity screening against P. xylostella. Bioassay data suggested that Si-ace1_003 and Si-ace2_001 at a concentration of 3 µg cm−2 displayed the best insecticidal activity with 73.7% and 89.0%, mortality, respectively. Additional bioassays were used to obtain the acute lethal concentrations of LC50 and LC90 for Si-ace2_001, which were 53.66 µg/ml and 759.71 µg/ml, respectively. Quantitative Real-time PCR was used to confirm silencing and detected that the transcript levels of P. xylostella AChE2 (PxAChE2) were reduced by 5.7-fold compared to the control group. Consequently, AChE activity was also reduced by 1.7-fold. Finally, effects of the siRNAs on treated plants of Brassica oleracea and Brassica alboglabra were investigated with different siRNA doses. Our results showed that Si-ace2_001 had no negative effects on plant morphology, color and growth of vein under our experimental conditions. Conclusions The most important finding of this study is the discovery that chemically synthesized and modified siRNA corresponding to P. xylostella AChE genes cause significant mortality of the insect both under laboratory and field conditions, which provides a novel strategy to control P. xylostella and to develop bio-pesticides based on the RNA interference technology. PMID:23667556

  6. The Effect of Variety and Growing Conditions on the Chemical Composition and Nutritive Value of Wheat for Broilers

    PubMed Central

    Ball, M. E. E.; Owens, B.; McCracken, K. J.

    2013-01-01

    The aim of this study was to examine the effect of variety and growing conditions of wheat on broiler performance and nutrient digestibility. One hundred and sixty-four wheat samples, collected from a wide range of different sources, locations, varieties and years, were analyzed for a range of chemical and physical parameters. Chemical and physical parameters measured included specific weight, thousand grain weight (TG), in vitro viscosity, gross energy, N, NDF, starch, total and soluble non-starch polysaccharides (NSP), lysine, threonine, amylose, hardness, rate of starch digestion and protein profiles. Ninety-four of the wheat samples were selected for inclusion in four bird trials. Birds were housed in individual wire metabolizm cages from 7 to 28 d and offered water and feed ad libitum. Dry matter intake (DMI), live weight gain (LWG) and gain:feed were determined weekly. A balance collection was carried out from 14 to 21 d for determination of apparent metabolizable energy (AME), ME:gain, DM retention, oil and NDF digestibility. At 28 d the birds were sacrificed, the contents of the jejunum removed for determination of in vivo viscosity and the contents of the ileum removed for determination of ileal DM, starch and protein digestibility. The wheat samples used in the study had wide-ranging chemical and physical parameters, leading to bird DMI, LWG, gain:feed, ME:GE, AME content and ileal starch and protein digestibility being significantly (p<0.05) affected by wheat sample. A high level of N fertilizer application to the English and NI wheat samples tended to benefit bird performance, with increases of up to 3.4, 7.2 and 3.8% in DMI, LWG and gain:feed, respectively. Fungicide application also appeared to have a positive effect on bird performance, with fungicide treated (+F) wheat increasing bird DMI, LWG and gain:feed by 6.6, 9.3 and 2.7%, over the non-fungicide treated (-F) wheats. An increase (p<0.1) of 9.3% in gain:feed was also observed at the low seed rate of 40 compared to 640 seeds/m2. It was concluded that the type of wheat sample and environmental growing conditions significantly affects bird performance when fed wheat-based diets. PMID:25049800

  7. Laboratory insights into the chemical and kinetic evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    Poch, O.; Kaci, S.; Stalport, F.; Szopa, C.; Coll, P.

    2014-11-01

    The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars' exploration. Understanding the chemical evolution of organic molecules under current martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? This paper presents the results of laboratory investigations dedicated to monitor the evolution of organic molecules when submitted to simulated Mars surface ultraviolet radiation (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) conditions. Experiments are done with the MOMIE simulation setup (for Mars Organic Molecules Irradiation and Evolution) allowing both a qualitative and quantitative characterization of the evolution the tested molecules undergo (Poch, O. et al. [2013]. Planet. Space Sci. 85, 188-197). The chemical structures of the solid products and the kinetic parameters of the photoreaction (photolysis rate, half-life and quantum efficiency of photodecomposition) are determined for glycine, urea, adenine and chrysene. Mellitic trianhydride is also studied in order to complete a previous study done with mellitic acid (Stalport, F., Coll, P., Szopa, C., Raulin, F. [2009]. Astrobiology 9, 543-549), by studying the evolution of mellitic trianhydride. The results show that solid layers of the studied molecules have half-lives of 10-103 h at the surface of Mars, when exposed directly to martian UV radiation. However, organic layers having aromatic moieties and reactive chemical groups, as adenine and mellitic acid, lead to the formation of photoresistant solid residues, probably of macromolecular nature, which could exhibit a longer photostability. Such solid organic layers are found in micrometeorites or could have been formed endogenously on Mars. Finally, the quantum efficiencies of photodecomposition at wavelengths from 200 to 250 nm, determined for each of the studied molecules, range from 10-2 to 10-6 molecule photon-1 and apply for isolated molecules exposed at the surface of Mars. These kinetic parameters provide essential inputs for numerical modeling of the evolution of Mars' current reservoir of organic molecules. Organic molecules adsorbed on martian minerals may have different kinetic parameters and lead to different endproducts. The present study paves the way for the interpretation of more complex simulation experiments where organics will be mixed with martian mineral analogs.

  8. Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KLII&III, KLI) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

    SciTech Connect

    Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas; Bylaska, Eric J.; Vjunov, Aleksei; Pin, Sonia; Smurthwaite, Tricia D.

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KLII&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&III and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle under Contract # AC05-76RL01830.

  9. Applicability of DLVO Approach to Predict Trends in Iron Oxide Colloid Mobility Under Various Physical And Chemical Soil Conditions

    NASA Astrophysics Data System (ADS)

    Florian Carstens, Jannis; Bachmann, Jörg; Neuweiler, Insa

    2014-05-01

    In soil and groundwater, highly mobile iron oxide colloids can act as "shuttles" for transport of adsorbed contaminants such as heavy metals and radionuclides. Artificial iron oxide colloids are injected into polluted porous media to accelerate bacterial degradation of pollutants in the context of bioremediation purposes. The mobility of iron oxide colloids is strongly affected by the hydraulic, physical and chemical conditions of the pore space, the solid particle surface properties, the fluid phase, and the colloids themselves. Most pioneering studies focused on iron oxide colloid transport and retention in simplified model systems. The aim of this study is to investigate iron oxide colloid mobility under more complex, soil-typical conditions that have as yet only been applied for model microspheres, i.e. functionalized latex colloids. Among these conditions is the pivotal impact of organic matter, either dissolved or adsorbed onto solid particles, modifying wettability properties. Of particular importance was to determine if effective chemical surface parameters derived from contact angle and zeta potential measurements can be used as a tool to predict general tendencies for iron oxide colloid mobility in porous media. In column breakthrough experiments, goethite colloids (particle size: 200-900 nm) were percolated through quartz sand (grain size: 100-300 µm) at pH 5. The impact of a multitude of conditions on colloid mobility was determined: dissolved organic matter (DOM) concentration, ionic strength, flow velocity, flow interruption, partial saturation, and drying with subsequent re-wetting. The solid matrix consisted of either clean sand, organic matter-coated sand, goethite-coated sand, or sand hydrophobized with dichlorodimethylsilane. Additionally, contact angles and zeta potentials of the materials applied in the column experiments were measured. By means of these surface parameters, traditional DLVO interaction energies based on zeta potential as well as extended DLVO energies including Lewis acid-base parameters based on contact angle measurements were estimated. The results elucidate that high mobility of goethite colloids was distinctly restricted to a narrow set of conditions: presence of DOM, sufficient flow velocity and constant flow, low ionic strength, full saturation as well as an uncoated and hydrophilic quartz sand matrix. Any deviation from these favorable transport conditions led from varying degrees of colloid retention up to complete immobilization. Results yielded by both traditional and extended DLVO interaction energy calculations demonstrated that increasing secondary minimum depth correlated well with higher colloid retention. Extended DLVO calculations revealed strong repulsive forces due to Lewis acid-base interactions at close distances that did not comply with experimental data. It is likely that Lewis acid-base interactions were limited due to surface roughness of the sand grains and colloids. It can be concluded that the impact of various soil and hydraulic conditions on goethite colloid mobility is in principle assessable with column flow experiments. Moreover, with restrictions for the interpretation of close-distance interactions, DLVO interaction energies are capable of predicting general trends of goethite colloid mobility.

  10. Chemical Soil Physics Phenomena for Chemical Sensing of Buried UXO

    SciTech Connect

    Phelan, James, M.; Webb, Stephen W.

    1999-06-14

    Technology development efforts are under way to apply chemical sensors to discriminate inert ordnance and clutter from live munitions that remain a threat to reutilization of military ranges. However, the chemical signature is affected by multiple environmental phenomena that can enhance or reduce its presence and transport behavior, and can affect the distribution of the chemical signature in the environment. For example, the chemical can be present in the vapor, aqueous, and solid phases. The distribution of the chemical among these phases, including the spatial distribution, is key in designing appropriate detectors, e.g., gas, aqueous or solid phase sampling instruments. A fundamental understanding of the environmental conditions that affect the chemical signature is needed to describe the favorable and unfavorable conditions of a chemical detector based survey to minimize the consequences of a false negative. UXO source emission measurements are being made to estimate the chemical flux from a limited set of ordnance items. Phase partitioning analysis has been completed to show what the expected concentrations of chemical analytes would be fi-om total concentrations measured in the soil. The soil moisture content in the dry region has been shown to be critical in the attenuation of soil gas concentrations by increased sorption to soil particles. Numerical simulation tools have been adapted to include surface boundary conditions such as solar radiation, surface boundary layer (which is a function of wind speed), precipitation and evaporation, and plant cover/root density to allow transport modeling and evaluate long term processes. Results of this work will provide performance targets for sensor developers and support operational decisions regarding field deployments.

  11. A novel low cost non-aqueous chemical route for giant dielectric constant CaCu3Ti4O12 ceramic

    NASA Astrophysics Data System (ADS)

    Singh, Laxman; Kim, Ill Won; Woo, Won Seok; Sin, Byung Cheol; Lee, Hyung-il; Lee, Youngil

    2015-05-01

    This paper reports a simple, fast, low cost and environment-friendly route for preparing a highly crystalline giant dielectric material, CaCu3Ti4O12 (CCTO), through combustion of metal nitrates in non-aqueous precursor solution using inexpensive solid TiO2 powder. The route to producing pure phase CCTO ceramic using stable solid TiO2 is better than other several sol-gel routes reported earlier in which expensive alkoxides, oxynitrates, or chlorides of titanium are used as the titanium sources. X-ray diffraction revealed the formation of cubic perovskite CCTO. Scanning electron microscopy image showed the average grain sizes in the range of 1.5-5 μm. At 10 kHz and room temperature, the best CCTO ceramic exhibited a high dielectric constant, ε‧ ∼43325.24, with low dielectric loss, tan δ ∼0.088. The dielectric relaxation behavior was rationalized from impedance and modulus studies and the presence of a non-Debye type of relaxation was confirmed.

  12. Capillary electrophoresis with capacitively coupled contactless conductivity detection applied to the quantitation and to the determination of physical-chemical properties of peroxycarboxylates in aqueous medium.

    PubMed

    Vidal, Denis T R; do Lago, Claudimir L

    2013-07-01

    CE with C⁴D (CE-C⁴D) was successfully applied to the investigation of performate, peracetate, and perpropionate in aqueous medium. Ionic mobilities, diffusion coefficients, and hydrodynamic radii were obtained for the first time for these species. CE-C⁴D was also used to estimate the pKa values of the peroxycarboxylic acids. Because the peroxycarboxylates (POCs) undergoes hydrolysis while migrating, a simple calibration curve cannot be used for quantitation. Thus, an indirect calibration approach was used. The new method was used to monitor the formation of peroxycarboxylic acids from hydrogen peroxide and the carboxylic acid as well as to the quantitation of peracetic acid in a commercial sample. The CE-C⁴D method compares favorably with the conventional titration method because of the possibility of speciation of the POC, the low sample consumption, and the low LOD (14, 8, and 24 μmol/L for performate, peracetate, and perpropionate, respectively). Although POCs are structural isomers of monoalkyl carbonates, they have greater hydrodynamic radii, which suggests that the positions of the oxygen atoms in the molecules have a direct impact in the charge density and consequently on the hydration atmosphere. PMID:23595363

  13. Influence of annealing conditions on the crystallographic structure, chemical composition and luminescence of ZnO thin films

    NASA Astrophysics Data System (ADS)

    Khojier, K.; Savaloni, H.; Amani, E.

    2014-01-01

    ZnO thin films have many applications in semiconductor devices, such as semiconductor lasers, amplifiers, solar cells, chemical and ultraviolet sensors. We produced ZnO thin films on Si (4 0 0) substrates, using e-beam technique and subsequently annealed them under different conditions (i.e., temperature (200-800), time (60 min and 180 min) and environment (air and oxygen flow). The ZnO (0 0 2) preferred orientation which increases in intensity with annealing temperature and annealing time is deduced from X-ray diffraction (XRD) results. Dislocation density was higher for the films annealed in air which may be caused by the impurities (nitrogen and other species in the air) embedded in the film structure. No significant change in the nano-strain of each group of the samples (annealed under different conditions) was observed. The FESEM images showed a granular structure for annealed samples at 200 C and 800 C and a mixed structure of nanowires and nanosheets for samples annealed at 350 C and 500 C. Two peaks of UV emission and green emission were observed in the photoluminescence (PL) spectra of the produced samples. The UV emission increased with annealing temperature and annealing time showing higher crystal quality while the behavior of the green emission was opposite to that of the UV emission. The ZnO films resulted from annealing in the air showed stronger green emission than those annealed with flow of oxygen indicating higher impurity concentration and oxygen vacancies in the sample.

  14. Chemical Emergencies

    MedlinePlus

    Chemical Emergencies Under certain conditions, chemicals which are normally safe can be poisonous or harmful to your health. A major chemical emergency is an accident that releases a hazardous amount ...

  15. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-04-01

    The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor of 5 when mixed with nontronite at a concentration of 2.6×10-2 mole per gram. Moreover when the amount of nontronite in the sample of glycine is increased by a factor of two, the gain of photoprotection is multiplied by a factor of five. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect, but is at least partly due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate, in strong contrast with the other two molecules.

  16. Aqueous Chemistry

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.; Kargel, Jeffrey S.

    In Chapter 2, the book begins with a discussion of classical thermodynamics introducing the first and second laws of thermodynamics and the basic properties of systems such as internal energy (U), enthalpy (H), entropy (S), and Gibbs energy (G). From these quantities, we derive chemical potentials, activities, activity coefficients, and equilibrium constants. These are the basic principles upon which our equilibrium chemical thermodynamic model rests. Since one of our primary tasks is to present the Pitzer approach for modeling concentrated electrolyte solutions, his Thermodynamics textbook is ideally organized in laying out the basic principles upon which these models rest. Also, different authors sometimes define terms such as the Debye-Hückel slope somewhat differently, which can lead to confusion. In this work, we carefully followed Pitzer’s definitions (Pitzer, 1991, 1995). Next, we examine the Pitzer approach for defining chemical thermodynamic properties of highly concentrated solutions. The model developed in this work was originally designed to deal with freezing processes that can quickly concentrate solutes. Therefore, the Pitzer approach was ideally suited for this purpose.

  17. Facilitated attachment of nanoparticles at primary minima by nanoscale roughness is susceptible to hydrodynamic drag under unfavorable chemical conditions.

    PubMed

    Shen, Chongyang; Jin, Yan; Li, Baoguo; Zheng, Wenjuan; Huang, Yuanfang

    2014-01-01

    This study investigated effects of flow velocity on attachment of nanoparticles at primary minima in the presence of surface roughness under unfavorable chemical conditions. Saturated sand-packed column experiments were conducted at 0.1 and 0.2M NaCl using 30 nm polystyrene latex nanoparticles as model colloids. Particle attachment at primary minima was unambiguously determined by removing particles attached at secondary minima through introducing deionized water and excavating the packed beds. The calculated primary-minimum attachment efficiency was found to decrease with increasing flow velocity, indicating that the fraction of a collector surface that is available for attachment at primary minima decreases with increasing flow velocity. The torque analysis, however, showed that the adhesive torque that the particle experiences at primary minima is much larger than the maximum hydrodynamic drags of a porous medium for the flow velocities used. We attributed the discrepancy to the reason that the sand surface is very rough and the roughness mainly causes the attachment in primary minima under the experimental conditions used in this study. By considering influence of surface roughness in the torque analysis, our calculations show that while particle attachment in primary minima is favored atop of nanoasperities under unfavorable conditions, the adhesive torque that the particle experiences can be greatly reduced and, thus, the attachment is susceptible to flow drag. Whereas the increase of adhesive torque by surface roughness has been widely recognized in the literature, our study indicates that the rough asperities can also decrease adhesive torques for particles attached atop of them. PMID:24013017

  18. Mobilization and transport of metal-rich colloidal particles from mine tailings into soil under transient chemical and physical conditions.

    PubMed

    Lu, Cong; Wu, Yaoguo; Hu, Sihai; Raza, Muhammad Ali; Fu, Yilin

    2016-04-01

    Exposed mine tailing wastes with considerable heavy metals can release hazardous colloidal particles into soil under transient chemical and physical conditions. Two-layered packed columns with tailings above and soils below were established to investigate mobilization and transport of colloidal particles from metal-rich mine tailings into soil under transient infiltration ionic strength (IS: 100, 20, 2 mM) and flow rate (FR: 20.7, 41, and 62.3 mm h(-1)), with Cu and Pb as representatives of the heavy metals. Results show that the tailing particles within the colloidal size (below 2 μm) were released from the columns. A step-decrease in infiltration IS and FR enhanced, whereas a step-increase in the IS and FR restrained the release of tailing particles from the column. The effects of step-changing FR were unexpected due to the small size of the released tailing particles (220-342 nm, being not sensitive to hydrodynamic shear force), the diffusion-controlled particle release process and the relatively compact pore structure. The tailing particles present in the solution with tested IS were found negatively charged and more stable than soil particles, which provides favorable conditions for tailing particles to be transported over a long distance in the soil. The mobilization and transport of Cu and Pb from the tailings into soil were mediated by the tailing particles. Therefore, the inherent toxic tailing particles could be considerably introduced into soil under certain conditions (IS reduction or FR decrease), which may result in serious environmental pollution. PMID:26780043

  19. An investigation on the chemical stability and a novel strategy for long-term stabilization of diphenylalanine nanostructures in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nezammahalleh, H.; Amoabediny, G.; Kashanian, F.; Foroughi Moghaddam, M. H.

    The stability of diphenylalanine (FF) microwires and microtubes in phosphate buffer solution was investigated and a novel strategy was developed for their chemical stabilization. This stability investigation was carried out by optical microscopy and by high performance liquid chromatography (HPLC). These microstructures dissolve in the solution depending upon their degree of FF saturation. The dissolution mechanisms of the structures in kinetically limited processes were found by accurately fitting the experimental dissolution data to a theoretical kinetic equation. The dissolution data were well fitted to the particular Avrami-Erofe'ev kinetic expression (R2 > 0.98). These findings suggest that the structures can be stabilized by a decrease in the hydration of the constituent molecules thorough a chemical conformational induced transition upon heat treatment. The stable microtubes were fabricated in a novel three step procedure consisting of the reduction of silver ions in unstable FF microtubes by a citrate reductant, the stabilization by chemical conformational induced transition upon heat treatment, and the consequent oxidation of the reduced silver by a persulfate oxidant. These materials were characterized by electron microscopy and powder X-ray diffraction techniques. The long-term stability of both structures was also confirmed by optical microscopy and HPLC.

  20. Hematite Spherules in Basaltic Tephra Altered Under Aqueous, Acid-Sulfate Conditions on Mauna Kea Volcano, Hawaii: Possible Clues for the Occurrence of Hematite-Rich Spherules in the Burns Formation at Meridiani Planum, Mars

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Ming, D. W.; Graff, T. G.; Arvidson, R. E.; Bell, J. F., III; Squyres, S. W.; Mertzman, S. A.; Gruener, J. E.; Golden, D. C.; Robinson, G. A.

    2005-01-01

    Iron-rich spherules (>90% Fe2O3 from electron microprobe analyses) approx.10-100 microns in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe/Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H2O and/or /OH. The transmission Moessbauer spectrum of a spherule-rich separate is dominated by a hematite (alpha-Fe2O3) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al(3+) for Fe(3+) substitution and structural H2O and/or /OH. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.

  1. Ionic liquid-aqueous solution ultrasonic-assisted extraction of three kinds of alkaloids from Phellodendron amurense Rupr and optimize conditions use response surface.

    PubMed

    Wang, Wenchao; Li, Qingyong; Liu, Yuhui; Chen, Binbin

    2015-05-01

    In this paper, we chose diffident kinds of ionic liquids to optimal selection an optimal one to extract alkaloids from Phellodendron amurense Rupr. Four ionic liquids with diffident carbon chains or anions have been investigated and 1-butyl-3-methylimidazolium bromide with best productivity. Then, selections have been optimized in different conditions, including concentration of ionic liquid, time for ultrasonic treatment, ultrasonic power and solid-liquid ratio. Moreover, three conditions have been comprehensively assessment by response surface methodology, the optimal conditions were determined as follows ultrasonic power 100 W, extraction time 75 min and ratio of solvent to raw material 1:14. Under these conditions, the yield% (MIX) was 106.7% (extracted by heat reflux being defined 100%). Comparing with other methods, the advantages are saving conserving, time saving, high yield% and especially pollution-free. PMID:25443277

  2. Thermal behavior of aqueous iron oxide nano-fluid as a coolant on a flat disc heater under the pool boiling condition

    NASA Astrophysics Data System (ADS)

    Salari, E.; Peyghambarzadeh, S. M.; Sarafraz, M. M.; Hormozi, F.; Nikkhah, V.

    2016-04-01

    This paper experimentally focuses on the pool boiling heat transfer characteristics of gamma Fe3O4 aqueous nano-fluids on a flat disc heater. The nano-fluid used in this research was prepared using two-step method and was stabilized using nonylphenol ethoxylate nonionic surfactant, pH setting, and sonication process as well. Influence of different operating parameters such as heat flux (0-1546 kW/m2), mass concentration of nano-fluids (weight concentration 0.1-0.3 %), bubble formation, critical heat flux (1170 kW/m2 for water, 1230 kW/m2 (wt% = 0.1), 1320 kW/m2 (wt% = 0.2), 1450 kW/m2 (wt% = 0.3) and fouling on pool boiling heat transfer coefficient of nano-fluid as a thermal performance index were experimentally investigated and briefly discussed. Results demonstrated that the pool boiling heat transfer coefficient increases with increasing the mass concentration and the applied heat flux. In addition, the rate of bubble formation is significantly intensified at higher heat fluxes and subsequently, larger bubbles detach the surface due to the intensification of bubble coalescence. In terms of fouling formation, it can be stated that fouling of nano-fluids is a strong function of time and rate of deposition is increased over the extended time while the pool boiling heat transfer coefficient was not decreased over the time, as porous deposited layer on the surface are detached from the surface by bubble interactions. In terms of critical heat flux, capillary action of the deposited layer was found to be the main reason responsible for increasing the critical heat flux as liquid is stored inside the porous deposited layer, which enhances the surface toleration against the critical heat flux crisis.

  3. Bioenhanced dissolution of dense non-aqueous phase of trichloroethylene as affected by iron reducing conditions: model systems and environmental samples.

    PubMed

    Paul, Laiby; Smolders, Erik

    2015-01-01

    The anaerobic biotransformation of trichloroethylene (TCE) can be affected by competing electron acceptors such as Fe (III). This study assessed the role of Fe (III) reduction on the bioenhanced dissolution of TCE dense non-aqueous phase liquid (DNAPL). Columns were set up as 1-D diffusion cells consisting of a lower DNAPL layer, a layer with an aquifer substratum and an upper water layer that is regularly refreshed. The substrata used were either inert sand or sand coated with 2-line ferrihydrite (HFO) or two environmental Fe (III) containing samples. The columns were inoculated with KB-1 and were repeatedly fed with formate. In none of the diffusion cells, vinyl chloride or ethene was detected while dissolved and extractable Fe (II) increased strongly during 60 d of incubation. The cis-DCE concentration peaked at 4.0 cm from the DNAPL (inert sand) while it was at 3.4 cm (sand+HFO), 1.7 cm and 2.5 cm (environmental samples). The TCE concentration gradients near the DNAPL indicate that the DNAPL dissolution rate was larger than that in an abiotic cell by factors 1.3 (inert sand), 1.0 (sand+HFO) and 2.2 (both environmental samples). This results show that high bioavailable Fe (III) in HFO reduces the TCE degradation by competitive Fe (III) reduction, yielding lower bioenhanced dissolution. However, Fe (III) reduction in environmental samples was not reducing TCE degradation and the dissolution factor was even larger than that of inert sand. It is speculated that physical factors, e.g. micro-niches in the environmental samples protect microorganisms from toxic concentrations of TCE. PMID:25460750

  4. Aqueous electrolyte modeling in ASPEN PLUS{trademark}

    SciTech Connect

    Bloomingburg, G.F. |; Simonson, J.M.; Moore, R.C.; Mesmer, R.E.; Cochran, H.D.

    1995-02-01

    The presence of electrolytes in aqueous solutions has long been recognized as contributing to significant departures from thermodynamic ideality. The presence of ions in process streams can greatly add to the difficulty of predicting process behavior. The difficulties are increased as temperatures and pressures within a process are elevated. Because many chemical companies now model their processes with chemical process simulators it is important that such codes be able to accurately model electrolyte behavior under a variety of conditions. Here the authors examine the electrolyte modeling capability of ASPEN PLUS{trademark}, a widely used simulator. Specifically, efforts to model alkali metal halide and sulfate systems are presented. The authors show conditions for which the models within the code work adequately and how they might be improved for conditions where the simulator models fail.

  5. Simulation of size-segregated aerosol chemical composition over northern Italy in clear sky and wind calm conditions

    NASA Astrophysics Data System (ADS)

    Landi, T. C.; Curci, G.; Carbone, C.; Menut, L.; Bessagnet, B.; Giulianelli, L.; Paglione, M.; Facchini, M. C.

    2013-05-01

    The present article compares the outputs of the 3-D regional chemistry-transport model (CTM) CHIMERE against observations of the size-resolved aerosol chemical composition over northern Italy in clear sky and wind calm conditions. Two 4-day intensive field campaigns were carried out in July 2007 and February 2008 at three sites (urban, rural and mountain backgrounds) in the framework of the AEROCLOUDS project. Predicted levels are in reasonable agreement with observations for the urban and rural sites. Bias ranges from - 30%, for the rural site in winter, to + 38%, for the urban site during summer. In addition, the model is able to capture both the daily evolution of the bulk aerosol mass as well as its spatial gradients. Aerosol size distribution and chemical composition remain difficult to predict. The largest discrepancies were found for secondary organic aerosol (SOA) during summer and nitrates during the cold season. Compared with observations, modelled size distribution is shifted towards fine mode in winter, and towards coarse mode in summer. More accurate predictions can be achieved for both seasons by tuning the gas to particle absorption process. By reducing the SOA absorption rate by 25% at the urban sampling site in summer, the correlation between observed and simulated SOA size distributions increases from - 0.30 to + 0.70, and the bias is reduced from 200% to 0%. In winter, increasing the intra-sectional flux of particles from smaller to larger ones by a factor of 5, the Pearson correlation coefficient calculated over the nitrate size distribution goes up to + 0.85, compared to + 0.50 from CTRL, also resulting in a better agreement with the size distribution of PM10. As expected, the nitrate bulk mass concentration does not vary with respect to the base-case, and therefore nitrate overestimation remains present in the model.

  6. State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

    SciTech Connect

    Chase, Zizwe; Kasakov, Stanislav; Shi, Hui; Vjunov, Aleksei; Fulton, John L.; Camaioni, Donald M.; Balasubramanian, Mahalingam; Zhao, Chen; Wang, Yong; Lercher, Johannes A.

    2015-11-09

    The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was determined during aqueous phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy (EXAFS). On sulfonated carbon and HZSM-5 supports, the NiO and Ni(OH)2 were readily reduced to Ni(0) under reaction conditions (~35 bar H2 in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). On the silica support, less than 70% of the Ni was converted to Ni(0) under reaction conditions, which is attributed to the formation of Ni phyllosilicates. Over a broad range of reaction conditions there was no leaching of Ni from the supports. In contrast, rapid leaching of the Ni(II) from HZSM-5 was observed, when 15 wt. % aqueous acetic acid was substituted for the aqueous phenol solution. Once the metallic state of Ni was established there was no leaching in 15 wt. % acetic acid at 473 K and 35 bar H2. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. The STEM was supported under the Laboratory Directed Research and Development Program: Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), a multi-program national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. STEM was performed at EMSL, a DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research and located at PNNL.

  7. Anthemis xylopoda flowers aqueous extract assisted in situ green synthesis of Cu nanoparticles supported on natural Natrolite zeolite for N-formylation of amines at room temperature under environmentally benign reaction conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Hatamifard, Arezo

    2015-12-15

    Zeolites, which are nontoxic, abundant, and cheap, are very promising supports for the design and preparation of new and environmentally benign catalysts. In this study, Cu nanoparticles (NPs) were immobilized on the surface of natural Natrolite zeolite by Anthemis xylopoda flowers aqueous extract as a reducing and stabilizing agent. Afterward, the catalytic performance of the prepared catalyst was investigated for N-formylation of amines at room temperature under environmentally benign reaction conditions. The catalyst could be reused at least 5 times without any decrease in activity. The advantages of the present protocol include the use of green catalyst, easy isolation of the products, reusability of catalyst, absence of nontoxic reagents, and excellent yield of the products. PMID:26319331

  8. Effects of catalyst support and chemical vapor deposition condition on synthesis of multi-walled carbon nanocoils

    NASA Astrophysics Data System (ADS)

    Suda, Yoshiyuki; Iida, Tetsuo; Takikawa, Hirofumi; Harigai, Toru; Ue, Hitoshi; Umeda, Yoshito

    2016-02-01

    Multi-walled carbon nanocoil (MWCNC) is a carbon nanotube (CNT) with helical shape. We have synthesized MWCNCs and MWCNTs hybrid by chemical vapor deposition (CVD). MWCNCs are considered to be a potential material in nanodevices, such as electromagnetic wave absorbers and field emitters. It is very important to take into account the purity of MWCNCs. In this study, we aimed to improve the composition ratio of MWCNCs to MWCNTs by changing catalyst preparation and CVD conditions. As a catalyst, Fe2O3/zeolite was prepared by dissolving Fe2O3 fine powder and Y-type zeolite (catalyst support material) in ethanol with an Fe density of 0.5wt.% and with a zeolite density of 3.5wt.%. The catalyst-coated Si substrate was transferred immediately onto a hotplate and was heated at 80°C for 5 min. Similarly, Fe2O3/Al2O3, Co/zeolite/Al2O3, Co/zeolite, and Co/Al2O3 were prepared. The effect of the difference of the composite catalysts on synthesis of MWCNCs was considered. The CVD reactor was heated in a tubular furnace to 660-790°C in a nitrogen atmosphere at a flow rate of 1000 ml/min. Subsequently, acetylene was mixed with nitrogen at a flow rate ratio of C2H2/N2 = 0.02-0.1. The reaction was kept under these conditions for 10 min. MWCNTs and MWCNCs were well grown by the catalysts of Co/zeolite and Co/Al2O3. The composition ratio of MWCNCs to MWCNTs was increased by using a combination of zeolite and Al2O3. The highest composition ratio of MWCNCs to MWCNTs was 12%.

  9. Aqueous cleaning design presentation

    NASA Technical Reports Server (NTRS)

    Maltby, Peter F.

    1995-01-01

    The phase-out of CFC's and other ozone depleting chemicals has prompted industries to re-evaluate their present methods of cleaning. It has become necessary to find effective substitutes for their processes as well as to meet the new cleaning challenges of improved levels of cleanliness and to satisfy concerns about environmental impact of any alternative selected. One of the most popular alternatives being selected is aqueous cleaning. This method offers an alternative for removal of flux, grease/oil, buffing compound, particulates and other soils while minimizing environmental impact. What I will show are methods that can be employed in an aqueous cleaning system that will make it environmentally friendly, relatively simple to maintain and capable of yielding an even higher quality of cleanliness than previously obtained. I will also explore several drying techniques available for these systems and other alternatives along with recent improvements made in this technology. When considering any type of cleaning system, a number of variables should be determined before selecting the basic configuration. Some of these variables are: (1) Soil or contaminants being removed from your parts; (2) The level of cleanliness required; (3) The environmental considerations of your area; (4) Maintenance requirements; and (5) Operating costs.

  10. Thermal response of intravascular and rectal tissue to temperature changes and chemical conditions in the rumen of sheep

    PubMed Central

    Mendel, V. E.; Raghavan, G. V.

    1966-01-01

    1. Experiments were conducted with two wether sheep which were fitted with rumen cannulae and chronically implanted intravascular thermocouples. An attempt was made to study the thermal response of intravascular and rectal tissue to temperature changes and chemical conditions in the rumen. 2. When ice or hot water were placed in the rumen there was an immediate fall or rise in the intravascular temperature accompanied by a similar change in rectal temperature. The intravascular temperatures returned to their precooling or preheating level of 40° C within 130 min, the rectal temperatures required 6-8 hr to return to their pretreatment values. 3. When 0·5 M acetic acid was infused into the rumen there was a marked rise in the intravascular temperature, over and above the diurnal rhythm but not in rectal temperatures. Infusion of mixtures of acetic plus propionic or acetic plus n-butyric acids caused an intravascular temperature rise on feeding within the range of the diurnal pattern. In fasted animals, infusions of volatile fatty acids resulted in no rise in intravascular temperature. PMID:5937414

  11. Chemical composition and anticancer activity of essential oils of Mediterranean sage (Salvia officinalis L.) grown in different environmental conditions.

    PubMed

    Russo, Alessandra; Formisano, Carmen; Rigano, Daniela; Senatore, Felice; Delfine, Sebastiano; Cardile, Venera; Rosselli, Sergio; Bruno, Maurizio

    2013-05-01

    Salvia officinalis L. can be found worldwide and its leaves are commonly used as ingredient in food industry. Sage essential oil is applied in the treatment of a range of diseases and has been shown to possess different biological activities. The objectives of our research were to study the effects of environment on crop, chemical composition and anticancer activity on S. officinalis essential oil. Sage was cultivated at eighteen experimental sites in south-central Italy (Molise) in different growing environments. The essential oils (S1-S18), extracted by hydrodistillation, were analyzed by GC and CG/MS. Results show that the main components were α-thujone, camphor, borneol, γ-muurolene and sclareol for all the samples, but the percentages of these compounds varied depending on environmental factors such as altitude, water availability and pedo-climatic conditions. The growth-inhibitory and proapoptotic effects of the eighteen sage essential oils were evaluated in three human melanoma cell lines, A375, M14, and A2058. PMID:23291326

  12. Short-term variability of the phytoplankton community in coastal ecosystem in response to physical and chemical conditions' changes

    NASA Astrophysics Data System (ADS)

    Pannard, Alexandrine; Claquin, Pascal; Klein, Cécile; Le Roy, Bertrand; Véron, Benoît

    2008-11-01

    The short-term dynamics (time scale of a few days) of phytoplankton communities in coastal ecosystems, particularly those of toxic species, are often neglected. Such phenomena can be important, especially since these very species can endanger the sustainability of shellfish farming. In this study, we investigated the short-term changes in phytoplankton community structure (species succession) in two coastal zones in parallel with physical and chemical conditions. Mixing events with allochtonous waters could thus be distinguished from local processes associated with population growth when it was associated with a change in light or nutrient limitation. Mixing events and water advection influenced fluctuations in total phytoplankton biomass and concentration of dominant species, while local processes influenced delayed changes in community structure. The estuarine species Asterionellopsis glacialis increased in concentration when the water mass mixed with the nearest estuarine water masses. The biological response, measured as photosynthetic capacity, occurred after a time-lag of a few hours, while the changes in community structure occurred after a time-lag of a few days. Finally, the coastal water mass was constantly mixed with both the nearest estuarine and marine water masses, leading in turn to delayed changes in phytoplankton community structure. These changes in species composition and dominance were observed on a time scale of a few days, which means that some toxic species may be missed with a bi-weekly sampling strategy.

  13. Aqueous chemical growth of Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films: Air annealing and photoelectrochemical properties

    SciTech Connect

    Shinde, N.M.; Deshmukh, P.R.; Patil, S.V.; Lokhande, C.D.

    2013-05-15

    Highlights: ? Facile and efficient route for synthesis of CZTS film. ? Effect of annealing on structural, morphological and electrical properties of CZTS films. ? Solar cell study. - Abstract: In present investigation, Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films have been deposited on to glass substrates by novel chemical successive ionic layer adsorption and reaction (SILAR) method. The effect of air annealing in the temperature range between 573 and 773 K on the structural, morphological, optical and electrical properties has been studied. The X-ray diffraction studies revealed the formation of polycrystalline CZTS films. The surface morphological study showed smooth, compact and uniform film formation after annealing formation. The band gap was in between range from 1.5 to 1.8 eV depending on annealing temperature. The thermo emf measurement revealed that the CZTS exhibits p-type electrical conductivity. Further, photoactivity of CZTS thin films was tested by forming the photoelectrochemical cell.

  14. Large-scale green chemical synthesis of adjacent quaternary chiral centers by continuous flow photodecarbonylation of aqueous suspensions of nanocrystalline ketones.

    PubMed

    Hernández-Linares, María Guadalupe; Guerrero-Luna, Gabriel; Pérez-Estrada, Salvador; Ellison, Martha; Ortin, Maria-Mar; Garcia-Garibay, Miguel A

    2015-02-01

    To demonstrate the ease of scale-up and synthetic potential of some organic solid state reactions, we report the synthesis, crystallization, and solid state photochemistry of acyclic, homochiral, hexasubstituted (+)-(2R,4S)-2-carbomethoxy-4-cyano-2,4-diphenyl-3-pentanone 1. We demonstrate that solid state photodecarbonylation of (+)-(2R,4S)-1 affords (+)-(2R,3R)-2-carbomethoxy-3-cyano-2,3-diphenyl-butane 2 with two adjacent stereogenic, all-carbon substituted quaternary centers, in quantitative chemical yield and 100% diastereoselectivity and enantiomeric excess. The efficient multigram photodecarbonylation of (+)-(2R,4S)-1 as a nanocrystalline suspension in water using a continuous flow photoreactor shows that the large-scale synthesis of synthetically challenging compounds using photochemical synthesis in the solid state can be executed in a remarkably simple manner. PMID:25578232

  15. Synthesis Under 'Greener' Conditions: Role of Sustainable Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

  16. Photo-Fenton degradation of the herbicide 2,4-D in aqueous medium at pH conditions close to neutrality.

    PubMed

    Conte, Leandro O; Schenone, Agustina V; Alfano, Orlando M

    2016-04-01

    A theoretical and experimental study of the photo-Fenton degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in water is presented. A kinetic model derived from a reaction sequence is proposed using the ferrioxalate complex as iron source for conditions of pH = 5. The kinetic model was employed to predict the concentrations of 2,4-D, 2,4-dichlorophenol (2,4-DCP), hydrogen peroxide (HP) and oxalate (Ox) in a flat plate laboratory reactor irradiated with a solar simulator. Two types of incident irradiation levels were tested by different combinations of attenuation filters. The effects of the oxalate/Fe(+3) molar ratio (Ox/Fe), the reaction temperature (T) and the 2,4-D/HP molar ratio (R) on the photo-Fenton process were also investigated. For low radiation level and operating conditions of R = 50 and T = 50 °C, a 2,4-D conversion of 95.6% was obtained after 180 min. Moreover, the 2,4-D conversion was almost 100% in only 120 min when the system was operated under the same operating conditions and high radiation level. From the proposed model and the experimental data, the corresponding kinetic parameters were estimated applying a nonlinear regression method. A good agreement between the kinetic model and experimental data, for a wide range of simulated solar operating conditions, was observed. For 2,4-D, 2,4-DCP, HP and Ox concentrations, the calculated RMSE were 1.21 × 10(-2), 5.45 × 10(-3), 2.86 × 10(-1) and 2.65 × 10(-2) mM, respectively. PMID:26800432

  17. [The working conditions and morbidity with temporary loss of work capacity for those engaged in the manufacture of household chemical preparations].

    PubMed

    Amirov, N Kh; Khamitova, R Ia

    1992-01-01

    Workers engaged in production of household chemical goods (paints, synthetic detergents, aerosols) are exposed to harmful factors (noise levels higher than the maximal allowable ones, concentration of chemical agents in the air surpassing the MACs). Such work conditions are estimated as unfavourable according to the hygienic classification. The total morbidity and some nosologic forms (respiratory, digestive, locomotor systems and skin) are growing in number especially in workers of aerosol production. Statistic analysis revealed that the length of service was directly related to the level of total morbidity and the incidence of gastrointestinal diseases in the workers engaged in manufacture of household chemical goods. PMID:1427316

  18. PHYSIOLOGICAL ONTOGENY : A. CHICKEN EMBRYOS. II. CATABOLISM. CHEMICAL CHANGES IN FERTILE EGGS DURING INCUBATION. SELECTION OF STANDARD CONDITIONS.

    PubMed

    Murray, H A

    1925-09-20

    As this paper goes to press a complete review of the chemistry of the fertile egg will be appearing (19). The author, Mr. J. Needham, was kind enough to allow me to inspect his manuscript and thus avail myself of the comprehensive bibliography and discussion. It is surprising that no biochemists have estimated the changing water content of the egg during incubation. Many of the analyses reported in Needham's review were expressed in per cent of total weight or per cent of dry solid, and consequently are of questionable value, since these latter functions are themselves changing; the former due to water evaporation and the latter through the addition of shell constituents and the burning of oxidizable organic compounds. Moreover, there has been no statistical treatment of the results, and the reliability of the average, figures obtained has consequently been difficult to estimate. Tangl's work, quoted throughout this paper, except for its lack of statistical treatment is more enlightening. However, his concept of the so called "Energy of Embryogenesis" which he propounds, seems to me misleading and unwarranted. What Tangl measured was the amount and the caloric value of the solid material burned and thus the quantity of energy lost during the embryonic period. The latter is equivalent to the usual measurements of catabolism. In the case of the embryo it is not basal metabolism which is being estimated, since the conditions are not basal. The embryo is absorbing and assimilating nutriment all the while at a relatively rapid rate. The calorific value of the oxidized solid, which is in truth the amount of energy lost during a certain chosen interval, in Tangl's judgment stands for the energy of embryogenesis; i.e., the energy of development (growth + differentiation). We believe that this conception is erroneous. The two processes, anabolism and catabolism, occur together and undoubtedly have some relationship, but surely one is not a measure of the other. In a starving animal, and so probably in a starving embryo, there is a considerable amount of so called basal metabolism. Thus if the "Embryogenetic Energy" were measured under these conditions a figure would be obtained for which there was no growth to correspond, or in other words there would be a value for something which did not exist. It will be seen in our later communications that the changes with age of metabolic rate and growth rate do not coincide. The amount of catabolism under certain circumstances does not accelerate growth or anabolism, but seems rather to be a limiting factor. It is as if when the absorbed energy were constant an increase of catabolism would make inroads upon the amount of energy which otherwise would remain for storage (growth). If, as Pembrey's (20) experiments would tend to show, there is an increase of metabolism in the oldest embryos when the outside temperature is lowered, one would find at the end of incubation in such cases that there was a greater amount of so called "Energy of Development" but smaller embryo. It seems that the potential energy amassed as growth comes from that remaining after the needs of the body have been satisfied. The results of the experiments described in this paper have formed the basis for judgment in the selection of suitable standard conditions for the incubation of hen's eggs. Standardization was necessary so that in future experiments the more important environmental factors might be kept uniform within a certain appropriate range and therefore not be held accountable for deviations observed in the embryos. Henceforth in this series of papers the term "standard incubation conditions" will signify that (1) the temperature was constantly at 38.8 +/- 0.4 degrees C., (2) the humidity at 67.5 +/- 2.5 per cent, (3) there was a continuous flow of warm air into the incubator to provide the necessary circulation, and (4) the eggs were rolled once a day within the constant temperature room. The incubator, a double-walled copper cabinet, stands in a constant temperature room, the fluctuations of which are +/- 1.0 degrees C. The space between the walls of the incubator is filled with water which serves as a buffer to outer variations. It might be repeated that all the eggs are from White Leghorn hens, are incubated 2 days after laying, and that they are kept cold during the interval necessary for transportation. With the figures from our chemical analyses and metabolic rate experiments, it was possible to calculate values for the concentration of total solids, fat, and nitrogen throughout the incubation period. These data were necessary as a general chemical background for further work. The results of the calculations are obviously rough. Because of the great variability of the eggs a satisfactory degree of accuracy could not have been attained without a very large number of analyses supplemented by complete statistical treatment. The necessity for such a comprehensive study was not evident, and it is our belief that the approximations reached in this paper are sufficiently close to serve our present purposes. The chief facts that have been ascertained in this investigation are (1) Loss of water by the egg during incubation is a function of the atmospheric humidity in its immediate environment. More rapid circulation of air lowers the humidity around the egg and thus increases evaporation. Other facts influencing evaporation are (a) atmospheric temperature, (b) thickness and surface area of the shell, and (c) conditions within the egg, the most important of which, it is suggested, is the amount of heat produced by the embryo. The latter factor, in turn, depends upon its size and age, and a significant change does not become apparent until the last 3 or 4 days of incubation, that is to say, when the embryo is of sufficient mass to exert a measurable force. (2) The surface area of the eggs in sq. cm. may be approximately represented by the formula S = K W(2/3), where K = 5.07 +/- 0.10, and W = the weight of the whole egg in gm. (3) There is a loss of weight by the shell during incubation. This is most noticeable near the end of the cycle, when the loss seems to parallel in general the weight of the embryo. (4) There is also a loss of solid matter during incubation. Chemical analyses indicate that about 98 per cent of the material oxidized is fat. This conclusion is corroborative of previous work by Hasselbalch, Hasselbalch and Bohr, and Tangl. (5) Carbon dioxide may be measured with relative accuracy. When it is assumed that it is derived from the oxidation of fat, satisfactory corroboration of the chemical analyses is obtained. These experiments have furnished the data from which the values have been calculated for total solids, fats, and protein in the whole egg throughout incubation. The figures may be used later for comparison with the concentration of these substances within the embryo. PMID:19872226

  19. Aqueous Geochemistry at High Pressures and High Temperatures

    SciTech Connect

    Bass, Jay D.

    2015-05-21

    This project is aimed at experimental characterization of the sound velocities, equations of state (EOS), and derived physical and chemical properties of aqueous solutions and carbon dioxide at extreme pressure and temperature conditions relevant to processes occurring in the interior of the Earth. Chemical transport, phase changes (including melting), fluid-solid reactions, and formation of magmatic liquids at convergent plat boundaries are a key motivation for this project. Research in this area has long been limited by the extreme experimental challenges and lack of data under the appropriate pressure-temperature (P-T) conditions. The vast majority of studies of aqueous geochemistry relevant to terrestrial problems of fluid-rock interactions have been conducted at 0.3 GPa or less, and the widely used Helgeson-Kirkham-Flowers equation of state for