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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

  2. 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

  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 (delta

  4. 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

  5. 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.

  6. 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

  7. Chemical conditioning of sludge.

    PubMed

    Novak, J T; Park, C

    2004-01-01

    With all the advances made in understanding the structure and composition of sewage sludges, chemical conditioning remains a trial and error process, both with regard to the type and dose of conditioner needed. Recent studies at Virginia Tech have found that biological floc consists of two types of biopolymer, material associated with iron and aluminium and material associated with calcium and magnesium. These materials behave differently when sludges undergo digestion. This results in very different material being released into solution during digestion and very different conditioning requirements. This study shows that the primary materials released during anaerobic digestion are proteins and coagulation of the colloidal protein fraction in solution is the primary mechanism for conditioning. For aerobically digested sludges, both proteins and polysaccharides make up the colloid fraction, which interferes with dewatering. This research also shows that the effectiveness of the digestion process as characterized by volatile solids destruction is directly related to the chemical dose required for conditioning. That is, as the solids destruction increases, the conditioning chemical requirement also increases. Well digested sludges dewater more poorly and require more conditioning chemical than those with less volatile solids destruction. PMID:15259940

  8. CHEMICAL TRANSFORMATIONS USING NON-TRADITIONAL APPROACHES: MICROWAVE-ASSISTED GREENER SYNTHESES IN AQUEOUS MEDIA OR UNDER SOLVENT-FREE 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<...

  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

  11. CHEMICAL SYNTHESES IN AQUEOUS MEDIA USING MICROWAVES

    EPA Science Inventory

    The development of efficient, selective and eco-friendly synthetic methods has remained a major focus of our research group. Microwave (MW) irradiation as alternative energy source in conjunction with water as reaction media has proven to be a successful 'greener' chemical appro...

  12. 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

  13. 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-Hückel), solvent-ion, and ion-ion interactions. The solvent-ion and ion-ion interaction parameters show less dependence on pressure and

  14. 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.

  15. Timescales and conditions for the aqueous alteration of chondrites

    NASA Astrophysics Data System (ADS)

    Jilly, Christine E.

    It has become well-recognized that water played a critical role in the early geological evolution of materials through observation of hydrated phases in chondritic meteorites. However, details about the mechanism, timing, and conditions of aqueous alteration are poorly constrained. This dissertation investigates water-driven processes in Renazzo-like (CR) carbonaceous chondrites, with some comparison to the heavily altered and Mighei-like (CM) chondrites. CR chondrites were chosen as the focus of this study, as they are the only chondrite group to range from practically anhydrous to completely hydrated, providing petrographic context for the aqueous alteration process. The central goal of the thesis is to elucidate the complete mechanism of aqueous alteration, from primary anhydrous components to secondary minerals. This research uses a variety of micro-analytical techniques to address three main objectives: 1) to detail the petrographic context, 2) to quantify the onset and duration of alteration using radiometric dating, and 3) to constrain the fluid chemistry and conditions for aqueous alteration. On a microscopic scale, fine-grained matrices and glassy mesostases were the first phases to become altered, allowing for elemental transport over short distances (< 100 microns). As alteration progressed, the iron-metal was oxidized, and silicate phenocrysts were pseudomorphically replaced. 53Mn-53 Cr radiometric dating of secondary carbonates in CR chondrites show that aqueous alteration began quickly after accretion of the parent body, ~4 Myr after the beginning of the Solar System. This is contemporaneous with dolomite formation in the CM chondrite Sutter's Mill and with carbonate formation in other CM chondrites. However, the calcite age from a heavily hydrated CR lithology indicates that late-stage alteration occurred ~12 Myr after the beginning of the Solar System. The oxygen isotopic compositions of magnetite and carbonate minerals reveal that altering fluid

  16. Chemical Reactivity at Metal Oxide-Aqueous Solution Interfaces

    NASA Astrophysics Data System (ADS)

    Brown, Gordon E., Jr.

    2005-03-01

    The chemical reactivity of metal oxide surfaces in contact with aqueous solutions, with respect to cations and anions, is controlled by the composition, structure, and charging properties of the surface, the dielectric properties of the bulk oxide, and the stability of the aqueous cation or anion complex versus its sorption complex. These points will be illustrated for selected cations, anions, and metal oxides using macroscopic uptake and EXAFS spectroscopy results, x-ray standing wave data, and crystal truncation rod diffraction data. The reactivity of metal oxide surfaces with respect to low molecular weight (LMW) carboxylic acids is also dependent on the types of ring structures formed between surface functional groups and the LMW organic molecules. These types of interactions will be illustrated using ATR-FTIR data and dissolution measurements as a function of pH for oxalate, maleate, phthalate, and pyromellitate interacting with boehmite (AlOOH). Co-Authors are Tae Hyun Yoon, Stephen B. Johnson, Dept. of Geological & Environmental Sciences, Stanford University, Stanford CA 94305-2115; Thomas P. Trainor, Dept. of Chemistry and Biochemistry, University of Alaska Fairbanks, Fairbanks, AK 99775; Anne M. Chaka, National Institute of Standards and Technology, Gaithersburg, MD 20899

  17. 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

  18. Hydrodefluorination and hydrogenation of fluorobenzene under mild aqueous conditions.

    PubMed

    Baumgartner, Rebekka; McNeill, Kristopher

    2012-09-18

    Fluorinated organic compounds are increasingly used in many applications, and their release to the environment is expected. It is therefore important to find suitable methods for degradation of fluorinated compounds under environmentally relevant conditions. In this study, a simple heterogeneous rhodium-based catalytic system (Rh/Al(2)O(3) and H(2)) for hydrodefluorination and hydrogenation of fluorobenzene under mild aqueous conditions (1 atm of H(2), ambient temperature) was developed and the underlying reaction mechanism was investigated. Fluorobenzene degraded rapidly (t(1/2) ≈ 0.2 h) to form cyclohexane and fluoride (F(-)) as the stable end products, with benzene and cyclohexene observed as intermediates. Cyclohexadiene intermediates were not observed but were expected to form during the hydrogenation of benzene. Three postulated but unobserved fluorinated intermediates were subjected to the catalytic reaction conditions, and it was concluded that they most likely do not form during the fluorobenzene degradation reaction. Isotope labeling experiments showed that the unsaturated intermediates undergo rapid and reversible hydrogenation/dehydrogenation under the reaction conditions and also that fully saturated compounds are unreactive in the catalytic system. Both molecular hydrogen and water were sources of hydrogen in the final cyclohexane product. Kinetic fitting indicated that sorption/desorption of fluorobenzene onto the catalyst surface plays an important role in the mechanism. PMID:22871102

  19. Optical spectroscopy of simple aqueous solutions under extreme conditions

    NASA Astrophysics Data System (ADS)

    Vass, H.; Edington, D.; Crain, J.

    2003-06-01

    We report the results of an extensive series of Brillouin scattering experiments on simple aqueous solutions with a view to exploring their dynamical properties over a wide range of temperatures and pressures. For all solutes studied that inhibit freezing and allow access to temperatures far below the normal supercooling limit of water, we find clear spectroscopic evidence of GHz-range viscoelastic behavior below ≈-40 °C. This is manifested by a dramatic rise in the Brillouin mode frequencies accompanied by initial broadening and subsequent narrowing of the spectral linewidths on cooling. We find similar behavior in pure compressed (to between 2 and 4 kbar) supercooled water. This suggests that the low-temperature viscoelastic dynamics of these solutions is dominated by the behavior of the aqueous component which evidently exhibits a pronounced decrease in relaxation time though the temperature range over which it occurs is inaccessible unless freezing is suppressed either by pressure or the presence of solutes. No firm conclusion can be drawn concerning the proposed second critical point at these very low temperatures though it is not required for a consistent interpretation of the data. In the high-temperature regime, where the hydrogen bond structure is disrupted, we find considerable chemical sensitivity (even among the three chloride salts NaCl, CsCl, and CaCl2) in the dynamics especially in the vicinity of the liquid-gas critical point. This is in contrast to the low-temperature case where the cooperative dynamics of the water network dominates and appears to remain intact in the presence of a wide variety of solutes.

  20. 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...

  1. An experimental study of magnesite precipitation rates at neutral to alkaline conditions and 100-200 °C as a function of pH, aqueous solution composition and chemical affinity

    NASA Astrophysics Data System (ADS)

    Saldi, Giuseppe D.; Schott, Jacques; Pokrovsky, Oleg S.; Gautier, Quentin; Oelkers, Eric H.

    2012-04-01

    Magnesite precipitation rates were measured at temperatures from 100 to 200 °C as a function of saturation state and reactive fluid composition in mixed flow reactors. Measured rates were found to increase systematically with increasing saturation state but to decrease with increasing reactive fluid aqueous CO32- activity and pH. Measured rates are interpreted through a combination of surface complexation models and transition state theory. In accord with this formalism, constant saturation state BET surface area normalized magnesite precipitation rates (rMg) are a function of the concentration of protonated Mg sites at the surface (>MgOH2+) and can be described using: rMg=kMg-Kn 1-ΩMgn where kMg- represents a rate constant, KOH and KCO3 stand for equilibrium constants, ai designates the activity of the subscripted aqueous species, n refers to a reaction order equal to 2, and ΩMg denotes the saturation state of the reactive solution with respect to magnesite. Retrieved values of n are consistent with magnesite precipitation control by a spiral growth mechanism. The temperature variation of the rate constant can be described using kMg-=Aaexp(-Ea/RT), where Aa represents a pre-exponential factor equal to 5.9 × 10-5 mol/cm2/s, Ea designates an activation energy equal to 80.2 kJ/mol, R denotes the gas constant, and T corresponds to the absolute temperature. Comparison of measured magnesite precipitation rates with corresponding forsterite dissolution rates suggest that the relatively slow rates of magnesite precipitation may be the rate limiting step in mineral carbonation efforts in ultramafic rocks.

  2. Determination of Gibbs energies of formation in aqueous solution using chemical engineering tools.

    PubMed

    Toure, Oumar; Dussap, Claude-Gilles

    2016-08-01

    Standard Gibbs energies of formation are of primary importance in the field of biothermodynamics. In the absence of any directly measured values, thermodynamic calculations are required to determine the missing data. For several biochemical species, this study shows that the knowledge of the standard Gibbs energy of formation of the pure compounds (in the gaseous, solid or liquid states) enables to determine the corresponding standard Gibbs energies of formation in aqueous solutions. To do so, using chemical engineering tools (thermodynamic tables and a model enabling to predict activity coefficients, solvation Gibbs energies and pKa data), it becomes possible to determine the partial chemical potential of neutral and charged components in real metabolic conditions, even in concentrated mixtures. PMID:26965669

  3. '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...

  4. Effects of surface condition on aqueous corrosion and environmental embrittlement of iron aluminides

    SciTech Connect

    Perrin, R.L.; Buchanan, R.A.

    1996-08-01

    Effects of retained high-temperature surface oxides, produced during thermomechanical processing and/or heat treatment, on the aqueous-corrosion and environmental-embrittlement characteristics of Fe{sub 3}Al-based iron aluminides (FA-84, FA-129 and FAL-Mo), a FeAl-based iron aluminide (FA-385), and a disordered low-aluminum Fe-Al alloy (FAPY) were evaluated. All tests were conducted at room temperature in a mild acid-chloride solution. In cyclic-anodic-polarization testing for aqueous-corrosion behavior, the surface conditions examined were: as-received (i.e., with the retained high-temperature oxides), mechanically cleaned and chemically cleaned. For all materials, the polarization tests showed the critical pitting potentials to be significantly lower in the as-received condition than in the mechanically-cleaned and chemically-cleaned conditions. These results indicate detrimental effects of the retained high-temperature oxides in terms of increased susceptibilities to localized corrosion. In 200-hour U-bend stress-corrosion-cracking tests for environmental-embrittlement behavior, conducted at open-circuit corrosion potentials and at a hydrogen-charging potential of {minus}1500 mV (SHE), the above materials (except FA-385) were examined with retained oxides and with mechanically cleaned surfaces. At the open-circuit corrosion potentials, none of the materials in either surface condition underwent cracking. At the hydrogen-charging potential, none of the materials with retained oxides underwent cracking, but FA-84, FA-129 and FAL-Mo in the mechanically cleaned condition did undergo cracking. These results suggest beneficial effects of the retained high-temperature oxides in terms of increased resistance to environmental hydrogen embrittlement.

  5. 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

  6. 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

  7. 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.

  8. 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

    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

  9. Method for Non-Invasive Determination of Chemical Properties of Aqueous Solutions

    NASA Technical Reports Server (NTRS)

    Todd, Paul W. (Inventor); Jones, Alan (Inventor); Thomas, Nathan A. (Inventor)

    2016-01-01

    A method for non-invasively determining a chemical property of an aqueous solution is provided. The method provides the steps of providing a colored solute having a light absorbance spectrum and transmitting light through the colored solute at two different wavelengths. The method further provides the steps of measuring light absorbance of the colored solute at the two different transmitted light wavelengths, and comparing the light absorbance of the colored solute at the two different wavelengths to determine a chemical property of an aqueous solution.

  10. A comparison of the chemical sinks of atmospheric organics in the gas and aqueous phase

    NASA Astrophysics Data System (ADS)

    Epstein, S. A.; Nizkorodov, S. A.

    2012-09-01

    Photochemical reactions represent the main pathway for the removal of non-methane volatile organic compounds (VOCs) in the atmosphere. VOCs may react with hydroxyl radical (OH), the most important atmospheric oxidant, or they can be photolyzed by actinic radiation. In the presence of clouds and fog, VOCs may partition into the aqueous phase where they can undergo aqueous photolysis and/or reaction with dissolved OH. The significance of direct aqueous photolysis is largely uncertain due to the lack of published absorption cross sections and photolysis quantum yields. In light of this, we strive to identify atmospherically relevant VOCs where removal by aqueous photolysis may be a significant sink. The relative importance of different photochemical sinks is assessed by calculating the ratios of the removal rates inside air parcels containing cloud and fog droplets. This relative approach provides useful information in spite of the limited aqueous photolysis data. Results of this work should help guide researchers in identifying molecules that are the most likely to undergo aqueous OH oxidation and photolysis. For example, we find that out of the 27 atmospherically relevant species investigated, the removal of glyceraldehyde and pyruvic acid by aqueous photolysis is potentially an important sink. We also determine the relative magnitudes of these four chemical sinks for the set of relevant organic compounds.

  11. A comparison of the chemical sinks of atmospheric organics in the gas and aqueous phase

    NASA Astrophysics Data System (ADS)

    Epstein, S. A.; Nizkorodov, S. A.

    2012-04-01

    Photochemical reactions represent the main pathway for the removal of non-methane volatile organic compounds (VOCs) in the atmosphere. VOCs may react with hydroxyl radical (OH), the most important atmospheric oxidant, or they can be photolyzed by actinic radiation. In the presence of clouds and fog, VOCs may partition into the aqueous phase where they can undergo aqueous photolysis and/or reaction with dissolved OH. The significance of direct aqueous photolysis is largely uncertain due to the lack of published absorption cross sections and photolysis quantum yields. In light of this, we strive to identify atmospherically relevant VOCs where removal by aqueous photolysis may be a significant sink. The relative importance of different photochemical sinks is assessed by calculating the ratios of the removal rates inside air parcels containing cloud and fog droplets. This relative approach provides useful information in spite of the limited aqueous photolysis data. Results of this work should help guide researchers in identifying molecules that are the most likely to undergo aqueous OH oxidation and photolysis. We find that out of the 27 atmospherically relevant species investigated, the removal of glyceraldehyde and pyruvic acid by aqueous photolysis is potentially an important sink. We also determine the relative magnitudes of these four chemical sinks for the set of relevant organic compounds.

  12. 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.

  13. Optical techniques for nanoscale probing and chemical detection in aqueous environments

    NASA Astrophysics Data System (ADS)

    Pristinski, Denis

    substrates from aqueous solution. We have shown that the coverage density of Ag nanoparticles on the glass substrates correlates with the amount of adsorbed PAH. The SERS-active substrates were robust and stable in 0.5 M NaCl solutions, as well in extreme acidic and basic conditions. Rhodamine 6G dye (R6G) was chosen as a model molecule for SERS spectra acquisition. The glass substrates with immobilized non-aggregated Ag nanoparticles exhibited SERS enhancement and provided in situ detection sensitivity of R6G at 5 ppt level, with estimated surface coverage of 2 to 4 R6G molecules per silver particle. The results will improve the design of SERS-active photonic crystal fibers for highly sensitive chemical and biological detection.

  14. 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

  15. Effect of surface condition on the aqueous corrosion behavior of iron aluminies

    SciTech Connect

    Buchanan, R.A.; Perrin, R.L.

    1995-08-01

    The effects of retained high-temperature surface oxides, produced during thermomechanical processing and/or heat treatment, on the aqueous-corrosion characteristics of Fe-Al-based alloys were evaluated by electrochemical methods. Cyclic anodic polarization evaluations were conducted at room temperature in a mild acid-chloride solution (pH = 4,200 ppm Cl{sup {minus}}) on the Fe{sub 3}Al-based iron aluminides, FA-84 (Fe-28Al-2Cr-0.05B, at %), FA-129 (Fe-28Al-5Cr-0.5Nb-0.2C, at %), and FAL-Mo (Fe-28Al-5Cr-1Mo-0.04B-0.08Zr, at %), on the FeAl-based iron aluminide, FA-385 (Fe-35.65Al-0.20Mo-0.05Zr-0.11C, at %). The surface conditions evaluated were: As received (i.e. with the retained high-temperature oxides), mechanically cleaned (ground through 600-grit SiC paper), and chemically cleaned (10% HNO{sub 3}, 2%HF, at 43 {degree}C). The principal electrochemical parameter of interest was the critical putting potential with lower values indicating less resistance to chloride-induced localized corrosion. For all materials evaluated, the critical pitting potential was found to be significantly lower in the as-received condition than in the mechanically-cleaned and chemically-cleaned conditions. Mechanisms responsible for the detrimental high-temperature-oxide effect are under study.

  16. Oxygen Tension in the Aqueous Humor of Human Eyes under Different Oxygenation Conditions

    PubMed Central

    Sharifipour, Farideh; Idani, Esmaeil; Zamani, Mitra; Helmi, Toktam; Cheraghian, Bahman

    2013-01-01

    Purpose To measure oxygen tension in the aqueous humor of human eyes under different oxygenation conditions. Methods This prospective comparative interventional case series consisted of two parts. In the first part, 120 consecutive patients scheduled for cataract surgery were randomized into group I (control group) in which surgery was performed under local anesthesia inhaling 21% oxygen; group II in whom general anesthesia using 50% oxygen was employed; and group III receiving general anesthesia with 100% oxygen. After aspirating 0.2 ml aqueous humor under sterile conditions, the aqueous sample and a simultaneously drawn arterial blood sample were immediately analyzed using a blood gas analyzer. In part II the same procedures were performed in 10 patients after fitting a contact lens and patching the eye for 20 minutes (group IV) and in 10 patients after transcorneal delivery of oxygen at a flow rate of 5 L/min (group V). Results Mean aqueous PO2 in groups I, II and III was 112.3±6.2, 141.1±20.4, and 170.1±27 mmHg, respectively (P values <0.001) and mean arterial PO2 was 85.7±7.9, 184.6±46, and379.1±75.9 mmHg, respectively (P values <0.001). Aqueous PO2 was 77.2±9.2 mmHg in group IV and 152.3±10.9 mmHg in group V (P values <0.001). There was a significant correlation between aqueous and blood PO2 (r=0.537, P<0.001). The contribution of atmospheric oxygen to aqueous PO2 was 23.7%. Conclusion Aqueous oxygen tension is mostly dependent on the systemic circulation and in part on the atmosphere. Increasing inspiratory oxygen and transcorneal oxygen delivery both increase aqueous PO2 levels. PMID:23943686

  17. 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.

  18. 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.

  19. 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

  20. Heterogeneous Catalytic Conversion of Biobased Chemicals into Liquid Fuels in the Aqueous Phase.

    PubMed

    Wu, Kejing; Wu, Yulong; Chen, Yu; Chen, Hao; Wang, Jianlong; Yang, Mingde

    2016-06-22

    Different biobased chemicals are produced during the conversion of biomass into fuels through various feasible technologies (e.g., hydrolysis, hydrothermal liquefaction, and pyrolysis). The challenge of transforming these biobased chemicals with high hydrophilicity is ascribed to the high water content of the feedstock and the inevitable formation of water. Therefore, aqueous-phase processing is an interesting technology for the heterogeneous catalytic conversion of biobased chemicals. Different reactions, such as dehydration, isomerization, aldol condensation, ketonization, and hydrogenation, are applied for the conversion of sugars, furfural/hydroxymethylfurfural, acids, phenolics, and so on over heterogeneous catalysts. The activity, stability, and reusability of the heterogeneous catalysts in water are summarized, and deactivation processes and several strategies are introduced to improve the stability of heterogeneous catalysts in the aqueous phase. PMID:27158985

  1. 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...

  2. Polyelectrolyte brushes: a novel stable lubrication system in aqueous conditions.

    PubMed

    Kobayashi, Motoyasu; Terada, Masami; Takahara, Atsushi

    2012-01-01

    Surface-initiated controlled radical copolymerizations of 2-dimethylaminoethyl methacrylate (DMAEMA), 2-(methacryloyloxy)ethyl phosphorylcholine (MPC), 2-(methacryloyloxy)ethyltrimethylammonium chloride) (MTAC), and 3-sulfopropyl methacrylate potassium salt (SPMK) were carried out on a silicon wafer and glass ball to prepare polyelectrolyte brushes with excellent water wettability. The frictional coefficient of the polymer brushes was recorded on a ball-on-plate type tribometer by linear reciprocating motion of the brush specimen at a selected velocity of 1.5 x 10(-3) m s-1 under a normal load of 0.49 N applied to the stationary glass ball (d = 10 mm) at 298 K. The poly(DMAEMA-co-MPC) brush partially cross-linked by bis(2-iodoethoxy)ethane maintained a relatively low friction coefficient around 0.13 under humid air (RH > 75%) even after 200 friction cycles. The poly(SPMK) brush revealed an extremely low friction coefficient around 0.01 even after 450 friction cycles. We supposed that the abrasion of the brush was prevented owing to the good affinity of the poly(SPMK) brush for water forming a water lubrication layer, and electrostatic repulsive interactions among the brushes bearing sulfonic acid groups. Furthermore, the poly(SPMK-co-MTAC) brush with a chemically cross-linked structure showed a stable low friction coefficient in water even after 1400 friction cycles under a normal load of 139 MPa, indicating that the cross-linking structure improved the wear resistance of the brush layer. PMID:23285641

  3. 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

  4. Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

    NASA Astrophysics Data System (ADS)

    Monod, A.; Chevallier, E.; Durand Jolibois, R.; Doussin, J. F.; Picquet-Varrault, B.; Carlier, P.

    The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were JMHP=4.5 (±1.0)×10 -5 s -1 and JEHP=3.8 (±1.0)×10 -5 s -1 for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10 8 M -1 s -1 and 5.8 (±1.9)×10 8 M -1 s -1 relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10 9 M -1 s -1 relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.

  5. 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.

  6. 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...

  7. 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

  8. 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

  9. 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.

  10. 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##

  11. 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

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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...

  19. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. PMID:21246746

  20. 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 Earth’s 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] <  ∼ 0.3). We suggest that elevated concentrations of HCl in the remote marine boundary layer are sufficient to modify Ca-rich particles in dust storms and can play a more important role in forming a deliquescent layer on the particle surfaces as they are transported toward remote ocean regions. PMID:20921372

  1. A review of chemical, electrochemical and biological methods for aqueous Cr(VI) reduction.

    PubMed

    Barrera-Díaz, Carlos E; Lugo-Lugo, Violeta; Bilyeu, Bryan

    2012-07-15

    Hexavalent chromium is of particular environmental concern due to its toxicity and mobility and is challenging to remove from industrial wastewater. It is a strong oxidizing agent that is carcinogenic and mutagenic and diffuses quickly through soil and aquatic environments. It does not form insoluble compounds in aqueous solutions, so separation by precipitation is not feasible. While Cr(VI) oxyanions are very mobile and toxic in the environment, Cr(III) cations are not. Like many metal cations, Cr(III) forms insoluble precipitates. Thus, reducing Cr(VI) to Cr(III) simplifies its removal from effluent and also reduces its toxicity and mobility. In this review, we describe the environmental implications of Cr(VI) presence in aqueous solutions, the chemical species that could be present and then we describe the technologies available to efficiently reduce hexavalent chromium. PMID:22608208

  2. 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

  3. Chemical disinfection under conditions of microgravity

    NASA Astrophysics Data System (ADS)

    Marchin, George L.

    1997-01-01

    There is enormous potential for point-of-use water purifiers where central water treatment does not exist or distribution systems are faulty and allow incursion of pathogenic organisms after primary treatment. Manned space missions on the Space Shuttle and planned missions on the Space Station also employ point-of-use water purifiers termed microbial check valves (MCVs). Polyiodide resin materials in use on the Space Shuttle within the MCV and in terrestrial water purifiers, silver and copper chelex resins, zirconium peroxide chelex resin, and a quaternary ammonium compound-Dow Corning 5700-polymerized to carbon and polystyrene beads, were compared for disinfection ability. Experiments were conducted in fluid processing apparatus (FPAs) at unit gravity and in microgravity conditions aboard seven STS missions. These new materials may have applications in both space and terrestrial water treatment devices.

  4. Zero-valent iron removal rates of aqueous Cr(VI) measured under flow conditions

    SciTech Connect

    Kaplan, Daniel I.; Gilmore, Tyler J.

    2004-06-30

    The rates of Cr(VI) removal from the aqueous phase by zero-valent iron Fe(0) was measured under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a gournwater remediation technology that replaces the sand in a filter pack of a conventioanl well with a reactive material, such as Fe(0).

  5. Assessment and correction of turbidity effects on Raman observations of chemicals in aqueous solutions.

    PubMed

    Sinfield, Joseph V; Monwuba, Chike K

    2014-01-01

    Improvements in diode laser, fiber optic, and data acquisition technologies are enabling increased use of Raman spectroscopic techniques for both in lab and in situ water analysis. Aqueous media encountered in the natural environment often contain suspended solids that can interfere with spectroscopic measurements, yet removal of these solids, for example, via filtration, can have even greater adverse effects on the extent to which subsequent measurements are representative of actual field conditions. In this context, this study focuses on evaluation of turbidity effects on Raman spectroscopic measurements of two common environmental pollutants in aqueous solution: ammonium nitrate and trichloroethylene. The former is typically encountered in the runoff from agricultural operations and is a strong scatterer that has no significant influence on the Raman spectrum of water. The latter is a commonly encountered pollutant at contaminated sites associated with degreasing and cleaning operations and is a weak scatterer that has a significant influence on the Raman spectrum of water. Raman observations of each compound in aqueous solutions of varying turbidity created by doping samples with silica flour with grain sizes ranging from 1.6 to 5.0 μm were employed to develop relationships between observed Raman signal strength and turbidity level. Shared characteristics of these relationships were then employed to define generalized correction methods for the effect of turbidity on Raman observations of compounds in aqueous solution. PMID:25357083

  6. Stability of lysozyme in aqueous extremolyte solutions during heat shock and accelerated thermal conditions.

    PubMed

    Avanti, Christina; Saluja, Vinay; van Streun, Erwin L P; Frijlink, Henderik W; Hinrichs, Wouter L J

    2014-01-01

    The purpose of this study was to investigate the stability of lysozyme in aqueous solutions in the presence of various extremolytes (betaine, hydroxyectoine, trehalose, ectoine, and firoin) under different stress conditions. The stability of lysozyme was determined by Nile red Fluorescence Spectroscopy and a bioactivity assay. During heat shock (10 min at 70°C), betaine, trehalose, ectoin and firoin protected lysozyme against inactivation while hydroxyectoine, did not have a significant effect. During accelerated thermal conditions (4 weeks at 55°C), firoin also acted as a stabilizer. In contrast, betaine, hydroxyectoine, trehalose and ectoine destabilized lysozyme under this condition. These findings surprisingly indicate that some extremolytes can stabilize a protein under certain stress conditions but destabilize the same protein under other stress conditions. Therefore it is suggested that for the screening extremolytes to be used for protein stabilization, an appropriate storage conditions should also be taken into account. PMID:24465983

  7. 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

  8. Electrical conductivity of single CdS nanowire synthesized by aqueous chemical growth

    NASA Astrophysics Data System (ADS)

    Long, Yunze; Chen, Zhaojia; Wang, Wenlong; Bai, Fenglian; Jin, Aizi; Gu, Changzhi

    2005-04-01

    In this Letter, we report on the temperature-dependent conductivity and current-voltage curve of a single CdS nanowire, which was synthesized by a simple aqueous chemical growth method. A pair of platinum microleads was fabricated on the single CdS nanowire by focused ion-beam deposition. The room-temperature conductivity and the band gap of the single CdS wire are 0.82Ω-1cm-1 and 0.055eV, respectively. When the applied electric field is larger than 1090Vcm-1, the CdS nanowire shows a nonlinear I-V curve at room temperature.

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

    SciTech Connect

    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.

  10. 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.

  11. 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

  12. 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...

  13. 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 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...

  14. 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 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...

  15. 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...

  16. 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 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...

  17. Alumino-silicate speciation in aqueous fluids at deep crustal conditions

    NASA Astrophysics Data System (ADS)

    Mookherjee, M.; Keppler, H.; Manning, C. E.

    2014-12-01

    Alumina and silica are major oxides in most crustal rocks. While SiO2 is quite soluble in aqueous fluids at metamorphic conditions, behavior of Al2O3 in crustal metamorphic fluids has been poorly understood. It is known that alumina is dramatically less soluble in aqueous fluids and hence it is difficult to explain the common occurrence of quartz with aluminous minerals in metamorphic veins. In order to understand this complex behavior of alumina, we investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 oC. In order to better understand the spectral features of the aqueous fluids, we used first principles simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with KOH solution in equilibrium with Al2O3 show a sharp band at ~620 cm-1 which could be attributed to the [Al(OH)4]1- species. The band grows in intensity with temperature along an isochore. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [Al(OH)4]1- species to dimers [(OH)2-Al-O2-Al(OH)2]2- or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. We are also investigating the effect of SiO2 on the solubility of Al2O3 and the relative energetics of formation of pure alumina dimer [(OH)3-Al-O-Al(OH)3]2- vs. the aluminosilicate dimers, [(OH)3-Al-O-Si(OH)3]2- at deep crustal conditions. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

  18. The distribution of methane in groundwater in Alberta (Canada) and associated aqueous geochemistry conditions

    NASA Astrophysics Data System (ADS)

    Humez, Pauline; Mayer, Bernhard; Nightingale, Michael; Becker, Veith; Kingston, Andrew; Taylor, Stephen; Millot, Romain; Kloppmann, Wolfram

    2016-04-01

    wide range of δ13CCH4 values in baseline groundwater samples, no conclusive evidence was found for deep thermogenic gas that had migrated in significant amounts into shallow aquifers either naturally or via anthropogenically induced pathways. This study shows that the combined interpretation of aqueous geochemistry data in concert with the chemical and isotopic composition of dissolved and/or free gas can yield unprecedented insights into formation or migration of methane in shallow groundwater. This enables the assessment of cross-formational methane migration and provides an understanding of alkane gas sources and pathways necessary for a stringent baseline definition in the context of current and future unconventional hydrocarbon exploration and exploitation.

  19. 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.

  20. 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

  1. 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...

  2. 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.

  3. 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.

  4. 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

  5. Quantum chemical prediction of redox reactivity and degradation pathways for aqueous phase contaminants: an example with HMPA.

    PubMed

    Blotevogel, Jens; Borch, Thomas; Desyaterik, Yury; Mayeno, Arthur N; Sale, Tom C

    2010-08-01

    Models used to predict the fate of aqueous phase contaminants are often limited by their inability to address the widely varying redox conditions in natural and engineered systems. Here, we present a novel approach based on quantum chemical calculations that identifies the thermodynamic conditions necessary for redox-promoted degradation and predicts potential degradation pathways. Hexamethylphosphoramide (HMPA), a widely used solvent and potential groundwater contaminant, is used as a test case. Its oxidation is estimated to require at least iron-reducing conditions at low to neutral pH and nitrate-reducing conditions at high pH. Furthermore, the transformation of HMPA by permanganate is predicted to proceed through sequential N-demethylation. Experimental validation based on LC/TOF-MS analysis confirms the predicted pathways of HMPA oxidation by permanganate to phosphoramide via the formation of less methylated as well as singly and multiply oxygenated reaction intermediates. Pathways predicted to be thermodynamically or kinetically unfavorable are similarly absent in the experimental studies. Our newly developed methodology will enable scientists and engineers to estimate the favorability of contaminant degradation at a specific field site, suitable approaches to enhance degradation, and the persistence of a contaminant and its reaction intermediates. PMID:20608732

  6. 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.

  7. 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.

  8. Aqueous suspension of anise “Pimpinella anisum” protects rats against chemically induced gastric ulcers

    PubMed Central

    Al Mofleh, Ibrahim A; Alhaider, Abdulqader A; Mossa, Jaber S; Al-Soohaibani, Mohammed O; Rafatullah, Syed

    2007-01-01

    AIM: To substantiate the claims of Unani and Arabian traditional medicine practitioners on the gastroprotective potential effect of a popular spice anise, “Pimpinella anisum L.” on experimentally-induced gastric ulceration and secretion in rats. METHODS: Acute gastric ulceration in rats was produced by various noxious chemicals including 80% ethanol, 0.2 mol/L NaOH, 25% NaCl and indomethacin. Anti-secretory studies were undertaken using pylorus-ligated Shay rat technique. Levels of gastric non-protein sulfhydryls (NP-SH) and wall mucus were estimated and gastric tissue was also examined histologically. Anise aqueous suspension was used in two doses (250 and 500 mg/kg body weight) in all experiments. RESULTS: Anise significantly inhibited gastric mu-cosal damage induced by necrotizing agents and indomethacin. The anti-ulcer effect was further confirmed histologically. In pylorus-ligated Shay rats, anise suspension significantly reduced the basal gastric acid secretion, acidity and completely inhibited the rumenal ulceration. On the other hand, the suspension significantly replenished ethanol-induced depleted levels of gastric mucosal NP-SH and gastric wall mucus concentration. CONCLUSION: Anise aqueous suspension possesses significant cytoprotective and anti-ulcer activities against experimentally-induced gastric lesions. The anti-ulcer effect of anise is possibly prostaglandin-mediated and/or through its anti-secretory and antioxidative properties. PMID:17373749

  9. 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.

  10. 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.

  11. 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.

  12. Physical and chemical interactions at the interface between atmospheric pressure plasmas and aqueous solutions

    NASA Astrophysics Data System (ADS)

    Lindsay, Alexander; Byrns, Brandon; Knappe, Detlef; Graves, David; Shannon, Steven

    2014-10-01

    Transport and reactions of charged species, neutrals, and photons at the interface between plasmas and liquids must be better quantified. The work presented here combines theoretical and experimental investigations of conditions in the gas and liquid phases in proximity to the interface for various discharges. OES is used to determine rotational and vibrational temperatures of OH, NO, and N2+; the relationship between these temperatures that characterize the distribution of internal energy states and gas and electron kinetic temperatures is considered. The deviation of OH rotational states from equilibrium under high humidity conditions is also presented. In contradiction with findings of other groups, high energy rotational states appear to become underpopulated with increasing humidity. In the aqueous phase, concentrations of longer-lived species such as nitrate, nitrite, hydrogen peroxide, and ozone are determined using ion chromatography and colorimetric methods. Spin-traps and electron paramagnetic resonance (EPR) are investigated for characterization of short-lived aqueous radicals like OH, O2-, NO, and ONOO-. Finally, experimental results are compared to a numerical model which couples transport and reactions within and between the bulk gas and liquid phases.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. On hematite as a target for dating aqueous conditions on Mars

    NASA Astrophysics Data System (ADS)

    Kula, Joseph; Baldwin, Suzanne L.

    2012-07-01

    Hematite spherules, identified by the Opportunity Mars Exploration Rover (MER), have been interpreted as in situ evidence for past aqueous conditions on the Martian surface. Hematite has also been demonstrated as a reliable (U-Th)/He chronometer, although it is not widely used. In the absence of post-formational diffusive He loss, (U-Th)/He ages measured from Martian hematite spherules should yield the time since water was present on Mars. Using published morphologic constraints and He diffusion kinetics for hematite we model He diffusive loss to assess whether Martian hematite spherules will retain original (U-Th)/He ages during long residence times (4.0 Ga) at surface conditions (22 °C). Fractional loss calculations predict <2% diffusive loss at 22 °C over 4.0 Ga, indicating Martian hematite will preserve ages within analytical precision of the (U-Th)/He technique. If present Mars conditions persisted since the Noachian (e.g. 4.0 Ga), hematite spherules likely record ages reflecting the timing of aqueous mineralization. For the 'wetting-upwards' Burn Formation at Meridiani Planum, hematite from the lower eolian dune subunit would be postdepositional providing a minimum age on deposition, while hematite from the upper interdune/playa unit may be syndepositional thus yielding the age of the deposit. Therefore (U-Th)/He hematite ages obtained from samples collected along a vertical profile could potentially constrain the timing and rates of water saturation of the rock column, and the timing of the transition from wet to dry conditions at Meridiani Planum. Determining an absolute paleohydrologic timescale on Mars may reveal if water was available for sufficient durations required for the development of life.

  18. 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

  19. ZERO-VALENT IRON REMOVAL RATES OF AQUEOUS Cr(VI) MEASURED UNDER FLOW CONDITIONS

    SciTech Connect

    Kaplan, Daniel I.; Gilmore, Tyler J.

    2004-06-01

    The rates of Cr(VI) removal from the aqueous phase by zero-valent iron, Fe(0), was measured under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a groundwater remediation technology that replaces the sand in a filter pack of a conventional well with a reactive material, such as Fe(0). Dissolved Cr(VI) concentration, dissolved O2 concentration, and Eh data indicated that Cr(VI) removal from the aqueous phase was mass-transfer limited. All pseudo-first-order regression fits to the data were significant (P≤0.05), however, they did not capture many of the salient aspects of the data, including that the removal rate often decreased as contact time increased. As such, application of these rate coefficients to predict long-term Cr(VI) removal were compromised. The rate coefficients measured under flow conditions were comparable to those measured previously under batch conditions with significantly greater solution:solid ratios. Between the range of 20 and 100 wt-% Fe(0) in the column, there was little measurable change in the reaction kinetics. Thus, it may be possible to include sand into the reactive filter packs in the event it is necessary to increase filter pack porosity or to decrease the accumulation of secondary reaction products that may lead to filter pack plugging. Background water chemistry (0.2 M NaHCO3, distilled water, and a carbonate-dominated groundwater) had only marginal, if any, effects on reaction rate coefficients. The reaction rates measured in this study indicated that an Fe(0) filter pack could be used to lower Cr(VI) concentrations by several orders of magnitude in a once-through mode of operation of the Reactive Well Technology.

  20. 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...

  1. 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.

  2. 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

  3. 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

  4. 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...

  5. 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.

  6. 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)

  7. Removal Rates of Aqueous Cr(VI) by Zero-Valent Iron Measured Under Flow Conditions

    SciTech Connect

    Kaplan, D.I.

    2002-05-10

    Studies were undertaken to measure the rate of Cr(VI) removal from the aqueous phase by zero-valent iron, Fe(0), under flow conditions. The intent of this work was to generate removal rate coefficients that would be applicable to the Reactive Well Technology, a groundwater remediation technology that replaces the sand in a filter pack of a conventional well with a reactive material, such as Fe(0). The pseudo-first-order rate coefficients measured under flow conditions were comparable to those previously measured under batch conditions that had significantly greater ratios of solution volume to Fe(0) surface area. Between the range of 20 and 100 weight percent Fe(0), there was little measurable change in the reaction kinetics. Thus, it may be possible to include sand into the reactive filter packs in the event it is necessary to increase filter pack porosity or to decrease the accumulation of secondary reaction products that may lead to filter pack plugging. Background water chemistry had only marginal effects on reaction rate coefficients. The reaction rates measured in this study indicated that an Fe(0) filter pack could be used to lower Cr(VI) concentrations by several orders of magnitude in a once-through mode of operation of the Reactive Well Technology.

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

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.; Kargel, Jeffrey S.; Catling, David C.; Jakubowski, Scott 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 (γ) > activity of water (a w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. 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

  9. 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

  10. Evaluation of an evanescent fiber optic chemical sensor for monitoring aqueous volatile organic compounds

    SciTech Connect

    Blair, D.S.

    1997-04-01

    Linear chemometric algorithms were used to model the quantitative response of an evanescent fiber optic chemical sensor in aqueous mixtures with concentrations between 20 and 300 ppm. Four data sets were examined with two different experimental arrangements. Two data sets contained trichloroethene, 1,1,2 trichloroethane, and toluene. Partial Least Squares, PLS, and Principal Component Regression, PCR, algorithms performed comparably on these calibration sets with cross-validated root mean squared errors of prediction (RMSEP) for trichloroethene, 1,1,1 trichloroethane, and toluene of approximately 26, 29 and 22 ppm, respectively. The third data set contained trichloroethene, 1,1,2 trichloroethane, toluene, and chloroform and the fourth contained these four analytes as well as tetrachloroethene. Again, both chemometric algorithms performed comparably on a given data set with RMSEP for trichloroethene, 1,1,2 trichloroethane, toluene, and chloroform of approximately 6, 6, 9, and 16 ppm from the first set, and 7, 11, 13, and 31 ppm from the second set with tetrachloroethene RMSEP of 31 ppm. The decrease in the quantitative performance of the sensor for modeling toluene and chloroform upon addition of tetrachloroethene to the sample solutions is due to increased cladding absorption features in the spectral response matrix. These features overlap with the analyte absorption features of toluene and chloroform. These results suggest one of the limitations with this type of sensing format.

  11. Chemical etching of stainless steel 301 for improving performance of electrochemical capacitors in aqueous electrolyte

    NASA Astrophysics Data System (ADS)

    Jeżowski, P.; Nowicki, M.; Grzeszkowiak, M.; Czajka, R.; Béguin, F.

    2015-04-01

    The main purpose of the study was to increase the surface roughness of stainless steel 301 current collectors by etching, in order to improve the electrochemical performance of electrical double-layer capacitors (EDLC) in 1 mol L-1 lithium sulphate electrolyte. Etching was realized in 1:3:30 (HNO3:HCl:H2O) solution with times varying up to 10 min. For the considered 15 μm thick foil and a mass loss around 0.4 wt.%, pitting was uniform, with diameter of pits ranging from 100 to 300 nm. Atomic force microscopy (AFM) showed an increase of average surface roughness (Ra) from 5 nm for the as-received stainless steel foil to 24 nm for the pitted material. Electrochemical impedance spectroscopy realized on EDLCs with coated electrodes either on as-received or pitted foil in 1 mol L-1 Li2SO4 gave equivalent distributed resistance (EDR) of 8 Ω and 2 Ω, respectively, demonstrating a substantial improvement of collector/electrode interface after pitting. Correlatively, the EDLCs with pitted collector displayed a better charge propagation and low ohmic losses even at relatively high current of 20 A g-1. Hence, chemical pitting of stainless steel current collectors is an appropriate method for optimising the performance of EDLCs in neutral aqueous electrolyte.

  12. 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.

  13. 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.

  14. Chemically induced compaction bands: Triggering conditions and band thickness

    NASA Astrophysics Data System (ADS)

    Stefanou, Ioannis; Sulem, Jean

    2014-02-01

    During compaction band formation, various mechanisms can be involved at different scales. Mechanical and chemical degradation of the solid skeleton and grain damage are important factors that may trigger instabilities in the form of compaction bands. Here we explore the conditions of compaction band formation in quartz- and carbonate-based geomaterials by considering the effect of chemical dissolution and grain breakage. As the stresses/deformations evolve, the grains of the material break, leading to an increase of their specific surface. Consequently, their dissolution is accelerated and chemical softening is triggered. By accounting for (a) the mass diffusion of the system, (b) a macroscopic failure criterion with dissolution softening, and (c) the reaction kinetics at the microlevel, a model is proposed and the conditions for compaction instabilities are investigated. Distinguishing the microscale (grain level) from the macrolevel (representative elementary volume) and considering the heterogeneous microstructure of the representative elementary volume, it is possible to discuss the thickness and periodicity of compaction bands. Two case studies are investigated. The first one concerns a sandstone rock reservoir which is water flooded and the second one a carbonate rock in which CO2 is injected for storage. It is shown that compaction band instabilities are possible in both cases.

  15. 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.

  16. 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

  17. 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.

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

    PubMed

    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

  19. Protection of moisture-sensitive drugs with aqueous polymer coatings: importance of coating and curing conditions.

    PubMed

    Bley, O; Siepmann, J; Bodmeier, R

    2009-08-13

    The aim of this study was to better understand the importance of coating and curing conditions of moisture-protective polymer coatings. Tablets containing freeze-dried garlic powder were coated with aqueous solutions/dispersions of hydroxypropyl methylcellulose (HPMC), poly(vinyl alcohol), ethyl cellulose and poly(methacrylate-methylmethacrylates). The water content of the tablets during coating and during storage at different temperatures and relative humidities (RH) was determined gravimetrically. In addition, changes in the allicin (active ingredient in garlic powder) content were monitored. During the coating process, the water uptake was below 2.7% and no drug degradation was detectable. Thermally induced drug degradation occurred only at temperatures above the coating temperatures. Different polymer coatings effectively decreased the rate, but not the extent of water uptake during open storage at room temperature and 75% RH. Tablets coated with poly(vinyl alcohol) and poly(methacrylate-methylmethacrylates) showed the lowest moisture uptake rates (0.49 and 0.57%/d, respectively). Curing at elevated temperature after coating did not improve the moisture-protective ability of the polymeric films, but reduced the water content of the tablets. Drug stability was significantly improved with tablets coated with poly(vinyl alcohol) and poly(methacrylate-methylmethacrylates). PMID:19477253

  20. 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

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

    PubMed

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

    2014-07-01

    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. PMID:24882223

  2. 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.

  3. Modeling aqueous ozone/UV process using oxalic acid as probe chemical.

    PubMed

    Garoma, Temesgen; Gurol, Mirat D

    2005-10-15

    A kinetic model that describes the removal of organic pollutants by an ozone/UV process is described. Oxalic acid, which reacts with a very low rate constant with ozone and relatively high rate constant with hydroxyl radical (OH*), was used as the probe chemical to model the process. The model was verified by experimental data on concentrations of oxalic acid and hydrogen peroxide (H202) under various experimental conditions, i.e., ozone gas dosage, UV light intensity, and varying oxalic acid concentrations. PMID:16295862

  4. 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.

  5. Physical beneficiation of char and chemically conditioned coal

    SciTech Connect

    Warzinski, R.P.; Cavallaro, J.A.

    1986-04-01

    Demineralization of coals and coal-derived chars is part of an effort to develop alternative fuels from coal. Pyrolysis and some gasification processes yield chars containing a large fraction of the calorific value of the feed coal and essentially all of its mineral matter. In the work reported here, three gasification chars produced from anthracite, bituminous, and subbituminous coals have been subjected to specific gravity separation to determine their yield-ash relationships. Either low yields or high ash levels in the float products were observed. Also reported is preliminary work concerning the use of chemical conditioning to enhance the cleanability of coal prior to physical beneficiation. Conditioning of an Illinois No. 6 River King Mine coal with either supercritical methanol or cyclohexane resulted in an improved yield-ash relationship, whereas similar treatment with supercritical toluene had a negative effect.

  6. Physical properties of rocks and aqueous fluids at conditions simulating near- and supercritical reservoirs

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried

    2016-04-01

    The growing interest in exploiting supercritical geothermal reservoirs calls for a thorough identification and understanding of physico-chemical processes occuring in geological settings with a high heat flow. In reservoir engineering, electrical sounding methods are common geophysical exploration and monitoring tools. However, a realistic interpretation of field measurements is based on the knowledge of both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. Thus, laboratory studies at simulated in-situ conditions provide a link between the field data and the material properties in the depth. The physico-chemical properties of fluids change dramatically above the critical point, which is for pure water 374.21 °C and 221.2 bar. In supercritical fluids mass transfer and diffusion-controlled chemical reactions are enhanced and cause mineral alterations. Also, ion mobility and ion concentration are affected by the change of physical state. All this cause changes in the electrical resistivity of supercritical fluids and may have considerable effects on the porosity and hydraulic properties of the rocks they are in contact with. While there are some datasets available for physical and chemical properties of water and single component salt solutions above their critical points, there exist nearly no data for electrical properties of mixed brines, representing the composition of natural geothermal fluids. Also, the impact of fluid-rock interactions on the electrical properties of multicomponent fluids in a supercritical region is scarcely investigated. For a better understanding of fluid-driven processes in a near- and supercritical geological environment, in the framework of the EU-funded FP7 program IMAGE we have measured (1) the electrical resistivity of geothermal fluids and (2) physical properties of fluid saturated rock samples at simulated in-situ conditions. The permeability and electrical

  7. 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

  8. The Aqueous Complexation of Thorium with Citrate under Neutral to Basic Conditions

    SciTech Connect

    Felmy, Andrew R; Cho, Herman M; Dixon, David A; Xia, Yuanxian; Hess, Nancy J; Wang, Zheming

    2006-04-20

    The aqueous complexation of thorium with citrate was investigated under neutral to basic conditions and over a broad range of ionic strengths. The solubility data for ThO2(am) as a function of citrate concentration indicate the presence of stable species with citrate-to-metal ratios of between two to three. The dependence of the ThO2(am) solubilities on hydrogen ion concentration can also be readily explained by the classical assumption of hydrolysis of the central Th(IV) ion to form mixed thorium-hydroxide-citrate complexes. 13C NMR spectra of the species in solution confirm that the citrate-to-metal ratio of the species in solution is between two and three and show that the citrate attaches to the metal in a bidentate fashion through oxygens on the -carboxylate and -alkoxyl groups, rather than through the carboxylate groups. The 13C NMR spectra, as well as a density functional theory (DFT) electronic structure study of the presumptive complexes, suggests that the associated α-hydroxyl proton can be displaced during complex formation. These findings indicate an alternative explanation for the observed changes in solubility as a function of hydrogen ion concentration, the displacement of protons from the citrate alkoxyl groups via metal binding. Removal of protons from the alkoxyl groups or hydrolysis of the central Th(IV) cannot be distinguished by thermodynamic measurements, however the species with the α-hydroxyl proton removed (i.e., ThOH(Cit)25- and Th(Cit)38-) would appear to better represent the microscopic binding. Apparent equilibrium constants for the solution phase reactions of these species and the hydrous thorium oxide have been calculated as a function of ionic strength.

  9. Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: Implication for the nuclear waste storage

    NASA Astrophysics Data System (ADS)

    Truche, Laurent; Berger, Gilles; Destrigneville, Christine; Pages, Alain; Guillaume, Damien; Giffaut, Eric; Jacquot, Emmanuel

    2009-08-01

    Sulphate reduction by hydrogen, likely to occur in deep geological nuclear waste storage sites, was studied experimentally in a two-phase system (water + gas) at 250-300 °C and under 4-16 bars H 2 partial pressure in hydrothermal-vessels. The calculated activation energy is 131 kJ/mol and the half-life of aqueous sulphate in the presence of hydrogen and elemental sulphur ranges from 210,000 to 2.7 × 10 9 years at respective temperatures of 90 °C, the thermal peak in the site and 25 °C, the ambient temperature far from the site. The features and rate of the sulphate reduction by H 2 are close to those established for TSR in oil fields. The experiments also show that the rate of sulphate reduction is not significantly affected in the H 2 pressure range of 4-16 bars and in the pH range of 2-5, whereas a strong increase is measured at pH below 2. We suggest that the condition for the reaction to occur is the speciation of sulphate dominated by non symmetric species ( HSO4- at low pH), and we propose a three steps reaction, one for each intermediate-valence sulphur species, the first one requiring H 2S as electron donor rather than H 2. We distinguish two possible reaction pathways for the first step, depending on pH: reduction of sulphate into sulphur dioxide below pH 2 or into thiosulphate or sulphite + elemental sulphur in the pH range 2-5.

  10. 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.

  11. Sample preparation followed by HPLC under harmless 100% aqueous conditions for determination of oxytetracycline in milk and eggs.

    PubMed

    Furusawa, Naoto

    2004-05-01

    A simple and hazardous chemical-free method for the high-performance liquid chromatographic determination of oxytetracycline (OTC) residues in milk and eggs has been developed. Sample preparation consists in homogenization with an aqueous solution by means of a handheld ultrasonic homogenizer followed by centrifugal ultrafiltration. HPLC is performed with an isocratic aqueous mobile phase and a photodiode array detector. Average recoveries of OTC (0.05, 0.1, and 0.2 microg mL(-1) for milk; 0.1, 0.2, and 0.4 microg mL(-1) for eggs) were > or =84% with relative standard deviations of < or =2.3%. The total time required for the analysis of one sample and LOQs were <30 min and <0.1 microg mL(-1), respectively. In all the processes, no organic solvents or hazardous reagents were used. PMID:15335039

  12. Double torsion fracture mechanics testing of shales under chemically reactive conditions

    NASA Astrophysics Data System (ADS)

    Chen, X.; Callahan, O. A.; Holder, J. T.; Olson, J. E.; Eichhubl, P.

    2015-12-01

    Fracture properties of shales is vital for applications such as shale and tight gas development, and seal performance of carbon storage reservoirs. We analyze the fracture behavior from samples of Marcellus, Woodford, and Mancos shales using double-torsion (DT) load relaxation fracture tests. The DT test allows the determination of mode-I fracture toughness (KIC), subcritical crack growth index (SCI), and the stress-intensity factor vs crack velocity (K-V) curves. Samples are tested at ambient air and aqueous conditions with variable ionic concentrations of NaCl and CaCl2, and temperatures up to 70 to determine the effects of chemical/environmental conditions on fracture. Under ambient air condition, KIC determined from DT tests is 1.51±0.32, 0.85±0.25, 1.08±0.17 MPam1/2 for Marcellus, Woodford, and Mancos shales, respectively. Tests under water showed considerable change of KIC compared to ambient condition, with 10.6% increase for Marcellus, 36.5% decrease for Woodford, and 6.7% decrease for Mancos shales. SCI under ambient air condition is between 56 and 80 for the shales tested. The presence of water results in a significant reduction of the SCI from 70% to 85% compared to air condition. Tests under chemically reactive solutions are currently being performed with temperature control. K-V curves under ambient air conditions are linear with stable SCI throughout the load-relaxation period. However, tests conducted under water result in an initial cracking period with SCI values comparable to ambient air tests, which then gradually transition into stable but significantly lower SCI values of 10-20. The non-linear K-V curves reveal that crack propagation in shales is initially limited by the transport of chemical agents due to their low permeability. Only after the initial cracking do interactions at the crack tip lead to cracking controlled by faster stress corrosion reactions. The decrease of SCI in water indicates higher crack propagation velocity due to

  13. 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.

  14. Chemical evolution: The mechanism of the formation of adenine under prebiotic conditions

    PubMed Central

    Roy, Debjani; Najafian, Katayoun; von Ragué Schleyer, Paul

    2007-01-01

    Fundamental building blocks of life have been detected extraterrestrially, even in interstellar space, and are known to form nonenzymatically. Thus, the HCN pentamer, adenine (a base present in DNA and RNA), was first isolated in abiogenic experiments from an aqueous solution of ammonia and HCN in 1960. Although many variations of the reaction conditions giving adenine have been reported since then, the mechanistic details remain unexplored. Our predictions are based on extensive computations of sequences of reaction steps along several possible mechanistic routes. H2O- or NH3-catalyzed pathways are more favorable than uncatalyzed neutral or anionic alternatives, and they may well have been the major source of adenine on primitive earth. Our report provides a more detailed understanding of some of the chemical processes involved in chemical evolution, and a partial answer to the fundamental question of molecular biogenesis. Our investigation should trigger similar explorations of the detailed mechanisms of the abiotic formation of the remaining nucleic acid bases and other biologically relevant molecules. PMID:17951429

  15. Experimental aqueous alteration of the Allende meteorite under oxidizing conditions: Constraints on asteroidal alteration

    NASA Astrophysics Data System (ADS)

    Jones, Catherine L.; Brearley, Adrian J.

    2006-02-01

    We have performed an experimental study of the aqueous alteration of the Allende CV3 carbonaceous chondrite under highly oxidizing conditions, in order to examine the alteration behavior of Allende's anhydrous mineralogy. The experiments were carried out at temperatures of 100, 150, and 200 °C, for time periods between 7 and 180 days, with water/rock ratios ranging from 1:1 to 9:1. Uncrushed cubes of Allende were used so that the spatial relationships between reactant and product phases could be examined in detail. Scanning electron microscope studies show that in all the experiments, even those of short duration (7 days), soluble salts of Ca and Mg (CaSO 4, CaCO 3, and MgSO 4) precipitated on the sample surface, indicating that these elements are rapidly mobilized during alteration. In addition, iron oxides and hydroxides formed on the sample surfaces. The sulfates, carbonates, and the majority of the iron-bearing secondary minerals are randomly distributed over the surface of samples. In some instances the iron oxides and hydroxides are constrained to the boundaries of altering mineral grains. Transmission electron microscope studies show that the FeO-rich olivine in the interior of the samples has altered to form interlayered serpentine/saponite and Fe-oxyhydroxides. The degree of alteration increases significantly with increasing water/rock ratio, and to a lesser extent with increasing duration of heating. The serpentine/saponite forms both by direct replacement of the olivine in crystallographically oriented intergrowths, and by recrystallization of an amorphous Si-rich phase that precipitates in pore space between the olivine grains. The alteration assemblage bears many similarities to those found in altered carbonaceous chondrites, although in detail there are important differences, which we attribute to (a) the relatively high temperatures of our experiments and (b) comparatively short reaction times compared with the natural examples. In terms of mineral

  16. 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...

  17. 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.

  18. 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 ...

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Immiscible Hydrocarbon and Aqueous Fluids Under Subduction Zone Conditions and Implications for the Deep Carbon Cycle

    NASA Astrophysics Data System (ADS)

    Huang, F.; Daniel, I.; Cardon, H.; Montagnac, G.; Sverjensky, D. A.

    2015-12-01

    Subducting slabs recycle rocks into the deep Earth releasing fluids which may cause partial melting and possible oxidation of the mantle wedge. Recent theoretical studies1 indicate that at pressures greater than about 3.0 GPa these fluids could contain high concentrations of organic and inorganic C-species with a wide range of C-oxidation states at equilibrium. If so, such fluids could play an important role in the deep carbon cycle, including the formation of diamond. However, direct experimental observations of the speciation in the fluids are needed. We studied 1.0 M aqueous Na-formate and 1.0 M Na-acetate solutions in the diamond anvil cell using Raman spectroscopy at 300 ºC and 3.0 GPa for up to 60 hours. Our preliminary results indicate that formate rapidly decomposed to bicarbonate/carbonate species and methane, with no detectable H2. Acetate decomposed much more slowly. Within the first two hours of heating, crystals of Na2CO3 precipitated in the fluid, and kept growing while immiscible droplets of hydrocarbon appeared and persisted throughout the experiments at elevated temperature and pressure. In the aqueous fluid, acetate and HCO3- were present during the first 6 hours, and then CO32- and acetate after 20 hours of heating. The final HCO3- /CO32- ratio was constant indicating a constant pH. This is the first in situ observation of persistent immiscible fluid hydrocarbons formed from an aqueous precursor at upper mantle pressures. Our results suggest that Earth's subduction zone fluids at high pressures might involve fluid hydrocarbon species as well as inorganic and organic aqueous C-species, which considerably broadens the picture of deep carbon sources, cycles and sinks. [1] Sverjensky et at. (2014), Nat. Geosci. 7, 909-913.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Dermal uptake of 18 dilute aqueous chemicals: in vivo disappearance-method measures greatly exceed in vitro-based predictions.

    PubMed

    Bogen, Kenneth T

    2013-07-01

    Average rates of total dermal uptake (Kup ) from short-term (e.g., bathing) contact with dilute aqueous organic chemicals (DAOCs) are typically estimated from steady-state in vitro diffusion-cell measures of chemical permeability (Kp ) through skin into receptor solution. Widely used ("PCR-vitro") methods estimate Kup by applying diffusion theory to increase Kp predictions made by a physico-chemical regression (PCR) model that was fit to a large set of Kp measures. Here, Kup predictions for 18 DAOCs made by three PCR-vitro models (EPA, NIOSH, and MH) were compared to previous in vivo measures obtained by methods unlikely to underestimate Kup . A new PCR model fit to all 18 measures is accurate to within approximately threefold (r = 0.91, p < 10(-5) ), but the PCR-vitro predictions (r > 0.63) all tend to underestimate the Kup measures by mean factors (UF, and p value for testing UF = 1) of 10 (EPA, p < 10(-6) ), 11 (NIOSH, p < 10(-8) ), and 6.2 (MH, p = 0.018). For all three PCR-vitro models, log(UF) correlates negatively with molecular weight (r(2) = 0.31 to 0.84, p = 0.017 to < 10(-6) ) but not with log(vapor pressure) as an additional predictor (p > 0.05), so vapor pressure appears not to explain the significant in vivo/PCR-vitro discrepancy. Until this discrepancy is explained, careful in vivo measures of Kup should be obtained for more chemicals, the expanded in vivo database should be compared to in vitro-based predictions, and in vivo data should be considered in assessing aqueous dermal exposure and its uncertainty. PMID:23051616

  10. Transformations of biomass-derived platform molecules: from high added-value chemicals to fuels via aqueous-phase processing.

    PubMed

    Serrano-Ruiz, Juan Carlos; Luque, Rafael; Sepúlveda-Escribano, Antonio

    2011-11-01

    Global warming issues and the medium-term depletion of fossil fuel reserves are stimulating researchers around the world to find alternative sources of energy and organic carbon. Biomass is considered by experts the only sustainable source of energy and organic carbon for our industrial society, and it has the potential to displace petroleum in the production of chemicals and liquid transportation fuels. However, the transition from a petroleum-based economy to one based on biomass requires new strategies since the petrochemical technologies, well-developed over the last century, are not valid to process the biomass-derived compounds. Unlike petroleum feedstocks, biomass derived platform molecules possess a high oxygen content that gives them low volatility, high solubility in water, high reactivity and low thermal stability, properties that favour the processing of these resources by catalytic aqueous-phase technologies at moderate temperatures. This tutorial review is aimed at providing a general overview of processes, technologies and challenges that lie ahead for a range of different aqueous-phase transformations of some of the key biomass-derived platform molecules into liquid fuels for the transportation sector and related high added value chemicals. PMID:21713268

  11. 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

  12. 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

  13. 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.

  14. 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...

  15. Solvent Effects in Chemical Processes. Water-Assisted Proton Transfer Reaction of Pterin in Aqueous Environment

    NASA Astrophysics Data System (ADS)

    Jaramillo, Paula; Coutinho, Kaline; Canuto, Sylvio

    2009-09-01

    Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for the isolated pterin by quantum mechanical second-order Møller-Plesset perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier. The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case, the free energy barrier is only 6.7 kcal/mol and the calculated relative Gibbs free energy for the two tautomers is -11.2 kcal/mol. This value is used to calculate the pKa value of 8.2 ± 0.6 that is in excellent agreement with the experimental result of 7.9.

  16. 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

  17. 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.

  18. ROS Initiated Oxidation of Dopamine under Oxidative Stress Conditions in Aqueous and Lipidic Environments

    PubMed Central

    2011-01-01

    Dopamine is known to be an efficient antioxidant and to protect neurocytes from oxidative stress by scavenging free radicals. In this work, we have carried out a systematic quantum chemistry and computational kinetics study on the reactivity of dopamine toward hydroxyl (•OH) and hydroperoxyl (•OOH) free radicals in aqueous and lipidic simulated biological environments, within the density functional theory framework. Rate constants and branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the reactivity of dopamine toward hydroxyl radicals, in water at physiological pH, the main mechanism of the reaction is proposed to be the sequential electron proton transfer (SEPT), whereas in the lipidic environment, hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways contribute almost equally to the total reaction rate. In both environments, dopamine reacts with hydroxyl radicals at a rate that is diffusion-controlled. Reaction with the hydroperoxyl radical is much slower and occurs only by abstraction of any of the phenolic hydrogens. The overall rate coefficients are predicted to be 2.23 × 105 and 8.16 × 105 M–1 s–1, in aqueous and lipidic environment, respectively, which makes dopamine a very good •OOH, and presumably •OOR, radical scavenger. PMID:21919526

  19. 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

  20. Chemical characterization of the main secondary organic aerosol (SOA) products formed through aqueous-phase photonitration of guaiacol

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    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 in the atmospheric 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 low-volatility SOA 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 H2O2 and nitrite. The formed guaiacol reaction products were concentrated by using solid-phase extraction (SPE) and then purified by means of semi-preparative high-performance liquid chromatography (HPLC). The fractionated individual compounds were isolated as pure solids and further analyzed with liquid-state 1H, 13C and 2D 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 UV and visible light, 4,6DNG could be an important constituent of atmospheric "brown" carbon, especially in regions affected by biomass burning.

  1. Oxidation of 1,4-dichloro-2-butene by aqueous sodium hypochlorite under phase transfer conditions

    SciTech Connect

    Grigoryan, G.S.; Karoyan, I.L.; Malkhasyan, A.Ts.; Martirosyan, G.T.; Artamkina, G.A.; Beletskaya, I.P.

    1987-11-10

    In the industrial process for the production of chloroprene from butadiene, the problem of reducing the organic impurities in the waste water to 2000 mg/liter has not yet been solved. A method has been patented for the oxidation of organic compounds by sodium hypochlorite at high temperatures and high pressure but this method is limited by the oxidation of soluble organic compounds. The oxidation of 1,4-dichloro-2-butene by aqueous sodium hypochlorite was studied. A sharp increase in the reaction rate was found in the presence of phase transfer catalysts and surfactants. The involvement of oxygen as a cooxiant and the effect of surfactants on the absorption of atmospheric oxygen by the reaction system were demonstrated.

  2. 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.

  3. Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H₂ evolution under fully aqueous conditions.

    PubMed

    Andreiadis, Eugen S; Jacques, Pierre-André; Tran, Phong D; Leyris, Adeline; Chavarot-Kerlidou, Murielle; Jousselme, Bruno; Matheron, Muriel; Pécaut, Jacques; Palacin, Serge; Fontecave, Marc; Artero, Vincent

    2013-01-01

    The viability of a hydrogen economy depends on the design of efficient catalytic systems based on earth-abundant elements. Innovative breakthroughs for hydrogen evolution based on molecular tetraimine cobalt compounds have appeared in the past decade. Here we show that such a diimine-dioxime cobalt catalyst can be grafted to the surface of a carbon nanotube electrode. The resulting electrocatalytic cathode material mediates H(2) generation (55,000 turnovers in seven hours) from fully aqueous solutions at low-to-medium overpotentials. This material is remarkably stable, which allows extensive cycling with preservation of the grafted molecular complex, as shown by electrochemical studies, X-ray photoelectron spectroscopy and scanning electron microscopy. This clearly indicates that grafting provides an increased stability to these cobalt catalysts, and suggests the possible application of these materials in the development of technological devices. PMID:23247177

  4. Experimental and Quantum Chemical Calculations of Imidazolium Appended Naphthalene Hybrid in Different Biomimicking Aqueous Interfaces.

    PubMed

    Yenupuri, Tej Varma; Mydlova, Lucia; Agarwal, Devesh S; Sharma, Ritika; Sakhuja, Rajeev; Makowska-Janusik, Malgorzata; Pant, Debi D

    2016-08-25

    The effect of solvent polarity and micellar headgroup on a newly designed imidazolium based ionic liquid (IL) conjugated with naphthalene, 1,2-dimethyl-3-((6-(octyloxy)naphthalen-2-yl)methyl)-1H-imidazol-3-ium chloride (IN-O8-Cl), was studied using steady state and time-resolved fluorescence techniques. We observed that the dipole moment in the excited state is remarkably higher than the ground state. The effect of micellar surface charge on the photophysics of IN-O8-Cl in aqueous phase at room temperature was investigated. Formation of premicellar aggregates in sodium dodecylsulfate (SDS) was perceived; further the microenvironment of IN-O8-Cl was examined using steady-state fluorescence spectroscopy. Micropolarity of the micellar environment of SDS was found to be lower than that of cetyltrimethylammonium bromide (CTAB) and triton X-100 (TX100) following the order SDS < TX-100 < CTAB. The binding constant (Kb) and edge excitation red shift (EERS) from the emission maximum suggest that the probe binds strongly to the micelles. Multiexponential behavior was observed in time-resolved fluorescence lifetime studies in all micellar environments. We have observed an increase in rotational correlation time as we move from pure aqueous phase to solution containing surfactants of different head charge. Varieties of spectral parameters were used to justify the region in which the probe is present. The experimentally obtained dipole moment data were justified and explained by the DFT calculations of the electronic properties of IN-O8-Cl molecules in gas phase and in selected solvents. PMID:27486828

  5. Chemical effects induced by gamma-irradiation in solid and in aqueous methanol solutions of 4-iodophenol

    NASA Astrophysics Data System (ADS)

    Mahfouz, R. M.; Siddiqui, M. R. H.; Al-Wassil, A. I.; Al-Resayes, S. I.; Al-Otaibi, A. M.

    2005-05-01

    The present work is a study on radiolyses of 4-iodophenol in aqueous methanol solutions. The radiolysis products are separated and identified using spectrophotometric and chromatographic techniques. The radiolytic products (I-2, I- and IO3-) formed in aerated solutions at room temperature were identified and the yields are investigated as a function of absorbed gamma-ray dose. The formation of I-2 is mainly dependent on the acidity of solution and produced via the pathway of secondary free radical reactions. Aromatic products of lower and higher molecular weight than the corresponding investigated compound were analysed and separated by HPLC. The results have been discussed in view of mechanisms based on free radicals and ion-molecule interactions. The chemical effects induced by gamma-irradiation in solid 4-iodophenol have also been investigated and the degradation products were identified in solid state by NMR, GC/MS experiments and HPLC after dissolution in aqueous methanol. The results were evaluated and compared with radiolysis data.

  6. 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.

  7. 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.

  8. 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

  9. Simulation of gas absorption with chemical reaction: The selective removal of hydrogen sulfide by aqueous methyldiethanolamine in packed columns

    SciTech Connect

    Lindner, J.R.

    1988-01-01

    The design of separation devices, particularly for solvent-based selective removal of H{sub 2}S from CO{sub 2}, requires an accurate mathematical model. Unfortunately, this requirement for high accuracy is often in conflict with the need for efficient computation. The addition of more and more complicated analyses, such as a move from Henry's law to a method incorporating gas and liquid activities for computing vapor liquid equilibria, may give a more accurate solution, but only at the cost of decreased computational efficiency. The efforts in this work have been directed toward two goals. The first was to develop an accurate mathematical model for the aqueous methyldiethanolamine (MDEA) system. The steady-state packed column model developed in this work has been tested with data from Schubert (1988) to verify its accuracy. The second goal was to modify the model to improve its computational efficiency. Areas such as vapor-liquid equilibrium calculations, flow hydrodynamics, and thermal effects were examined to determine what simplifications could be made, and how these simplifications affected both the accuracy and the efficiency of the model. The result of this effort is a mathematical model for multicomponent chemical absorption in a continuous contactor that balances computation efficiency with rigorous physical and chemical treatment. This model is useful not only for the analysis of the MDEA-H{sub 2}S-CO{sub 2} system, but the same framework also could be applied to other chemical absorption systems.

  10. 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.

  11. 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.

  12. NMR chemical shift analysis of the conformational transition between the monomer and tetramer of melittin in an aqueous solution.

    PubMed

    Miura, Yoshinori

    2016-05-01

    It is known that melittin in an aqueous solution undergoes a conformational transition between the monomer and tetramer by variation in temperature. The transition correlates closely with isomers of the proline residue; monomeric melittin including a trans proline peptide bond (trans-monomer) is involved directly in the transition, whereas monomeric melittin having a cis proline peptide bond (cis-monomer) is virtually not. The transition has been explored by using nuclear magnetic resonance spectroscopy in order to clarify the stability of the tetrameric conformation and the cooperativity of the transition. In the light of temperature dependence of chemical shifts of resonances from the isomeric monomers, we qualitatively estimate the temperature-, salt-, and concentration-dependence of the relative equilibrium populations of the trans-monomer and tetramer, and show that the tetramer has a maximum conformational stability at 30-45 °C and that the transition cooperativity is very low. PMID:26658745

  13. Exploration of interactions between bioactive solutes and vitamin B9 in aqueous medium by physico-chemical contrivances

    NASA Astrophysics Data System (ADS)

    Nath Roy, Mahendra; Chakraborti, Palash; Ekka, Deepak

    2014-09-01

    Molecular interaction prevailing in α-amino acids (glycine, L-alanine, L-valine) and aqueous solution of folic acid (FA) has been reported by physico-chemical properties as density (ρ), viscosity (η), refractive index (nD) and ultrasonic speed (u) at 298.15 K. The extent of interaction (solute-solvent interaction) is expressed in terms of the limiting apparent molar volume (φ0V), viscosity B-coefficient, molar refraction (RM) and limiting apparent molar adiabatic compressibility (φ0K). The trends in transfer volumes, Δφ0V, have been interpreted in terms of solute-cosolute interactions on the basis of a co-sphere overlap model. The role of the cosolute (FA), and the contribution of solute-solute and solute-solvent interactions to the solution complexes, has also been analysed through the derived properties.

  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. 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

  16. 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

  17. 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...

  18. 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...

  19. 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.

  20. 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

  1. 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

    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.

  2. '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...

  3. "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...

  4. Measurements of aerosol chemical composition in boreal forest summer conditions

    NASA Astrophysics Data System (ADS)

    ńijälä, M.; Junninen, H.; Ehn, M.; Petäjä, T.; Vogel, A.; Hoffmann, T.; Corrigan, A.; Russell, L.; Makkonen, U.; Virkkula, A.; Mäntykenttä, J.; Kulmala, M.; Worsnop, D.

    2012-04-01

    Boreal forests are an important biome, covering vast areas of the northern hemisphere and affecting the global climate change via various feedbacks [1]. Despite having relatively few anthropogenic primary aerosol sources, they always contain a non-negligible aerosol population [2]. This study describes aerosol chemical composition measurements using Aerodyne Aerosol Mass Spectrometer (C-ToF AMS, [3]), carried out at a boreal forest area in Hyytiälä, Southern Finland. The site, Helsinki University SMEAR II measurement station [4], is situated at a homogeneous Scots pine (Pinus sylvestris) forest stand. In addition to the station's permanent aerosol, gas phase and meteorological instruments, during the HUMPPA (Hyytiälä United Measurements of Photochemistry and Particles in Air) campaign in July 2010, a very comprehensive set of atmospheric chemistry measurement instrumentation was provided by the Max Planck Institute for chemistry, Johannes Gutenberg-University, University of California and the Finnish Meteorological institute. In this study aerosol chemical composition measurements from the campaign are presented. The dominant aerosol chemical species during the campaign were the organics, although periods with elevated amounts of particulate sulfates were also seen. The overall AMS measured particle mass concentrations varied from near zero to 27 μg/m observed during a forest fire smoke episode. The AMS measured aerosol mass loadings were found to agree well with DMPS derived mass concentrations (r2=0.998). The AMS data was also compared with three other aerosol instruments. The Marga instrument [5] was used to provide a quantitative semi-online measurement of inorganic chemical compounds in particle phase. Fourier Transform Infrared Spectroscopy (FTIR) analysis was performed on daily filter samples, enabling the identification and quantification of organic aerosol subspecies. Finally an Atmospheric Pressure Chemical Ionization Ion Trap Mass Spectrometer (APCI

  5. Ultrasonic relaxation and fast chemical kinetics of some carbohydrate aqueous solutions

    SciTech Connect

    Behrends, R. |; Cowman, M.K.; Majewski, J.; Petrucci, S.; Eggers, F.; Richmann, K.H.; Eyring, E.M.; Riech, M.; Kaatze, U.

    1997-03-05

    Molecular relaxation properties of the monosaccharides (a) D-glucose, (b) methyl {beta}-D-glucopyranoside, (c) methyl {alpha}-D-mannopyranoside, (d) D-xylose, (e) D-arabinose, (f) methyl {beta}-D-xylopyranoside, (g) methyl {beta}-D-arabinopyranoside, (h) methyl {alpha}-L-(6-deoxy)mannopyranoside, and (i) 1,6-anhydro-{beta}-D-glucopyranoside, all in aqueous solution, have been studied using broad band ultrasonic spectrometry in the frequency range 0.2-2000 MHz. Ultrasonic excess absorption with relaxation characteristics near 80 MHz was found for glucose and the methyl glucosides of D-glucose and D-mannose, but no relaxation process was detected for the other monosaccharides in the same frequency range. From structural aspects it is deduced that the most likely process causing the observed relaxation is the rotation of the exocyclic -CH{sub 2}OH group, placing rotational isomerization on the nanosecond time scale. Relaxation parameters for D-glucose and methyl {beta}-D-glucopyranoside solutions were further investigated as a function of concentration and temperature, in order to confirm the assignment of the relaxation process, and to determine some of its thermodynamic and kinetic parameters. 19 refs., 7 figs., 1 tab.

  6. [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

  7. Sonochemical degradation of perfluorinated chemicals in aqueous film-forming foams.

    PubMed

    Rodriguez-Freire, Lucia; Abad-Fernández, Nerea; Sierra-Alvarez, Reyes; Hoppe-Jones, Christiane; Peng, Hui; Giesy, John P; Snyder, Shane; Keswani, Manish

    2016-11-01

    Aqueous film-forming foams (AFFFs) are complex mixtures containing 1-5% w/w fluorocarbons (FCs). Here, we have investigated degradation of two commercial AFFF formulations, 3M and Ansul, using sound field at 500kHz and 1MHz, with varying initial concentrations ranging from 200 to 930× dilution. The foams were readily degraded by 1MHz, with percentage of defluorination ranging from 11.1±1.4% (200× dilution of 3M) to 47.1±5.8% (500× dilution of Ansul). Removal of total organic carbon (TOC) ranged from 16.0±1.4% (200× dilution Ansul) to 39.0±7.2% (500× dilution Ansul). Degradation of AFFF was affected by sound frequency with rates of defluorination 10-fold greater when the frequency was 1MHz than when it was 500kHz. Mineralization of TOC was 1.5- to 3.0-fold greater under 1MHz than 500kHz. Rate of fluoride release was 60% greater for the greatest initial concentration of FC in Ansul compared to the least initial concentration. While the rate of mineralization of AFFF was directly proportional to the initial concentration of Ansul, that was not the case for 3M, where the rates of mineralization were approximately the same for all three initial concentrations. Results of the study demonstrate that sonolysis is a promising technology to effectively treat AFFFs. PMID:27295064

  8. Pyrite oxidation by hexavalent chromium: investigation of the chemical processes by monitoring of aqueous metal species.

    PubMed

    Demoisson, Frédéric; Mullet, Martine; Humbert, Bernard

    2005-11-15

    Pyrite, an iron sulfide, occurs in many soils and sediments, making it an important natural reductant of toxic metal pollutants. This study investigated the processes leading to aqueous Cr(VI) reduction by pyrite in a closed thermostated (25 +/- 0.1 degrees C) system and under an argon atmosphere. Synthetic pyrite suspensions were reacted with a range of Cr(VI) solutions from 0 to 7 x 10(-4) M and at pH 2-8. Metal species concentrations were continuously monitored during a period lasting approximately 20 h. Preliminary experiments carried out in acidic media without Cr(VI) have shown that some pyrite dissolution occurred. Then, metal species concentration changes with time during pyrite oxidation by Cr(VI) solutions exhibited two distinct trends depending on the complete or incomplete Cr(VI) removal. As long as chromate existed in solution, the Cr-(Ill) to Fe(lIl) ratio was found to be an effective parameter to investigate the pyrite reaction stoichiometry with Cr(VI). Experimental values close to 2 suggest that sulfur compounds with oxidation states between 0 and 2 should be formed during pyrite oxidation by Cr(VI). If Cr(VI) was completely reduced from solution, then the pyrite oxidation by Fe(lll) ions took place to generate ferrous ions. PMID:16323772

  9. 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.

  10. 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.

  11. 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)

  12. 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.

  13. Charting the known chemical space for non-aqueous lithium-air battery electrolyte solvents.

    PubMed

    Husch, Tamara; Korth, Martin

    2015-09-21

    Li-air batteries are very promising candidates for powering future mobility, but finding a suitable electrolyte solvent for this technology turned out to be a major problem. We present a systematic computational investigation of the known chemical space for possible Li-air electrolyte solvents. It is shown that the problem of finding better Li-air electrolyte solvents is not only - as previously suggested - about maximizing Li(+) and O2(-) solubilities, but also about finding the optimal balance of these solubilities with the viscosity of the solvent. As our results also show that trial-and-error experiments on known chemicals are unlikely to succeed, full chemical sub-spaces for the most promising compound classes are investigated, and suggestions are made for further experiments. The proposed screening approach is transferable and robust and can readily be applied to optimize electrolytes for other electrochemical devices. It goes beyond the current state-of-the-art both in width (considering the number of compounds screened and the way they are selected), as well as depth (considering the number and complexity of properties included). PMID:26256846

  14. Charting the known chemical space for non-aqueous lithium-air battery electrolyte solvents

    NASA Astrophysics Data System (ADS)

    Husch, Tamara; Korth, Martin

    The Li-Air battery is a very promising candidate for powering future mobility, but finding a suitable electrolyte solvent for this technology turned out to be a major problem. We present a systematic computational investigation of the known chemical space for possible Li-Air electrolyte solvents. It is shown that the problem of finding better Li-Air electrolyte solvents is not only - as previously suggested - about maximizing Li+ and O2- solubilities, but about finding the optimal balance of these solubilities with the viscosity of the solvent. As our results also show that trial-and-error experiments on known chemicals are unlikely to succeed, full chemical sub-spaces for the most promising compound classes are investigated, and suggestions are made for further experiments. The proposed screening approach is transferable and robust and can readily be applied to optimize electrolytes for other electrochemical devices. It goes beyond the current state-of-the-art both in width (considering the number of compounds screened and the way they are selected), as well as depth (considering the number and complexity of properties included).

  15. Quantum chemical and molecular dynamics study of the coordination of Th(IV) in aqueous solvent.

    PubMed

    Réal, Florent; Trumm, Michael; Vallet, Valérie; Schimmelpfennig, Bernd; Masella, Michel; Flament, Jean-Pierre

    2010-12-01

    In this work, we investigate the solvation of tetravalent thorium Th(IV) in aqueous solution using classical molecular dynamics simulations at the 10 ns scale and based on polarizable force-field approaches, which treat explicitly the covalent character of the metal-water interaction (and its inherent cooperative character). We have carried out a thorough analysis of the accuracy of the ab initio data that we used to adjust the force-field parameters. In particular, we show that large atomic basis sets combined with wave function-based methods (such as the MP2 level) have to be preferred to density functional theory when investigating Th(IV)/water aggregates in gas phase. The information extracted from trajectories in solution shows a well-structured Th(IV) first hydration shell formed of 8.25 ± 0.2 water molecules and located at about 2.45 ± 0.02 Å and a second shell of 17.5 ± 0.5 water molecules at about 4.75 Å. Concerning the first hydration sphere, our results correspond to the lower bounds of experimental estimates (which range from 8 to 12.7); however, they are in very good agreement with the average of existing experimental data, 2.45 ± 0.02 Å. All our results demonstrate the predictable character of the proposed approach, as well as the need of accounting explicitly for the cooperative character of charge-transfer phenomena affecting the Th(IV)/water interaction to build up reliable and accurate force-field approaches devoted to such studies. PMID:21070066

  16. Polyurethane foam loaded with sodium dodecylsulfate for the extraction of 'quat' pesticides from aqueous medium: Optimization of loading conditions.

    PubMed

    Vinhal, Jonas O; Lima, Claudio F; Cassella, Ricardo J

    2016-09-01

    The cationic herbicides paraquat, diquat and difenzoquat are largely used in different cultures worldwide. With this, there is an intrinsic risk of environmental contamination when these herbicides achieve natural waters. The goal of this work was to propose a novel and low-cost sorbent for the removal of the cited herbicides from aqueous medium. The proposed sorbent was prepared by loading polyurethane foam with sodium dodecylsulfate. The influence of several parameters (SDS concentration, HCl concentration and shaking time) on the loading process was investigated. The results obtained in this work demonstrated that all studied variables influenced the loading process, having significant effect on the extraction efficiency of the resulted PUF-SDS. At optimized conditions, the PUF was loaded by shaking 200mg of crushed foam with 200mL of a solution containing 5.0×10(-3)molL(-1) SDS and 0.25molL(-1) HCl, for 30min. The obtained PUF-SDS was efficient for removing the three herbicides from aqueous medium, achieving extraction percentages higher than 90%. The sorption process followed a pseudo second-order kinetics, which presented excellent predictive capacity of the amount of herbicide retained with time. PMID:27213562

  17. Hyphenation of sequential- and flow injection analysis with FTIR-spectroscopy for chemical analysis in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Lendl, B.; Schindler, R.; Kellner, R.

    1998-06-01

    A survey of the principles of sequential (SIA)-and flow injection analysis (FIA) systems with FTIR spectroscopic detection is presented to introduce these hyphenations as powerful techniques for performing chemical analysis in aqueous solution. The strength of FIA/SIA-FTIR systems lies in the possibility to perform highly reproducible and automated sample manipulations such as sample clean-up and/or chemical reactions prior to spectrum acquisition. It is shown that the hyphenation of FIA/SIA systems with an FTIR spectrometer enhances the problem solving capabilities of the FTIR spectrometer as also parameters which can not be measured directly (e.g. enzyme activities) can be determined. On the other hand application of FTIR spectroscopic detection in FIA or SIA is also of advantage as it allows to shorten conventional analysis procedures (e.g. sucrose or phosphate analysis) or to establish and apply a multivariate calibration model for simultaneous determinations (e.g. glucose, fructose and sucrose analysis). In addition to these examples two recent instrumental developments in miniaturized FIA/SIA-FTIR systems, a μ-Flow through cell based on IR fiber optics and a micromachined SI-enzyme reactor are presented in this paper.

  18. 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...

  19. 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.

  20. 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,…

  1. 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

  2. X-ray absorption spectroscopy studies of ionic association in aqueous solutions of zinc bromide from normal to critical conditions

    NASA Astrophysics Data System (ADS)

    Simonet, V.; Calzavara, Y.; Hazemann, J. L.; Argoud, R.; Geaymond, O.; Raoux, D.

    2002-08-01

    Ion-pairing and dehydration phenomena occurring in ZnBr2 aqueous solutions from normal to critical T, P conditions were investigated by x-ray absorption spectroscopy. The respective influences of temperature, pressure, and concentration were studied. The evolution of the density of solute ions, probed by the height of the absorption edge, allowed us to get information on phase diagrams and salt precipitation. The average structural evolution deduced from extended x-ray absorption fine structure was related to the formation of complexes identified from x-ray absorption near edge structure analysis. Consequently, in noncritical conditions, an increase of temperature or concentration produces dehydration and ion-pairing, while a rise of pressure destroys the ion-pairs. In contrast, concentration and pressure have weaker effects on the local order in high P, T conditions. Moreover, ion pairing formation is found not to be specifically enhanced when the fluid is close to supercritical conditions as it also occurs at lower temperatures. In a discussion, the modifications induced by a variation of the different structural parameters are related to the macroscopic properties of the solvent.

  3. 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

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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%.

  11. 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.

  12. Physico-chemical aspects of solubility of myosin in aqueous media.

    PubMed

    Das, M; Chattoraj, D K

    1989-10-01

    Solubility of fish (Labio rohita) myosin has been studied at varying temperatures in presence of various inorganic salts like NaCl, KCl, NaBr, Na2SO4, KI, and organic solutes like sucrose and urea. The effect of pH on the solubility has also been studied both in absence and presence of NaCl. Thermal denaturation temperatures of myosin in presence of NaCl, KCl, NaBr and Na2SO4 were found to be 40 degrees, 40 degrees, 45 degrees and 50 degrees C respectively. Thermodynamic parameters like changes in standard free energy (delta G degrees), enthalpy (delta H degrees) and entropy (delta S degrees) for precipitation of myosin from solution phase to gel phase have been evaluated and the physico-chemical aspects have been critically discussed. The average delta G degrees for gel formation varied only between -30 and -40 kJ/mole of myosin, although the nature of solutes, temperature and folding state of protein have been grossly altered. A compensation effect has also been exhibited from the linear plot of average values of delta H degrees against T delta S degrees for various solutes. PMID:2628269

  13. 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

  14. 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.

  15. Optimizing cyanobacteria growth conditions in a sealed environment to enable chemical inhibition tests with volatile chemicals.

    PubMed

    Johnson, Tylor J; Zahler, Jacob D; Baldwin, Emily L; Zhou, Ruanbao; Gibbons, William R

    2016-07-01

    Cyanobacteria are currently being engineered to photosynthetically produce next-generation biofuels and high-value chemicals. Many of these chemicals are highly toxic to cyanobacteria, thus strains with increased tolerance need to be developed. The volatility of these chemicals may necessitate that experiments be conducted in a sealed environment to maintain chemical concentrations. Therefore, carbon sources such as NaHCO3 must be used for supporting cyanobacterial growth instead of CO2 sparging. The primary goal of this study was to determine the optimal initial concentration of NaHCO3 for use in growth trials, as well as if daily supplementation of NaHCO3 would allow for increased growth. The secondary goal was to determine the most accurate method to assess growth of Anabaena sp. PCC 7120 in a sealed environment with low biomass titers and small sample volumes. An initial concentration of 0.5g/L NaHCO3 was found to be optimal for cyanobacteria growth, and fed-batch additions of NaHCO3 marginally improved growth. A separate study determined that a sealed test tube environment is necessary to maintain stable titers of volatile chemicals in solution. This study also showed that a SYTO® 9 fluorescence-based assay for cell viability was superior for monitoring filamentous cyanobacterial growth compared to absorbance, chlorophyll α (chl a) content, and biomass content due to its accuracy, small sampling size (100μL), and high throughput capabilities. Therefore, in future chemical inhibition trials, it is recommended that 0.5g/L NaHCO3 is used as the carbon source, and that culture viability is monitored via the SYTO® 9 fluorescence-based assay that requires minimum sample size. PMID:27196637

  16. 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%.

  17. 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/.

  18. 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

  19. Kirkwood-Buff Integrals for Aqueous Urea Solutions Based upon the Quantum Chemical Electrostatic Potential and Interaction Energies.

    PubMed

    Chiba, Shuntaro; Furuta, Tadaomi; Shimizu, Seishi

    2016-08-11

    Cosolvents, such as urea, affect protein folding and binding, and the solubility of solutes. The modeling of cosolvents has been facilitated significantly by the rigorous Kirkwood-Buff (KB) theory of solutions, which can describe structural thermodynamics over the entire composition range of aqueous cosolvent mixtures based only on the solution density and the KB integrals (KBIs), i.e., the net excess radial distribution functions from the bulk. Using KBIs to describe solution thermodynamics has given rise to a clear guideline that an accurate prediction of KBIs is equivalent to accurate modeling of cosolvents. Taking urea as an example, here we demonstrate that an improvement in the prediction of KBIs comes from an improved reproduction of high-level quantum chemical (QC) electrostatic potential and molecular pairwise interaction energies. This rational approach to the improvement of the KBI prediction stems from a comparison of existing force fields, AMOEBA, and the generalized AMBER force field, as well as the further optimization of the former to enable better agreement with QC interaction energies. Such improvements would pave the way toward a rational and systematic determination of the transferable force field parameters for a number of important small molecule cosolvents. PMID:27434200

  20. 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.

  1. 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.

  2. Corrosion phenomena on alloy 625 in aqueous solutions containing hydrochloric acid and oxygen under subcritical and supercritical conditions

    SciTech Connect

    Boukis, N.; Kritzer, P.

    1997-08-01

    Supercritical Water Oxidation (SCWO) is a very effective process to destroy hazardous aqueous wastes containing organic contaminants. The main target applications in the USA are the destruction of DOD and DOE wastes such as rocket fuels and explosives, warfare agents and organics present in low level radioactive liquid wastes. Alloy 625 is frequently used as reactor material for Supercritical Water Oxidation (SCWO) applications. This is due to the favorable combination of mechanical properties, corrosion resistance, price and availability. Nevertheless, the corrosion of alloy 625 like the corrosion of other Ni-base alloys during oxidation of hazardous organic waste containing chloride proceeds too fast and is a major problem in SCWO applications. In these experiments high pressure, high-temperature resistant tube reactors made of alloy 625 were used as specimens. They were exposed to SCWO conditions, without organics, at temperatures up to 500 C and pressures up to 37 MPa for up to 150 h. Simultaneously, coupons also made from alloy 625 are exposed inside the test tubes. The most important corrosion problem for alloy 625 is pitting and intercrystalline corrosion at temperatures near the critical temperature, i.e. in the preheater and cooling sections of the test tubes. Under certain conditions, stress corrosion cracking appears and leads to premature failure of the test reactors. The corrosion products were insoluble in supercritical water and formed thick layers in the supercritical part of the reactor. Under these layers only minor corrosion occurred. 33 refs.

  3. 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

  4. SIMULATION OF ECOLOGICALLY CONSCIOUS CHEMICAL PROCESSES: FUGITIVE EMISSIONS VERSUS OPERATING CONDITIONS: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-CIN-1531A Mata, T.M., Smith*, R.L., Young*, D., and Costa, C.A.V. "Simulation of Ecologically Conscious Chemical Processes: Fugitive Emissions versus Operating Conditions." Paper published in: CHEMPOR' 2001, 8th International Chemical Engineering Conference, Aveiro, Portu...

  5. 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 ...

  6. 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...

  7. 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.

  8. 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.

  9. Detection of native protein ions in aqueous solution under ambient conditions by electrospray laser desorption/ionization mass spectrometry.

    PubMed

    Shiea, Jentaie; Yuan, Cheng-Hui; Huang, Min-Zong; Cheng, Sy-Chyi; Ma, Ya-Lin; Tseng, Wei-Lung; Chang, Hui-Chiu; Hung, Wen-Chun

    2008-07-01

    Liquid electrospray laser desorption/ionization (ELDI) mass spectrometry allows desorption and ionization of proteins directly from aqueous solutions and biological fluids under ambient conditions. Native protein ions such as those of myoglobin, cytochrome c, and hemoglobin were obtained. A droplet (ca. 5 microL) containing the protein molecules and micrometer-sized particles (e.g., carbon graphite powder) is irradiated with a pulsed UV laser. The laser energy adsorbed by the inert particles is transferred to the surrounding solvent and protein molecules, leading to their desorption; the desorbed gaseous molecules are then postionized within an electrospray (ESI) plume to generate the ESI-like protein ions. With the use of this technique, we detected only the protonated protein ions in various biological fluids (including human tears, cow milk, serum, and bacterial extracts) without interference from their corresponding sodiated or potassiated adduct ions. In addition, we rapidly quantified the levels of glycosylated hemoglobin present in drops of whole blood obtained from diabetic patients without the need of sample pretreatment. PMID:18510347

  10. 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.

  11. 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.

  12. Preliminary investigation of the supply of chemical species to an aqueous solution using a hydrogen-oxygen flame.

    PubMed

    Uchida, Miho; Sogabe, Takahiro; Ikoma, Tadaaki; Okuwakit, Akitsugu

    2005-08-01

    A new method of supplying radical species to aqueous solutions using a hydrogen-oxygen flame is investigated. When a hydrogen-oxygen flame is directed on the surface of an aqueous solution, hydroxyl radicals (*OH) produced in the flame are extracted into the aqueous phase. The presence of *OH in the aqueous solution was confirmed by electron paramagnetic resonance with spin trapping using 5,5-dimethyl-1-pyrroline-N-oxide. The extraction of *OH into the aqueous solution was monitored using a quantitative analysis of hydrogen peroxide (H2O2). The effects of the hydrogen and oxygen gas flow rates, hydrogen/oxygen ratio, and atmosphere on H2O2 formation were studied. When the hydrogen-oxygen flame blew on a phosphate buffer solution (pH 6.7) under an Ar atmosphere, the concentration of H2O2 increased with the blowing time of the flame and the flow rate of hydrogen gas. Under air, nitrate and nitrite ions were formed in the aqueous phase in addition to H2O2, and the H2O2 concentration was lower than that under argon. The application of this new method to an aqueous solution of Cu(II)-ethylenediaminetetraacetic acid (EDTA) caused a remarkable decrease in the concentration of Cu(II)-EDTA and total organic carbon. PMID:16124325

  13. 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

  14. 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

  15. 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

  16. 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

  17. Evaluating Dense Non-Aqueous Phase Liquid Dissolution and Chemical Oxidation in a three-dimensional, bench-scale fracture network

    NASA Astrophysics Data System (ADS)

    Christensen, K.; McCray, J. E.; Schaefer, C.

    2011-12-01

    Dense non-aqueous phase liquid (DNAPL) present in fractured bedrock settings at residual saturation introduces remediation challenges that are dramatically different from porous media settings. Evaluating DNAPL distribution in a field-scale setting is generally impractical, yet DNAPL distribution plays a critical role in the DNAPL dissolution kinetics. This research uses a three-dimensional (3-D), bench-scale network comprised of low-porosity, fractured sandstone to evaluate the dissolution kinetics of tetrachloroethylene (PCE) DNAPL at residual saturation. DNAPL dissolution kinetics were evaluated during ambient groundwater conditions as well as during in situ chemical oxidation (ISCO) in the 3-D fractured sandstone experiment. DNAPL dissolution in the fracture network was evaluated and described using an effective parameter, the bulk mass transfer coefficient (KL). Results from dissolution experiments revealed a positive, statistically significant correlation between KL with DNAPL-water interfacial area and KL with DNAPL saturation. Results of ISCO experiments with potassium permanganate (KMnO4) determined that the formation of reaction products (manganese dioxides and carbon dioxide) likely altered the primary flow paths and decreased effectiveness of the ISCO application in the fracture network. The formation of reaction products was believed to cause flow bypassing and reduce the DNAPL-oxidant contact, which reduced mass transfer rates. The effectiveness of ISCO was improved (over dissolution alone) if the ISCO application was discontinued after an initial period of effective mass removal. The findings of this research indicate that DNAPL dissolution and oxidation effectiveness in a fracture network setting are not directly correlated to aperture size, which was unexpected, but appear to be primarily impacted by flow path variability and heterogeneous DNAPL distribution.

  18. Photoinduced chemical reactions on natural single crystals and synthesized crystallites of mercury(II) sulfide in aqueous solution containing naturally occurring amino acids.

    PubMed

    Pal, Bonamali; Ikeda, Shigeru; Ohtani, Bunsho

    2003-03-10

    Photoirradiation at >300 nm of aqueous suspensions of several natural crystal specimens and synthesized crystallites of mercury(II) sulfide (HgS) induced deaminocyclization of optically active or racemic lysine into pipecolinic acid (PCA) under deaerated conditions. This is the first example, to the best of our knowledge, of photoinduced chemical reactions of natural biological compounds over natural minerals. It was found that the natural HgS crystals had activity higher than those of synthesized ones but lower than those of other sulfides of transition metals, e.g., CdS and ZnS, belonging to the same II-IV chalcogenides. In almost all of the photoreactions, decompostion of HgS occurred to liberate hydrogen sulfide (H(2)S) and Hg(2+), and the latter seemed to have undergone in-situ reductive deposition on HgS as Hg(0) after a certain induction period (24-70 h) during the photoirradiation, as indicated by the darkened color of the suspensions. The formation of PCA, presumably through combination of oxidation of lysine and reduction of an intermediate, cyclic Schiff base, could also be seen after a certain induction time of the Hg(0) formation. This was supported by the fact that the addition of small amount of Hg(2+) (0.5 wt % of HgS) increased the PCA yield by almost 2-fold. We also tried to elucidate certain aspects of the plausible stereochemical reactions in relation to the chiral crystal structure of HgS. Although, in some experiments, slight enantiomeric excess of the product PCA was observed, the excess was below or equal to the experimental error and no other supporting analytical data could not be obtained; we cannot conclude the enantiomeric photoproduction of PCA by the natural chiral HgS specimen. PMID:12611518

  19. 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.

  20. 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

    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.

  1. The chemical stability of L-isoleucine, L-threonine, and L-serine in aqueous solutions of KCl at 298.15 K

    NASA Astrophysics Data System (ADS)

    Roy, Sanjay; Dolui, Bijoy Krishna

    2016-06-01

    The experimental saturated solubilities of L-isoleucine, L-threonine, and L-serine in aqueous mixtures of a KCl solution at 298.15 K are presented in this article. The solubilities are measured by gravimetric method. In the present study the theoretical calculation of the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy, dipole-dipole interaction effect have been computed. The chemical effects of the transfer Gibbs energies for the present amino acids have been obtained by subtracting the cavity effects and dipole-dipole interaction effects from the Δ G t 0 ( i). The stability of the experimental amino acids in aqueous KCl in terms of thermodynamic parameters is explained.

  2. Chemical stability of ecomustine, a new antitumor agent in aqueous and biological media as assessed by high-performance liquid chromatography.

    PubMed

    el Abed, I; Roger, P; Gosse, C; Atassi, G; Gouyette, A

    1991-01-01

    Ecomustine, or CY233 (NSC-609224), is a new water-soluble nitrosoureido sugar derived from acosamine. A high-performance liquid chromatographic assay (HPLC) developed to quantify the unchanged drug in aqueous solutions and biological specimens enabled us to study the chemical stability as a function of pH, light, and temperature. In buffered aqueous solutions, the kinetics of degradation of CY233 is a first-order process. The log k-pH profile demonstrated hydroxide ion-catalyzed solvolysis. The drug is most stable at pH 4, more stable than some other nitrosoureas in 5% glucose (t1/2, 62-67 h) and in 0.9% isotonic saline (t1/2, 25-37 h) solutions. Based on these findings, blood samples should be collected in cold tubes (4 degrees C) containing citrate buffer (pH 4) and all manipulations should be protected from heat and light. PMID:1998985

  3. 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

  4. 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.

  5. 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

  6. Chemical Kinetic Study of Toluene Oxidation Under Premixed and Nonpremixed Conditions

    SciTech Connect

    Costa, I D; Bozzelli, J W; Seiser, R; Pitz, W J; Westbrook, C K; Chen, C -; Fournet, R; Seshadri, K; Battin-Leclerc, F; Billaud, F

    2003-12-10

    A study was performed to elucidate the chemical-kinetic mechanism of combustion of toluene. A detailed chemical-kinetic mechanism for toluene was improved by adding a more accurate description of the phenyl + O{sub 2} reaction channels, toluene decomposition reactions and the benzyl + O reaction. Results of the chemical kinetic mechanism are compared with experimental data obtained from premixed and non-premixed systems. Under premixed conditions, predicted ignition delay times are compared with new experimental data obtained in shock tube. Also, calculated species concentration histories are compared to experimental flow reactor data from the literature. Under non-premixed conditions, critical conditions of extinction and autoignition were measured in strained laminar flows in the counterflow configuration. Numerical calculations are performed using the chemical-kinetic mechanism at conditions corresponding to those in the experiments. Critical conditions of extinction and autoignition are predicted and compared with the experimental data. Comparisons between the model predictions and experimental results of ignition delay times in shock tube, and extinction and autoignition in non-premixed systems show that the chemical-kinetic mechanism predicts that toluene/air is overall less reactive than observed in the experiments. For both premixed and non-premixed systems, sensitivity analysis was used to identify the reaction rate constants that control the overall rate of oxidation in each of the systems considered. Under shock tube conditions, the reactions that influence ignition delay time are H + O{sub 2} chain branching, the toluene decomposition reaction to give an H atom, and the toluene + H abstraction reaction. The reactions that influence autoignition in non-premixed systems involve the benzyl + HO{sub 2} reaction and the phenyl + O{sub 2} reaction.

  7. Sensitive determinations of Cu, Pb, Cd, and Cr elements in aqueous solutions using chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

    PubMed

    Yang, X Y; Hao, Z Q; Li, C M; Li, J M; Yi, R X; Shen, M; Li, K H; Guo, L B; Li, X Y; Lu, Y F; Zeng, X Y

    2016-06-13

    In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was for the first time applied to improve the detection sensitivities of trace heavy metal elements in aqueous solutions. Utilizing chemical replacement effect, heavy metal ions in aqueous solution were enriched on the magnesium alloy surface as a solid replacement layer through reacting with the high chemical activity metallic magnesium (Mg) within 1 minute. Unitary and mixed solutions with Cu, Pb, Cd, and Cr elements were prepared to construct calibration curves, respectively. The CR-SENLIBS showed a much better detection sensitivity and accuracy for both unitary and mixed solutions. The coefficients of determination R2 of the calibration curves were above 0.96, and the LoDs were of the same order of magnitude, i.e., in the range of 0.016-0.386 μg/mL for the unitary solution, and in the range of 0.025-0.420 μg/mL for the mixed solution. These results show that CR-SENLIBS is a feasible method for improving the detection sensitivity of trace element in liquid sample, which definitely provides a way for wider application of LIBS in water quality monitoring. PMID:27410358

  8. 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

  9. 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...

  10. 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