Sample records for aqueous chemical conditions

  1. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

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

  2. Aqueous chemical wash compositions

    SciTech Connect

    Bannister, C.E.

    1987-07-21

    This patent describes an aqueous, substantially unfoamed chemical wash composition having properties making it suitable for use as a pre-flush in well cementing operations and/or for removal of drilling mud from a borehole at a temperature of from about 150/sup 0/F to about 270/sup 0/F, the wash a. being predominantly composed of water, b. containing an active surfactant component comprising a combination of (1) from about 0.1 to about 1.5 weight percent (total weight basis) of a water soluble anionic surfactant; (2) from about 0.1 to about 1.5 weight percent (total weight basis) of a nonionic surfactant; and (3) from about 0.05 to about 0.54 weight percent (total weight basis) of at least one water soluble amphoteric surfactant, and c. having dispersed therein a heterogeneous mixture of distinct particles comprising both a first particulate oil soluble resin which is friable and a second particulate oil soluble resin which is pliable and where the size of the friable resin particles ranges from about 0.5 to about 300 microns and the size of the pliable resin particles ranges from about 0.05 to about 30 microns. The amount of the friable-pliable resin mixture is sufficient to impart effective fluid loss control to the chemical wash composition.

  3. 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

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

    PubMed

    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

  5. 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 (?G) 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 (?G < -3.5 kcal/mol), reversible (?G between +/-3.5 kcal/mol), or unfavorable (?G > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

  6. Aqueous Chemical Solution Deposition of Ferroelectric Thin Films

    Microsoft Academic Search

    M. K. Van Bael; D. Nelis; A. Hardy; D. Mondelaers; K. Van Werde; J. DHaen; G. Vanhoyland; H. Van Den Rul; J. Mullens; L. C. Van Poucke; F. Frederix; D. J. Wouters

    2002-01-01

    Thin films of various ferroelectric multimetal oxides such as (Bi 1 m x La x ) 4 Ti 3 O 12 (BLT), SrBi 2 Ta 2 O 9 (SBT) and PbZr 1 m x Ti x O 3 (PZT) have been prepared by an entirely aqueous chemical solution deposition (CSD) route. Two critical issues related with aqueous CSD have hereby

  7. Classes of Chemical Reactions Reactions in aqueous media

    E-print Network

    Zakarian, Armen

    Classes of Chemical Reactions Reactions in aqueous media · Precipitation reactions · Acid + electrolytes: a substance that conducts an electric current when dissolved in water Acids are donors of H+ (this is a definition) HBr ! H3O+ + Br¯ or HBr ! H+ + Br¯ Equations for Aqueous Ionic Reactions

  8. Explosivity Conditions of Aqueous Solutions and L. Mercury2

    E-print Network

    Paris-Sud XI, Université de

    1 Explosivity Conditions of Aqueous Solutions R. Thiéry1 and L. Mercury2 Revised version February of explosive boiling and gas exsolution of aqueous solutions from a thermodynamic point of view. Indeed, the kinetic nature of these processes, hence their explosivity, can be assessed by considering their relation

  9. Aqueous Alteration and Martian Bulk Chemical Composition

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

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

  10. Chemical cleaning of reverse osmosis and nanofiltration membranes fouled by licorice aqueous solutions

    Microsoft Academic Search

    M. R. Sohrabi; S. S. Madaeni; M. Khosravi; A. M. Ghaedi

    2011-01-01

    The aim of this work was finding optimum cleaning agents and conditions for cleaning reverse osmosis (RO) and nanofiltration (NF) membranes fouled by licorice aqueous solutions. The effect of various chemicals on flux recovery (FR) and resistance removal (RR) of the fouled membranes was investigated. For both membranes the results indicate that a combination of ethylene diamine tetra acetic acid

  11. Chemical Stability of Laponite in Aqueous Media

    E-print Network

    Shweta Jatav; Yogesh M Joshi

    2014-07-06

    In this work stability of Laponite against dissolution in its aqueous dispersions is investigated as a function of initial pH of water before mixing Laponite, and concentration of Laponite. Dissolution of Laponite is quantified in terms of concentration of leached magnesium in the dispersions. Interestingly the solvent pH is observed to play no role in dissolution of Laponite in dispersion over the explored range of 3 to 10. Furthermore, contrary to the usual belief that Laponite dissolves when pH of aqueous dispersion decreases below 9, dissolution of the same is observed even though dispersion pH is above 10 for low concentrations of Laponite (1 and 1.7 mass%). On the other hand, for dispersions having high concentration of Laponite (2.8 mass%) and pH in the similar range (>10) no dissolution is observed. Measurement of ionic conductivity of dispersion shows that concentration of sodium ions in dispersion increases with concentration of Laponite, which appears to have a role in preventing the dissolution of Laponite.

  12. REDEQL.EPAK: AQUEOUS CHEMICAL EQUILIBRIUM COMPUTER PROGRAM

    EPA Science Inventory

    This user's guide is a companion to the previously published report A User's Guide for REDEQL.EPA which explains the use of a computerized chemical equilibrium program for metals and ligands in aqueous systems. Changes in this guide include temperature correction for equilibrium ...

  13. 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...

  14. Physical-chemical conditions of ore deposition

    USGS Publications Warehouse

    Barton, P.B., Jr.

    1981-01-01

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

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

    PubMed

    Mou?ka, Filip; Nezbeda, Ivo; Smith, William R

    2013-09-28

    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. PMID:24089784

  16. 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 temperature than Vo or the Debye-Hückel term and non-ideal behavior is generally suppressed at higher pressures.

  17. Wetting under chemical equilibrium and nonequilibrium conditions

    Microsoft Academic Search

    I. A. Aksay; Carl E. Hoge; Joseph A. Pask

    1974-01-01

    The thermodynamics of a solid-liquid-vapor system both under chemical equilibrium and nonequilibrium conditions, based on the model of Gibbs, is discussed. Under chemical equilibrium conditions, the degree of wetting or nonwetting of a flat and nondeformable solid by the liquid is defined by Young's equation in terms of the static interfacial tensions. Under chemical nonequilibrium conditions, mass transfer across an

  18. Pavlovian conditioning and multiple chemical sensitivity.

    PubMed Central

    Siegel, S; Kreutzer, R

    1997-01-01

    Pavlovian conditioning processes may contribute to some symptoms of multiple chemical sensitivity (MCS). This review summarizes the potential relevance of the literature on conditional taste and olfactory aversions, conditional sensitization, and conditional immunomodulation to understanding MCS. A conditioning-based perspective on MCS suggests novel research and treatment strategies. PMID:9167990

  19. Improving chemical aqueous based intervention methods for microorganism elimination from fresh produce surfaces

    E-print Network

    Puerta-Gomez, Alex Frank

    2006-04-12

    the effectiveness of the chemical aqueous based intervention methods applied. Wettable surfaces (water contact angle < 90°) allowed more bacteria to attach after the washing and H2O2 chemical treatments. Roughness and surface polarity are intrinsic characteristics...

  20. Analyzing Aqueous Solution Imbibition into Shale and the Effects of Optimizing Critical Chemical Additives

    E-print Network

    Wiese, Matthew Michael

    2013-09-29

    ANALYZING AQUEOUS SOLUTION IMBIBITON INTO SHALE AND THE EFFECTS OF OPTIMIZING CRITICAL CHEMICAL ADDITIVES An Undergraduate Research Scholars Thesis by MATTHEW WIESE, SAMMAZO PLAMIN and MAHA QURESHI Submitted to Honors and Undergraduate... 21 APPENDIX A 22 1 ABSTRACT Analyzing Aqueous Solution Imbibition into Shale and the Effects...

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  2. One-step growth of structured ZnO thin films by chemical bath deposition in aqueous ammonia solution

    Microsoft Academic Search

    S M Huang; Z Q Bian; J B Chu; Z A Wang; D W Zhang; X D Li; H B Zhu; Z Sun

    2009-01-01

    Structured ZnO films have been fabricated on soda-lime glass slides at a low temperature (80-85 °C) by a chemical bath deposition method in one step without seed layers. Mixed aqueous solutions of zinc sulfate, ammonia and thiourea were used at alkaline conditions. The influence of the ammonia concentration in the initial solution on the property of the deposited film was

  3. One-step growth of structured ZnO thin films by chemical bath deposition in aqueous ammonia solution

    Microsoft Academic Search

    S M Huang; Z Q Bian; J B Chu; Z A Wang; D W Zhang; X D Li; H B Zhu; Z Sun

    2009-01-01

    Structured ZnO films have been fabricated on soda-lime glass slides at a low temperature (80–85 °C) by a chemical bath deposition method in one step without seed layers. Mixed aqueous solutions of zinc sulfate, ammonia and thiourea were used at alkaline conditions. The influence of the ammonia concentration in the initial solution on the property of the deposited film was

  4. '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...

  5. The Effect of Salt on Protein Chemical Potential Determined by Ternary Diffusion in Aqueous Solutions

    E-print Network

    Annunziata, Onofrio

    The Effect of Salt on Protein Chemical Potential Determined by Ternary Diffusion in Aqueous as a function of salt concentration, (b) compare the behavior of the protein chemical potential for the three salts, which we found to be consistent with the Hofmeister series, and (c) discuss our thermodynamic

  6. Chemical bath deposition of textured ZnO thin films in aqueous\\/ethanolic solution

    Microsoft Academic Search

    Mingsong Wang; Sung Hong Hahn; Jae Seong Kim; Soon Ho Hong; Kee-Kahb Koo; Eui Jung Kim

    2008-01-01

    ZnO thin films have been prepared by chemical bath deposition in aqueous\\/ethanolic solution. The film texture was successfully controlled by varying the volume ratio of water to ethanol. Films consisting of densely oriented nanorod arrays with the c-axis perpendicular to the substrate were fabricated in aqueous solution. The crystals became increasingly tilted as more ethanol was introduced to the solution,

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

    PubMed

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

    2014-09-17

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

  8. [Photo-chemical decomposition of perfluorooctanoic acids in aqueous periodate].

    PubMed

    Cao, Meng-Hua; Wang, Bei-Bei; Zhu, Hu-Di; Tan, Zhen-Ji; Zeng, You-Shi; Wang, Lin-Ling; Yuan, Song-Hu; Chen, Jing

    2011-01-01

    The influence of reaction atmosphere and TiO2 on photochemical decomposition of perfluorooctanoic acid (PFOA) in aqueous periodate was investigated using a type of low-pressure mercury lamps emitted at 254 nm. PFOA photolysis was slight with 254 nm light irradiation under nitrogen, whereas significant decomposition PFOA obtained with the addition of IO4-. In addition, oxygen restrained photochemical decomposition of PFOA. In UV/TiO2/IO4- system, PFOA degradation ratio was 54%, 15% lower than that for UV/IO4- system. *OH radicals generated from UV/TiO2 system exhausted a lot of IO4-, resulting in lower degree of IO3* production. IO3* was high reactive radical which great excitated PFOA decomposition. The accumulation of short-chain perfluorocarbonxylic acids (PFCAs) as products were identified with HPLC/MS. PFCAs bearing shorter perfluoroalkyl groups were formed in a stepwise way from PFCAs that bear longer perfluoroalkyl groups. PMID:21404676

  9. Chemical incorporation of thioxanthone into ?-cyclodextrin and its use in aqueous photopolymerization of methyl methacrylate

    Microsoft Academic Search

    Demet Karaca Balta; Emine Bagdatli; Nergis Arsu; Nuket Ocal; Yusuf Yagci

    2008-01-01

    Photoinitiated free radical polymerization of methyl methacrylate (MMA) in aqueous solution via hydrogen abstraction mechanism was described. For this purpose, thioxanthone (TX) chromophoric group was chemically incorporated into ?-cyclodextrin (?-CD) by a simple esterification process. The resulting thioxanthone photoinitiator (TX–?-CD) exhibited similar spectral characteristics and photoactivity to that of the parent TX molecule. Host guest complexes of MMA with TX–?-CD

  10. Adsorption of heavy metal ion from aqueous single metal solution by chemically modified sugarcane bagasse

    Microsoft Academic Search

    Osvaldo Karnitz; Leandro Vinicius Alves Gurgel; Júlio César Perin de Melo; Vagner Roberto Botaro; Tânia Márcia Sacramento Melo; Rossimiriam Pereira de Freitas Gil; Laurent Frédéric Gil

    2007-01-01

    This work describes the preparation of new chelating materials derived from sugarcane bagasse for adsorption of heavy metal ions in aqueous solution. The first part of this report deals with the chemical modification of sugarcane bagasse with succinic anhydride. The carboxylic acid functions introduced into the material were used to anchor polyamines, which resulted in two yet unpublished modified sugarcane

  11. ENDOCRINE DISRUPTING CHEMICALS - DEVELOPING LRPCD SOPS FOR AQUEOUS, BIOSOLIDS, AND SOLID SAMPLES

    EPA Science Inventory

    As part of research in the risk management of Endocrine Disrupting Chemicals (EDCs), analytical techniques to measure EDCs are needed. This project will result in 6 LRPCD SOPs: analysis of steroid hormones in aqueous samples, analysis of alkylphenol ethoxylates and bisphenol A i...

  12. A USER'S GUIDE FOR REDEQL.EPA. A COMPUTER PROGRAM FOR CHEMICAL EQUILIBRIA IN AQUEOUS SYSTEMS

    EPA Science Inventory

    This user's guide explains the use of the computerized chemical equilibrium program REDEQL.EPA. This program computes aqueous equilibria for up to 20 metals and 30 ligands in a system. The metals and ligands are selected from a list of 35 metals and 59 ligands for which thermodyn...

  13. Chemical transport in silicone rubber membranes from pure powders and saturated aqueous solutions

    Microsoft Academic Search

    Eugene E. Ley; Annette L. Bunge

    2007-01-01

    In this study membrane permeation was measured from finely divided pure powder and saturated aqueous solutions of two test chemicals with low vapor pressure, methyl paraben and 4-cyanophenol, through silicone rubber (polydimethylsiloxane) using diffusion cells operated to insure the concentration was negligible at the interface between the membrane and the receptor solution. The steady-state flux from the pure powder was

  14. 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

  15. Mechanism of Tertiary Oil Recovery by Aqueous Chemical Flooding

    Microsoft Academic Search

    Krishna Kamath; Anthony Zammerilli; Joseph Comberiati; Billy Taylor; Franklin Slagle

    1982-01-01

    The tertiary recovery of oil by chemical flooding is a complex process involving both micro and macroemulsions. Relying on fundamental considerations of theory, operation and economics it is suggested that in situ emulsification of the immobile residual oil (and mobile secondary oil) in the petroleum reservoir and its transport as such to the producing well is feasible and has many

  16. THE CHEMICAL COMPOSITION AND THE OSMOTIC PRESSURE OF THE AQUEOUS HUMOR AND PLASMA OF THE RABBIT

    PubMed Central

    Kinsey, V. Everett

    1951-01-01

    Measurements were made of the osmotic pressure of plasma, and of aqueous humor taken from the anterior chamber of the right and left eyes and from the posterior chamber of unanesthetized rabbits. Aqueous humor from the anterior chamber was found to be hypertonic to the plasma by approximately 3 mM/liter equivalent of sodium chloride. The aqueous humor from the anterior and posterior chambers of the right and left eyes was isotonic. The concentration of chloride in the anterior and posterior chambers was the same. The concentration of all the major components of the aqueous humor and plasma has been determined by chemical analysis on fluid samples obtained from unanesthetized rabbits at approximately the same time. The calculated osmotic pressure of the total of these substances in terms of sodium chloride equivalent agrees to within better than 1 per cent of the total osmotic pressure as measured experimentally. The distribution of some individual anions and cations of the aqueous humor and plasma was determined. This distribution is widely different from that which would obtain at a state of equilibrium. The positive and negative charges carried by the ions in the aqueous humor were approximately equal. Sources of error in the experiments are discussed. PMID:14824506

  17. 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 ?M-C). OH radicals (3.5E-2 ?M [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have effective vapor pressures that are orders of magnitude lower when ammonium hydroxide is present (pH 7) than without (at lower pH). In Po Valley experiments, nitrogen-containing organics were prominent precursors and intermediates. Pyruvate and oxalate were among the products. Importantly, formation of aqSOA helps to explain the high O/C ratios found in atmospheric aerosols. While uncertainties remain large, global modeling suggests that aqSOA is comparable in magnitude to SOA formed through gas phase chemistry and vapor pressure driven partitioning (gasSOA).

  18. 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.

  19. 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.

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

    DOEpatents

    Giese, Roger W. (Quincy, MA); Wang, Poguang (Medford, MA)

    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##

  1. Adsorption of Trace Levels of Arsenic from Aqueous Solutions by Conditioned LDH

    E-print Network

    Southern California, University of

    , cont. Batch Studies: Adsorption Kinetics Adsorption Isotherms Effect of Particle Size Effect of p 3000 4000 5000 Amountadsorbed(g/g) 180-300 90-180 75-90 53-75 #12;ADSORPTION ISOTHERMS Sips Isotherm 1Adsorption of Trace Levels of Arsenic from Aqueous Solutions by Conditioned LDH: Batch and Flow

  2. Nanostructured ZnO thin films by chemical bath deposition in basic aqueous ammonia solutions for photovoltaic applications

    Microsoft Academic Search

    J. B. Chu; S. M. Huang; D. W. Zhang; Z. Q. Bian; X. D. Li; Z. Sun; X. J. Yin

    2009-01-01

    This paper presents further insights and observations of the chemical bath deposition (CBD) of ZnS thin films using an aqueous medium involving Zn-salt, ammonium sulfate, aqueous ammonia, and thioure. Results on physical and chemical properties of the grown layers as a function of ammonia concentration are reported. Physical and chemical properties were analyzed using scanning electron microscopy (SEM), X-ray energy

  3. Nanostructured ZnO thin films by chemical bath deposition in basic aqueous ammonia solutions for photovoltaic applications

    Microsoft Academic Search

    J. B. Chu; S. M. Huang; D. W. Zhang; Z. Q. Bian; X. D. Li; Z. Sun; X. J. Yin

    2009-01-01

    This paper presents further insights and observations of the chemical bath deposition (CBD) of ZnS thin films using an aqueous\\u000a medium involving Zn-salt, ammonium sulfate, aqueous ammonia, and thioure. Results on physical and chemical properties of the\\u000a grown layers as a function of ammonia concentration are reported. Physical and chemical properties were analyzed using scanning\\u000a electron microscopy (SEM), X-ray energy

  4. A combined chemical-enzymatic method to remove selected aromatics from aqueous streams

    SciTech Connect

    Xu, X.; John, V.T.; McPherson, G.L. [Tulane Univ., New Orleans, LA (United States)] [and others

    1995-12-31

    Aromatics are major pollutants found in aqueous environments and in sediments. Although there are many chemical and biochemical processes to remove and/or treat these contaminants, they have to be considered in light of the economics and the time scales for treatment. We describe our initial work on a hybrid chemical-enzymatic technique to remove aromatics from aqueous streams. The aromatic is first converted to the corresponding phenol through classical Fenton-type chemistry involving catalysis by Fe(II). The phenol is subsequently polymerized through an enzymatic mechanism, using horseradish peroxidase as the oxidative enzyme. The polymer is insoluble in water and can be easily recovered. In addition, such phenolic polymers are useful products with varied applications in coatings and resins technologies. Thus, the pollutants can be eventually converted to useful products.

  5. 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.

  6. Removal of Acid Dyes from Aqueous Solutions using Chemically Activated Carbon

    Microsoft Academic Search

    Özgül Gerçel; H. Ferdi Gerçel

    2009-01-01

    Textile dyes (Acid Yellow 17 and Acid Orange 7) were removed from its aqueous solution in batch and continuous packed bed adsorption systems by using thermally activated Euphorbia macroclada carbon with respect to contact time, initial dye concentration, and temperature. The activated carbon was prepared using a cheap plant-based material called Euphorbia macroclada, which was chemically modified with K2CO3. Lagergren-first-order

  7. 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...

  8. 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.

  9. Predicting Chemical Fingerprints of Vadose Zone Soil Gas and Indoor Air from NonAqueous Phase Liquid Composition

    Microsoft Academic Search

    Allen D. Uhler; Kevin J. McCarthy; Stephen D. Emsbo-Mattingly; Scott A. Stout; Gregory S. Douglas

    2010-01-01

    Complex mixtures of volatile organic chemical (VOC) vapors can exist over subsurface accumulations of non-aqueous phase liquids (NAPLs) and contaminated soils. The ability to predict the relative soil gas chemical composition arising from such NAPLs is relevant to studies of the sources and fate of soil gas, and in assessing the possible intrusion of soil gas chemical constituents to indoor

  10. Aspects of glycosidic bond formation in aqueous solution: chemical bonding and the role of water.

    PubMed

    Stubbs, John M; Marx, Dominik

    2005-04-22

    A model of the specific acid-catalyzed glycosidic bond formation in liquid water at ambient conditions is studied based on constrained Car-Parrinello ab initio molecular dynamics. Specifically the reaction of alpha-D-glucopyranose and methanol is found to proceed by a D(N)A(N) mechanism. The D(N) step consists of a concerted protonation of the O(1) hydroxyl leaving group; this process results in the breaking of the C(1)-O(1) bond, and oxocarbenium ion formation involving C(1)=O(5). The second step, A(N), is the formation of the C(1)-O(m) glycosidic bond, deprotonation of the methanol hydroxyl group O(m)H(m), and re-formation of the C(1)-O(5) single bond. A focus of this study is the analysis of the electronic structure during this condensed phase reaction relying on both Boys/Wannier localized orbitals and the electron localization function ELF. This analysis allows the clear elucidation of the chemical bonding features of the intermediate bracketed by the D(N) and A(N) steps, which is a non-solvent equilibrated oxocarbenium cation. Most interestingly, it is found that the oxygen in the pyranose ring becomes "desolvated" upon double bond/oxocarbenium formation, whereas it is engaged in the hydrogen-bonded water network before and after this period. This demonstrates that hydrogen bonding and thus the aqueous solvent play an active role in this reaction implying that microsolvation studies in the gas phase, both theoretical and experimental, might lead to qualitatively different reaction mechanisms compared to solution. PMID:15729673

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  12. Adsorption of Pb(II) From Aqueous Solutions by Chemically Modified Zeolite Supported Carbon Nanotubes: Equilibrium, Kinetic and Thermodynamic Studies

    Microsoft Academic Search

    D. K. Venkata Ramana; D. Harikishore Kumar Reddy; B. Naresh Kumar; K. Seshaiah; G. Purna Chandra Rao; Chungsying Lu

    2012-01-01

    Zeolite supported carbon nanotubes (ZCNTs) were synthesized by the catalytic chemical vapor deposition (CCVD) method. The physical and chemical properties such as surface area, pore diameter, surface functional groups and total acidic and basic sites of the ZCNTs were studied. They were employed as adsorbent to study the adsorption characteristics of Pb(II) in aqueous solution. The adsorption of Pb(II), increase

  13. Sensitivity analysis of a chemical mechanism for aqueous-phase atmospheric chemistry

    SciTech Connect

    Pandis, S.N.; Seinfeld, J.H. (California Inst. of Tech., Pasadena (USA))

    1989-01-20

    The sensitivity analysis of a comprehensive chemical mechanism for aqueous-phase atmospheric chemistry is performed. The main aqueous-phase reaction pathways for the system are the oxidation of S(IV) by H{sub 2}O{sub 2}, OH, O{sub 2} (catalyzed by Fe{sup 3+} and Mn{sup 2+}), O{sub 3} and HSO{sub 5}{sup {minus}}. The HO{sub 2}(aq), respectively. The dominant pathway for HNO{sub 3}(aq) acidity is scavenging of the nitric acid from the gas phase. HCOOH is produced because of the reaction of HCHO(aq) with OH(aq). The gas-phase concentrations of SO{sub 2}, H{sub 2}O{sub 2}, HO{sub 2}, OH, O{sub 3}, HCHO, NH{sub 3}, HNO{sub 3}, and HCl are of primary importance. An increase in the liquid water content of the cloud results in a decrease of the sulfate concentration but an increase of the total sulfate amount in the aqueous phase. A condensed mechanism is derived from the analysis.

  14. CO? 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

  15. Analysis of chemical kinetics at the gas-aqueous interface for submicron aerosols.

    PubMed

    Remorov, R G; George, C

    2006-11-14

    The effect of kinetics of chemical reactions in the gas-liquid interface between atmospheric gases and reactive solute in dilute aqueous aerosols is analysed in order to see if such processes will affect the overall uptake rate. Accordingly, a parameterization of such heterogeneous reactions was derived, taking into account interfacial reactions. Gibbs surface excess concentration of both reactive compounds and stable compounds leads to higher heterogeneous reaction rates in comparison to aqueous phase bulk reactions. An analytical formulation shows that the surface reactions may be of considerable importance for the uptake process in the case of small liquid aerosols even in the absence of organic film on the surface. In particular, we demonstrate that the uptake rate of atmospheric gas-phase oxidants (such as OH, NO(3) or O(3)) reacting with volatile organic compounds (such as ethanol or methanol) is increased by more than 10% for atmospheric aerosols with diameters lower than 0.1 microm. This effect is in addition intensified in the case of reactions of atmospheric oxidants with liquid aerosols containing organic surfactants, such as semi-volatile organic compounds, i.e., the chemical reactions at the gas-liquid interface may be dominant in the main uptake process for atmospheric submicron aerosols. PMID:17066179

  16. Comprehensive study of the chemical reactions resulting from the decomposition of chloroform in alkaline aqueous solution

    NASA Astrophysics Data System (ADS)

    Estevez Mews, Jorge

    Chloroform (CHCl3) is a volatile liquid, which has a rather slow rate of decomposition in ground water. It is a known carcinogen and one of the most common contaminants found at toxic waste sites. The dominant degradation process for chloroform in both the atmosphere and the groundwater is the reaction with the hydroxyl radical or hydroxide ion. This process triggers a sequence of reactions which ultimately yield carbon monoxide, hydrogen chloride, and formic acid. The rate of chloroform degradation is considerably larger in solution than that in the gas phase and it increases dramatically with increasing pH. However, only one of the viable reactions had been studied previously at a high level of theory in solution. It is of great interest to gain a deeper understanding of the decomposition reaction mechanism. Quantum mechanical methods are well suited for studying the mechanism of organic reactions. However, a full quantum mechanical treatment of the entire fluid system is not computationally feasible. In this work, combined quantum mechanical and molecular mechanical (QM/MM) methods are used for studying chemical reactions in condensed phases. In these calculations, the solute molecules are treated quantum mechanically (QM), whereas the solvent molecules are approximated by empirical (MM) potential energy functions. The use of quantum mechanics and statistical sampling simulation is necessary to determine the reaction free energy profile. In the present study, the ab initio Hartree-Fock theory along with the 3-21G basis set was used in the quantum mechanical calculations to elucidate the reaction pathways of chloroform decomposition, with a focus on basic reaction conditions. Statistical mechanical Monte Carlo approach was then applied in molecular mechanical simulations, employing the empirical TIP3P model for water. We employed state-of-the-art electronic structure methods to determine the gas-phase inter-nuclear potential energy profile for all the relevant reactions. Each gas-phase potential energy profile obtained at a high level of theory was used as a post-correction of the corresponding reaction free energy profile in aqueous solution. A detailed picture of the actual mechanism driving the decomposition pathway of chloroform has emerged from these simulations.

  17. 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...

  18. 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.

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

    SciTech Connect

    Dante, D.A.; Tiller, C.L.; Pennell, K.D. [Georgia Inst. of Technology, Atlanta, GA (United States)

    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.

  20. A chemical reaction-based boundary condition for flow electrification

    Microsoft Academic Search

    A. P. Washabaugh; M. Zahn

    1997-01-01

    A physical model is developed for the charge transfer boundary condition in semi-insulating liquids. The boundary condition is based upon interfacial chemical reactions and extends established relations for the interface by including the effects of interfacial surface charge and charge desorption at the interface. A steady state model for flow electrification in a rotating cylindrical electrode apparatus incorporated this boundary

  1. Removal of naphthalene from aqueous solution on chemically modified activated carbons.

    PubMed

    Ania, C O; Cabal, B; Pevida, C; Arenillas, A; Parra, J B; Rubiera, F; Pis, J J

    2007-01-01

    The aim of this work was to correlate the textural and chemical features of carbonaceous adsorbents with the adsorption capacity of naphthalene from aqueous phase, at the concentration in which this compound is usually found in wastewater from coke ovens. The study reveals that the adsorption capacity in different carbon materials depends not only on the textural characteristics of the material but also on the functionalities of the activated carbons. The micropores of the adsorbents, particularly those of narrower diameter, were found to be active sites for the retention of naphthalene. In contrast, the modification of the surface chemistry of the carbon materials led to a decrease in the adsorption capacities. Dispersive forces play an important role, and adsorbents with a higher non-polar character have proven to be more efficient for the naphthalene adsorption. This behaviour has been linked to the presence of specific interactions between the basal planes and the polyaromatic structure of the naphthalene molecule. PMID:17126375

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

    SciTech Connect

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

    2009-06-03

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

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

    NASA Astrophysics Data System (ADS)

    Erdo?an, S.; Önal, Y.; Akmil-Ba?ar, C.; Bilmez-Erdemo?lu, S.; Sar?c?-Özdemir, Ç.; Köseo?lu, E.; ?çduygu, 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.

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

    SciTech Connect

    Yaohiro Inagaki; Toshitaka Imamura; Kazuya Idemitsu; Tatsumi Arima [Kyushu University, Fukuoka, 819-0395 (Japan); Osamu Kato [Kobe Steel Inc., Kobe, 657-0845 (Japan); Hidekazu Asano; Tsutomu Nishimura [RWMC, Tokyo, 105-0001 (Japan)

    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)

  5. QUANTITATIVE ANALYSIS OF 68 POLAR COMPOUNDS FROM TEN CHEMICAL CLASSES BY DIRECT AQUEOUS INJECTION GAS CHROMATOGRAPHY

    EPA Science Inventory

    Porous polymer packings have been used successfully in many applications of direct aqueous injection gas chromatography. The authors have expanded the use of aqueous injection to the quantitative analysis of 68 alcohols, acetates, ketones, ethers, sulfides, aldehydes, diols, dion...

  6. 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

  7. Thermodynamic and experimental study of chemical bath deposition of Zn(S,O,OH) buffer layers in basic aqueous ammonia solutions. Cell results with electrodeposited CuIn(S,Se) 2 absorbers

    Microsoft Academic Search

    C. Hubert; N. Naghavi; B. Canava; A. Etcheberry; D. Lincot

    2007-01-01

    This paper presents a thermodynamic study of Chemical Bath Deposition (CBD) of zinc sulphide based films in aqueous ammonia solutions. The aim is a better understanding of ammonia and temperature effects on the deposition conditions and films composition. The formation of solid phases has been predicted by means of the precipitation conditions of ZnO, Zn(OH)2 and ZnS as a function

  8. 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.

  9. Amphiphilic lauryl ester derivatives from aromatic amino acids: significance of chemical architecture in aqueous aggregation properties.

    PubMed

    Vijay, R; Singh, Jasmeet; Baskar, Geetha; Ranganathan, Radha

    2009-10-22

    Lauryl esters of L-tyrosine (LET) and L-phenylalanine (LEP) were, in a previous interface adsorption study, found to adopt very different interfacial conformations. The present study is an investigation of their aqueous aggregation properties with the goal of elucidating the effects of the presence in LET and absence in LEP of the phenolic OH group on their aqueous aggregate structures and micellar conformations of the surfactant monomers. The measured properties included aggregation numbers from time-resolved fluorescence quenching (TRFQ), interface hydration index and microviscosity by electron spin resonance (ESR), chemical shifts of (1)H resonance lines by NMR, and Krafft temperatures and enthalpies of structural transitions by differential scanning calorimetry (DSC). The TRFQ, ESR, and NMR experiments were conducted at various temperatures from 23 to 70 degrees C for various surfactant concentrations from 0.050 to 0.200 M. Markedly different temperature dependences of aggregation number and (1)H NMR chemical shifts are exhibited by LET and LEP micelles. LET and LEP form ionic micelles. The aggregation number of LEP decreases as is characteristic of ionic micelles, but that of LET increases slightly with temperature. The changes with temperature in the NMR chemical shifts and width of the resonance lines are significantly greater for the various LEP protons than for those of LET. The differences in these properties and other fluorescence decay characteristics of fluorophores incorporated into the micelles could be attributed to the difference in the micellar conformations of LET and LEP which are postulated to be similar to that at oil-water interfaces. The phenolic group is hypothesized to be in the micelle-water interface as part of the headgroup in LET micelles, and its location does not change with temperature. On the other hand, in LEP micelles, the phenyl ring is folded into the core overlapping with the flexible hydrophobic chains. The resulting closer proximity between the phenyl ring and the flexible hydrocarbon chain causes interdependence of the phenyl ring and chain proton resonances, leading to the observed temperature dependence of the chemical shifts in LEP. The TRFQ and ESR data are combined together in a molecular space-filling model, referred to as the polar shell model, to derive the geometrical properties of the micelle. The DSC scans in the temperature range 10-55 degrees C showed the presence of distinctly different endotherms for LET and LEP. The Krafft temperatures, K(T), and the enthalpies were determined. The higher K(T) and broader peak of the DSC endotherm of LET as compared to LEP are attributed to the stabilization of fiberlike structures below the Krafft temperature due to its chirality and the hydrogen bonding capability of the phenolic OH and also to the ion-dipole interactions. Thus, all of the observed differences between LET and LEP could be attributed to the difference in their chemical architecture. PMID:19778004

  10. Adsorption of Trace Levels of Arsenic from Aqueous Solutions by Conditioned Layered Double Hydroxides: Batch and Flow

    E-print Network

    Southern California, University of

    Waters. Water Res. 1972, 6, 1259. (2) Lepkowski, W.; Arsenic Crisis in Bangladesh. Chem. Eng. News 1998 in power plant discharges, as well as, in fresh water supplies. Inorganic As may be present in the 3+ (AsAdsorption of Trace Levels of Arsenic from Aqueous Solutions by Conditioned Layered Double

  11. Peptide synthesis in aqueous environments: the role of extreme conditions and pyrite mineral surfaces on formation and hydrolysis of peptides.

    PubMed

    Schreiner, Eduard; Nair, Nisanth N; Wittekindt, Carsten; Marx, Dominik

    2011-06-01

    A comprehensive study of free energy landscapes and mechanisms of COS-mediated polymerization of glycine via N-carboxy anhydrides (NCAs, "Leuchs anhydrides") and peptide hydrolysis at the water-pyrite interface at extreme thermodynamic conditions is presented. Particular emphasis is set on the catalytic effects of the mineral surface including the putative role of the ubiquitous sulfur vacancy defects. It is found that the mere presence of a surface is able to change the free energetics of the elementary reaction steps. This effect can be understood in terms of a reduction of entropic contributions to the reactant state by immobilizing the reactants and/or screening them from bulk water in a purely geometric ("steric") sense. Additionally, the pyrite directly participates chemically in some of the reaction steps, thus changing the reaction mechanism qualitatively compared to the situation in bulk water. First, the adsorption of reactants on the surface can preform a product-like structure due to immobilizing and scaffolding them appropriately. Second, pyrite can act as a proton acceptor, thus replacing water in this role. Third, sulfur vacancies are found to increase the reactivity of the surface. The finding that the presence of pyrite speeds up the rate-determining step in the formation of peptides with respect to the situation in bulk solvent while stabilizing the produced peptide against hydrolysis is of particular interest to the hypothesis of prebiotic peptide formation at hydrothermal aqueous conditions. Apart from these implications, the generality of the studied organic reactions are of immediate relevance to many fields such as (bio)geochemistry, biomineralization, and environmental chemistry. PMID:21561111

  12. Relationship of fatigue-crack growth rate in an aqueous corrosive medium to the electrochemical conditions at the crack tip

    Microsoft Academic Search

    V. V. Panasyuk; L. V. Ratych; I. N. Dmytrakh

    1984-01-01

    p of this data with the fatiguecrack growth rate in samples of 40Kh13 steel in an aqueous solution with pH 8 was studied. The electrochemical investigations and cyclic crack resistance tests were made on i0  20  150 mm beam samples of rectangular cross section of 40Kh13 steel, the chemical composition, heat-treat cycles, and mechanical properties of which were

  13. 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 (?) > activity of water (a w). The errors (%) in our model associated with these properties, however, fall in the order: ? > K > a w. The transposition between K and ? is due to a more accurate model for estimating K than for estimating ?. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements. To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO 4·12H 2O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.

  14. Oxidation of cyanide in aqueous solution by chemical and photochemical process.

    PubMed

    Sarla, M; Pandit, M; Tyagi, D K; Kapoor, J C

    2004-12-10

    Cyanide waste is found predominantly in industrial effluents generated from metallurgical operations. The toxicity of cyanide creates serious environmental problems. In this paper, oxidation of cyanide in aqueous solution was investigated using chemical and photochemical process. Chemical oxidation was studied at room temperature using H2O2 as oxidant and Cu2+ as catalyst. Photochemical oxidation was studied in an annular type batch photoreactor of 1l capacity using 25 W low-pressure (81.7% transmission at 254 nm wavelength) ultraviolet (UV) lamp along with H2O2 as oxidant. The effect of Cu2+ catalysis was also studied. It was observed that in absence of UV source, the degradation of cyanide by H2O2 alone was very slow, whereas copper ions accelerated the rate of reaction thereby acting as catalyst. Copper formed a complex with cyanide ion, i.e. tetracyanocuprate which had greater affinity for H2O2. Cyanate hydrolysis was also favoured by copper ions. As Cu2+ ion concentration was increased, rate of degradation also increased. Photochemical oxidation by H2O2 and Cu2+ was found to be the best system for cyanide degradation. CN- (100 mg/l) was degraded to non-detectable level in 9 min at pH 10.0 with optimum H2O2 dose of 35.5 mM and Cu2+ dose of 19 mg/l. Reaction kinetics of cyanide oxidation was found to be pseudo-first order and the rate constant has been determined for different processes. PMID:15561362

  15. Adsorption and chemical stability of a cationic aggregating ester - propantheline bromide - on silica surfaces in aqueous dispersions.

    PubMed

    Daniels, R; Rupprecht, H

    1985-07-01

    The adsorption behavior of cationic aggregating substances such as antimicrobial quats or phenothiazine derivatives on silica surfaces in aqueous media has been extensively investigated. However, the chemical stability of adsorbates in such systems was unknown. Propantheline bromide (PPBr) was selected as a model to investigate the stability of hydrolyzable substances in silica-containing aqueous dispersions or in adsorbates on silica carriers used for solid drugs. The quaternary ester PPBr showed an appreciable adsorption on the silica surface, the extent of which was increased by raising the pH of the aqueous phase or by the addition of neutral salts such as NaNO3. In parallel to the adsorption process, hydrolysis of PPBr occurs in these aqueous silica dispersions to yield xanthene carbonic acid and a quaternary alcohol component. Adsorption and hydrolysis were found to be mutually influencing reactions. Because of the adsorption of PPBr, the rate of ester decomposition was enhanced in these silica dispersions when compared to aqueous solutions of PPBr at the same pH. Simultaneously, an increase in PPBr adsorption is observed, as well as adsorption of the decomposition product xanthene carbonic acid. This result can be attributed to ion-pair adsorption of the latter with PPBr. The rate constants of PPBr decomposition were found to depend directly on the silica content of the dispersion, although at higher concentrations a decreased catalytic effect was observed. These phenomena are discussed on the basis of the adsorbate structure and exchange processes. PMID:24272808

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

    NASA Astrophysics Data System (ADS)

    Je?owski, 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 ?m 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 ? and 2 ?, 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.

  17. Control of dual stimuli-responsive vesicle formation in aqueous solutions of single-tailed ferrocenyl surfactant by varying pH and redox conditions.

    PubMed

    Hata, Shinichi; Takahashi, Hiro; Takahashi, Yutaka; Kondo, Yukishige

    2014-01-01

    This paper reports a method to control the formation and disruption of vesicles from a novel single-tailed surfactant (11-ferrocenylundecylammonium bromide, 11-FAB), which contains two stimuli-responsive groups corresponding to pH variation and redox reaction conditions, by external stimuli. Although 11-FAB is a single-tailed surfactant, pure 11-FAB spontaneously forms vesicles in water. Microscopic observations of 2.5 mM aqueous solutions of pure 11-FAB (pH = 5.2) show that a number of 11-FAB vesicles are giant, with diameters of 10-30 ?m. The disruption of vesicles is observed in aqueous 11-FAB solutions under basic conditions. The vesicles are then reformed under acidic conditions. Reduced 11-FAB also forms large vesicles in electrolyte solutions. These vesicles are disrupted by electrochemical oxidation and reformed by subsequent chemical reduction. This reversible disruption and reformation of vesicles is attributed to the drastic change in the molecular structure of 11-FAB. To our knowledge, this is the first report of control over the formation and disruption of vesicles using two stimuli responses. PMID:24492378

  18. Polyelectrolyte multilayer membranes for desalination of aqueous salt solutions and seawater under reverse osmosis conditions

    NASA Astrophysics Data System (ADS)

    Toutianoush, Ali; Jin, Wanqin; Deligöz, Hüseyin; Tieke, Bernd

    2005-06-01

    Ultrathin, multilayered membranes of polyvinylamine (PVA) and polyvinylsulfate (PVS) were electrostatically adsorbed on a porous polymer (polyacrylonitrile/polyethylene terephthalate) support. Their use for desalination of aqueous salt solutions, diluted and non-diluted artificial seawater was investigated under reverse osmosis conditions. Using 60 layer pairs of PVA/PVS as separating membrane, it was possible to completely reject MgCl 2 and MgSO 4 from feed solutions of 1 and 10 mM concentration independently from the operative pressure applied. The rejection of NaCl and Na 2SO 4 increased from 84 and 96% at 5 bar to 93.5 and 98.5% at 40 bar, respectively. From diluted seawater (1:10; 1:100; 1:1000), 99 ± 1% of Mg 2+, 97.0 ± 1% of Ca 2+, and 92.5 ± 1% of Na + were rejected at 40 bar, and from non-diluted seawater, 98 ± 1% of Mg 2+, 96.4 ± 1% of Ca 2+, and 74.5 ± 0.8% of Na + were rejected at 40 bar. The permeation flux J increased linearly with the pressure applied. For a membrane of 60 PVA/PVS layer pairs, a flux value of 4 ± 0.2 L m -2 h -1 was found at 40 bar. The influence of the number of deposited layer pairs on R and J was also investigated.

  19. Hierarchically organized silica-titania monoliths prepared under purely aqueous conditions.

    PubMed

    Flaig, Sylvia; Akbarzadeh, Johanna; Dolcet, Paolo; Gross, Silvia; Peterlik, Herwig; Hüsing, Nicola

    2014-12-22

    Hierarchically organized silica-titania monoliths were synthesized under purely aqueous conditions by applying a new ethylene glycol-modified single-source precursor, such as 3-[3-{tris(2-hydroxyethoxy)silyl}propyl]acetylacetone coordinated to a titanium center. The influence of the silicon- and titanium-containing single-source precursor, the novel glycolated organofunctional silane, and the addition of tetrakis(2-hydroxyethyl)orthosilicate on the formation of the final porous network was investigated by SEM, TEM, nitrogen sorption, and SAXS/WAXS. In situ SAXS measurements were performed to obtain insight into the development of the mesoporous network during sol-gel transition. IR-ATR, UV/Vis, XPS, and XAFS measurements showed that up to a Si/Ti ratio of 35:1, well-dispersed titanium centers in a macro-/mesoporous SiO2 network with a specific surface area of up to 582?m(2) ?g(-1) were obtained. An increase in Ti content resulted in a decrease in specific surface area and a loss of the cellular character of the macroporous network. With a 1:1 Si/Ti ratio, silica-titania powders with circa 100?m(2) ?g(-1) and anatase domains within the SiO2 matrix were obtained. PMID:25367386

  20. 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.

  1. Chemical compositions of aqueous fluid, silicate melt, and supercritical fluid in the vicinity of the second critical endpoint in the system peridotite-H2O

    NASA Astrophysics Data System (ADS)

    Mibe, K.; Kawamoto, T.; Ono, S.

    2012-12-01

    Knowing the chemical compositions of fluid and melt is fundamental in understanding the magma genesis and chemical differentiation in the Earth's interior. We investigated the stability fields of aqueous fluid, silicate melt, and supercritical fluid magma using in-situ x-ray radiography and the second critical endpoint in the system peridotite-H2O was determined to be around 3.8 GPa (Mibe et al., 2007, JGR). Using the quenched recovered samples obtained by Mibe et al. (2007), we determined the chemical compositions of aqueous fluid, silicate melt, and supercritical fluid in the vicinity of the second critical endpoint in the system peridotite-H2O by EPMA analyses. A 10- to 30-?m diameter electron beam was used to obtain the composition of quenched materials from aqueous fluid, silicate melt, and supercritical fluid. The compositions of coexisting aqueous fluid and silicate melt were determined at 3.3 GPa and 3.6 GPa and 1180°C. In both samples, olivine coexists with aqueous fluid and silicate melt. In the run at 3.3 GPa, the composition of aqueous fluid was high-Mg dacitic, whereas the composition of silicate melt was hydrous peridotite. In the run at 3.6 GPa, the composition of aqueous fluid was high-Mg andesitic, whereas the composition of silicate melt was hydrous komatiitic. Although aqueous fluids in both runs are high-Mg, both MgO and FeO preferentially enters into silicate melt compared to aqueous fluid.

  2. Thermal decomposition of the ammonium zinc acetate citrate precursor for aqueous chemical solution deposition of ZnO

    Microsoft Academic Search

    K. Van Werde; D. Mondelaers; G. Vanhoyland; D. Nelis; M. K. Van Bael; J. Mullens; L. C. Van Poucke; B. Van Der Veken; H. O. Desseyn

    2002-01-01

    The thermal decomposition of an aqueous chemical solution deposition Zn2+-precursor is studied by HT-DRIFT (high temperature diffuse reflectance infrared Fourier transform spectroscopy), on-line coupled TGA-EGA (thermogravimetric analysis - evolved gas analysis by Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS)), and HT-XRD (high temperature X-ray diffraction). Using these complementary techniques, it is found that the a-hydroxyl group of the

  3. Evaluation of a predictive ground-water solute-transport model at the Idaho National Engineering Laboratory, Idaho. Water-resources investigations (final). [Aqueous chemical and radioactive wastes

    Microsoft Academic Search

    B. D. Lewis; F. J. Goldstein

    1982-01-01

    Aqueous chemical and radioactive wastes discharged to shallow ponds and to shallow or deep wells on the Idaho National Engineering Laboratory (INEL) since 1952 have affected the quality of the ground water in the underlying Snake River Plain aquifer. The aqueous wastes have created large and laterally dispersed concentration plumes within the aquifer. The waste plumes with the largest areal

  4. Effects of aqueous chemical environments on crack and hydraulic fracture propagation and morphologies

    Microsoft Academic Search

    J. D. Dunning; W. L. Huf

    1983-01-01

    The role of surface active aqueous environments in chemomechanical weakening of geologic materials is examined using the results of hydraulic fracture tests in sandstone, calorimetric studies, and crack propagation tests in synthetic quartz. In hydraulic fracture tests it was found that the effective hydraulic fracture pressure was reduced, over that attained with distilled water, when 5 X 10⁻⁴ M aqueous

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

    SciTech Connect

    Dante, D.A.; Tiller, C.L.; Pennell, K.D. [Georgia Inst. of Technology, Atlanta, GA (United States)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  7. 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.

  8. Lead (II) Removal from Aqueous Solution by Spent Agaricus bisporus : Determination of Optimum Process Condition Using Taguchi Method

    Microsoft Academic Search

    Haiyan Huang; Guanglei Cheng; Lan Chen; Xiaoqiang Zhu; Heng Xu

    2009-01-01

    In this paper, Taguchi method was applied to determine the optimum condition for Pb (II) removal from aqueous solution by\\u000a spent Agaricus bisporus. An orthogonal array experiment design (L9(34) which is of four control factors (pH, t (contact time), m (sorbent mass), and C\\u000a 0 (initial Pb (II) concentration)) having three levels was employed. Biosorption capacity (mg metal\\/g biosorbent) and

  9. PROJECT SUMMARY. 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 contaminants by synthetic surfactants. Facilities throughout DOE have need for removal of organics (oils, PCBs, etc.) ...

  10. 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 (Deep River, CA); Wong, Chi F. (Pembroke, CA); Buckley, Leo P. (Deep River, CA)

    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.

  11. Use of chemically derivatized n-type silicon photoelectrodes in aqueous media: photooxidation of iodide, hexacyanoiron(II), and hexaammineruthenium(II) at ferrocene-derivatized photoanodes

    SciTech Connect

    Bocarsly, A.B.; Walton, E.G.; Wrighton, M.S.

    1980-05-07

    A procedure is described for the chemical derivatization of the surface of n-type semiconductor photoanodes to yield photosensitive interfaces for use in a large number of thermodynamically uphill oxidation processes. (1,1'-ferrocenediyl)dichlorosilane was used to derivatize n-type Si to yield a photoanode that can be used under conditions where the naked (nonderivatized) n-type Si undergoes photoanodic corrosion yielding an insulating SiO/sub x/ surface layer. The results of use of this derivatized n-type Si in aqueous solutions to investigate the photooxidation of iodide, hexacyanoiron(II), and hexaammineruthenium(II) are reported. This type photoelectrode has an operation range that is nearly ideal from the point of solar energy conversion. (BLM)

  12. 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.

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

    PubMed

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

    2007-10-30

    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. H(2)O- or NH(3)-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

  14. 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.

  15. 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

  16. Radiation-Chemical Reduction of Ni2+ Ions in Aqueous Solutions Saturated with Carbon Monoxide

    Microsoft Academic Search

    N. L. Sukhov; A. F. Seliverstov; B. G. Ershov

    2002-01-01

    Under the action of ionizing radiation on aqueous solutions containing noble (gold, silver, platinum, etc.) and other (cadmium, lead, cobalt, nickel, etc.) metal ions and organic compounds (alcohols, formates, etc.), the ions undergo reduction with the formation of metal precipitates (for example, see [1] and references therein). Using the pulse radiolysis technique [2, 3], we showed that short-lived metal atoms

  17. 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...

  18. Light-induced reversible hydrophilicity of ZnO structures grown by aqueous chemical growth

    E-print Network

    -generation of smart, self-cleaning surfaces [5]. Comparing various oxides and their wetting properties, one can easily structures deposited on glass and ITO substrates at low temperatures were studied, in relation to deposition by ACG on both glass and ITO substrates using an equimolar (0.01 m) aqueous solution of zinc nitrate

  19. The effects of aqueous chemical environments on crack and hydraulic fracture propagation and morphologies

    Microsoft Academic Search

    J. D. Dunning; W. L. Huf

    1983-01-01

    The role of surface active aqueous environments in chemomechanical weakening of geologic materials is examined in light of the results of hydraulic fracture tests in sandstone, calorimetric studies, and crack propagation tests in synthetic quartz. In hydraulic fracture tests employing Crab Orchard Sandstone it was found that the effective hydraulic fracture pressure was reduced, over that attained with distilled water,

  20. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    PubMed

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-01

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur. PMID:25368975

  1. PRECIPITATION CONDITIONS OF CHEVREUL'S SALT FROM SYNTHETIC AQUEOUS CuSO4 SOLUTIONS

    Microsoft Academic Search

    Turan Çalban; Soner Ku?lu; Sabri Çolak

    2009-01-01

    In this study, synthetic aqueous CuSO4 solution was prepared at various concentrations. Chevreul's salt was precipitated by passing SO2 through these solutions. Chevreul's salt, a mixed valence copper sulfite, Cu2SO3·CuSO3·2H2O, was characterized by XRD and SEM. The effects of parameters such as initial solution concentration, SO2 feeding rate, reaction time, and initial solution pH on precipitation of Chevreul's salt were

  2. Quantum-Chemical Calculations of Carbon-Isotope Fractionation in CO2(g), Aqueous Carbonate Species, and Carbonate Minerals

    SciTech Connect

    Rustad, James R.; Nelmes, Sierra L.; Jackson, Virgil E.; Dixon, David A.

    2008-01-24

    Quantum chemical calculations on large supermolecular carbonate-water and carbonate mineral clusters are used to predict equilibrium constants for 13,12C-isotope-exchange reactions between CO2(g), aqueous carbonate species, and the common carbonate minerals. For the aqueous species, we evaluate the influence of the size and conformational variability of the solvation shell, the exchange-correlation functional, and the basis set. The choice of exchange-correlation functional (PBE vs B3LYP), the basis set (6-31G* vs aug-cc-pVDZ), and solvation shell size (first shell only vs first shell and a partial second shell) each produce changes of ~5-10 per mil in the reduced partition function ratio. Conformational variability gives rise to a standard error of ~0.5 per mil using ~10 solute-solvent conformations. The best results are obtained with the B3LYP/ aug-cc-pVDZ combination, but because the improvements in the basis set and exchange correlation functional drive the reduced partition function ratios in opposite directions, reasonably good results are also obtained with the PBE/6-31G* combination. To construct molecular clusters representative of mineral environments, a new method is introduced on the basis of conservation of Pauling bond strength. Using these clusters as models for minerals, calculations of mineral-gas and mineral-aqueous carbon-isotope fractionation factors, are in good agreement with experimental measurements. Carbon-isotope fractionation factors for gas, aqueous, and mineral phases are thus integrated into a single theoretical/computational framework.

  3. Quantum-chemical calculations of carbon-isotope fractionation in CO2(g), aqueous carbonate species, and carbonate minerals.

    PubMed

    Rustad, James R; Nelmes, Sierra L; Jackson, Virgil E; Dixon, David A

    2008-01-24

    Quantum chemical calculations on large supermolecular carbonate-water and carbonate mineral clusters are used to predict equilibrium constants for 13,12C-isotope-exchange reactions between CO2(g), aqueous carbonate species, and the common carbonate minerals. For the aqueous species, we evaluate the influence of the size and conformational variability of the solvation shell, the exchange-correlation functional, and the basis set. The choice of exchange-correlation functional (PBE vs B3LYP), the basis set (6-31G* vs aug-cc-pVDZ), and solvation shell size (first shell only vs first shell and a partial second shell) each produce changes of approximately 5-10 per mil in the reduced partition function ratio. Conformational variability gives rise to a standard error of approximately 0.5 per mil using approximately 10 solute-solvent conformations. The best results are obtained with the B3LYP/aug-cc-pVDZ combination, but because the improvements in the basis set and exchange correlation functional drive the reduced partition function ratios in opposite directions, reasonably good results are also obtained with the PBE/6-31G* combination. To construct molecular clusters representative of mineral environments, a new method is introduced on the basis of conservation of Pauling bond strength. Using these clusters as models for minerals, calculations of mineral-gas and mineral-aqueous carbon-isotope fractionation factors, are in good agreement with experimental measurements. Carbon-isotope fractionation factors for gas, aqueous, and mineral phases are thus integrated into a single theoretical/computational framework. PMID:18166027

  4. 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.

  5. Control of convective dissolution by chemical reactions: general classification and application to CO(2) dissolution in reactive aqueous solutions.

    PubMed

    Loodts, V; Thomas, C; Rongy, L; De Wit, A

    2014-09-12

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO_{2} in aqueous solutions by a classical acid-base reaction. PMID:25259984

  6. 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

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

    SciTech Connect

    Lvova, T. V., E-mail: tatyana.lvova.12@mail.ru; Dunaevskii, M. S.; Lebedev, M. V. [Russian Academy of Sciences, Ioffe Physical-Technical Institute (Russian Federation); Shakhmin, A. L. [St. Petersburg State Polytechnical University (Russian Federation); Sedova, I. V.; Ivanov, S. V. [Russian Academy of Sciences, Ioffe Physical-Technical Institute (Russian Federation)

    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.

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

    PubMed

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

    2015-03-01

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

  9. Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

    Microsoft Academic Search

    Oleg S. Pokrovsky; Jacques Schott

    2004-01-01

    Dissolution and precipitation rates of brucite (Mg(OH)2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10?4 to 3 M), saturation index (?12 < log ? < 0.4) and aqueous magnesium concentrations (10?6 to 5·10?4 M). Brucite surface charge and isoelectric point (pHIEP) were determined by surface titrations in a limited

  10. Biosorption of heavy metals from aqueous solutions by chemically modified orange peel

    Microsoft Academic Search

    Ningchuan Feng; Xueyi Guo; Sha Liang; Yanshu Zhu; Jianping Liu

    2011-01-01

    Equilibrium, thermodynamic and kinetic studies were carried out for the biosorption of Pb2+, Cd2+ and Ni2+ ions from aqueous solution using the grafted copolymerization-modified orange peel (OPAA). Langmuir and Freundlich isotherm models were applied to describe the biosorption of the metal ions onto OPAA. The influences of pH and contact time of solution on the biosorption were studied. Langmuir model

  11. Aluminum oxidation catalysis under aqueous conditions: highly enantioselective sulfur oxidation catalyzed by Al(salalen) complexes.

    PubMed

    Matsumoto, Kazuhiro; Yamaguchi, Tetsufumi; Fujisaki, Junichi; Saito, Bunnai; Katsuki, Tsutomu

    2008-02-01

    Asymmetric oxidation catalysis with an aluminum-based complex was achieved by a combination of newly synthesized chiral aluminum(salalen) complexes (salalen = half-reduced salen = salan/salen-hybridized [ONNO]-type tetradentate ligand; salan = reduced salen, salen = N,N'-ethylenebis(salicylideneiminato)) derived from binol (1,1'-bi-2,2'-naphthol) with aqueous hydrogen peroxide as the oxidant. The combination was found to be efficient for asymmetric sulfur oxidation. Various sulfides were smoothly converted into the corresponding sulfoxides with high to excellent enantioselectivity. Thioacetals are also good substrates for the oxidation. PMID:18175304

  12. 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.

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

    PubMed

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

    2002-06-01

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

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

    Microsoft Academic Search

    Ralph Behrends; Mary K. Cowman; J. Majewski; S. Petrucci; F. Eggers; K. H. Richmann; E. M. Eyring; M. Riech; U. Kaatze

    1997-01-01

    Molecular relaxation properties of the monosaccharides (a) D-glucose, (b) methyl β-D-glucopyranoside, (c) methyl α-D-mannopyranoside, (d) D-xylose, (e) D-arabinose, (f) methyl β-D-xylopyranoside, (g) methyl β-D-arabinopyranoside, (h) methyl α-L-(6-deoxy)mannopyranoside, and (i) 1,6-anhydro-β-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

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

    NASA Astrophysics Data System (ADS)

    Kitanovski, Z.; ?usak, A.; Grgi?, 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.

  16. 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.

  17. The aqueous root extract of Aristolochia ringens (Vahl.) Aristolochiaceae inhibits chemically-induced inflammation in rodents.

    PubMed

    Ruth, Aigbe Flora; Olaide, Adeyemi Olufunmilayo; Oluwatoyin, Sofidiya Margaret

    2014-11-01

    The potential of the aqueous root extract of Aristolochia ringens (AR) (10-100 mg/kg p.o) to inhibit inflammation induced by phlogistics was evaluated using the carrageenan and egg albumin induced rat paw oedema, formaldehyde induced arthritic inflammation and xylene induced mouse ear oedema models. AR (10-50 mg/kg) dose-dependently decreased rat paw oedema in the carrageenan and egg albumin induced inflammation, producing comparable inhibition of 57.1% and 65.6% to the 57.9% and 63.9% of indomethacin and diclofenac (10 mg/kg p.o) respectively at 50 mg/kg. AR (10-50 mg/kg) also dose dependently inhibited formaldehyde-induced arthritic paw oedema over the 10 day observation period, with a greater inhibition of 50% at 50 mg/kg than the 40.8% inhibition by diclofenac (10 mg/kg i.p). AR (50 mg/kg) also produced greater inhibition of 84.78% than the 65.21% by dexamethasone (1 mg/kg) in xylene-induced ear oedema. Results show that the aqueous root extract of Aristolochia ringens possesses antiinflammatory activity. PMID:25362593

  18. The solubility of ozone and kinetics of its chemical reactions in aqueous solutions of sodium chloride

    NASA Astrophysics Data System (ADS)

    Levanov, A. V.; Kuskov, I. V.; Antipenko, E. E.; Lunin, V. V.

    2008-12-01

    The solubility of ozone and the kinetics of its decomposition and interaction with chloride ions in a 1 M aqueous solution of NaCl at 20°C and pH 8.4-10.8 were studied. The ratio between the concentration of O3 in solution and the gas phase was found to be 0.16 at pH 8.4-9.8. The concentration of dissolved ozone decreased sharply as pH increased to 10.8 because of a substantial increase in the rate of its decomposition. It was observed for the first time that the interaction of O3 with Cl- in alkaline media resulted in the formation of ClO{3/-} chlorate ions. The dependence of the rate of formation of ClO{3/-} on pH was determined; its maximum value was found to be 9.6 × 10-6 mol l-1 min-1 at pH 10.0 and the concentration of ozone at the entrance of the reactor 30.0 g/m3. A spectrophotometric method for the determination of chlorate ions (concentrations 1 × 10-5-3 × 10-4 M) in aqueous solutions was suggested.

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

    PubMed

    Huang, Lei; Guo, Zhixiong

    2012-02-17

    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. PMID:22248873

  20. 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

  1. Condition prediction of chemical complex systems based on Multifractal and Mahalanobis-Taguchi system

    Microsoft Academic Search

    Yanqing Lv; Jianmin Gao

    2011-01-01

    Abnormal condition is hazardous which may lead to accidents in chemical industry and effective condition prediction methods are imperative for chemical complex system. Comparing with traditional techniques of condition prediction without concerning nonlinearity of complex system, multifractal analysis elaborately reveals scale-invariance or self-similarity properties of observed data, which is one of the intrinsic characteristics of complex system. To predict the

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

    E-print Network

    Epstein, S. A; Nizkorodov, S. A

    2012-01-01

    complexity of possible VOC photo-oxidation mechanisms andVOC chemical sinks to simplify our analysis and focus on the competition between oxidationOxidation by hydroxyl radical is the most important atmo- spheric sink for many VOCs (

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

    NASA Astrophysics Data System (ADS)

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

    1991-12-01

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

  4. Chemical safety and health conditions among Hungarian hospital nurses.

    PubMed

    Tompa, Anna; Jakab, Mátyás; Biró, Anna; Magyar, Balázs; Fodor, Zoltán; Klupp, Tibor; Major, Jenö

    2006-09-01

    In the present study genotoxicological and immunotoxicological follow-up investigations were made on 811 donors including 94 unexposed controls and 717 nurses with various working conditions from different hospitals (The Hungarian Nurse Study). The nurses were exposed to different chemicals: cytostatic drugs, anesthetic, and sterilizing gases, such as ethylene oxide (ETO) and formaldehyde. The measured biomarkers were: clinical laboratory routine tests, completed with genotoxicological (chromosome aberrations [CA], sister chromatid exchange [SCE]), and immune-toxicological monitoring (ratio of lymphocyte subpopulations, lymphocyte activation markers, and leukocyte oxidative burst). The highest rate of genotoxicologically affected donors (25.4%) was found in the group of cytostatic drug-exposed nurses. Comparing geno- and immunotoxicological effect markers, we found that among genotoxicologically affected donors the frequency of helper T cell (Th) lymphocytes, the ratio of activated T and B cells increased, whereas the oxidative burst of leukocytes decreased. In hospitals with lack of protective measures increased CA yields were observed compared to those with ISO 9001 quality control or equivalent measures. Anemia, serum glucose level, thyroid dysfunctions, benign, and malignant tumors were more frequent in the exposed groups than in controls. The hygienic standard of the working environment is the basic risk factor for the vulnerability of nurses. On the basis of these results, it is suggested, that the used cytogenetic and immunological biomarkers are appropriate to detect early susceptibility to diseases. The Hungarian Nurse Study proved that the use of safety measures could protect against occupational exposure at work sites handling cytostatic drugs, anesthetic, and sterilizing gases. PMID:17119241

  5. Effects of Chemical Inhibition of N-WASP, a Critical Regulator of Actin Polymerization on Aqueous Humor Outflow through the Conventional Pathway

    PubMed Central

    Inoue, Toshihiro; Pattabiraman, Padmanabhan P.; Epstein, David L.; Rao, P. Vasantha

    2010-01-01

    The integrity of actin cytoskeletal organization in aqueous humor outflow pathway is thought to play a critical role in modulation of aqueous humor outflow through the trabecular meshwork. Our understanding of the regulation of actin cytoskeletal dynamics in outflow pathway, however, is very limited. To explore the potential importance of Neural Wiskott-Aldrich syndrome protein (N-WASP), a critical regulator of actin polymerization/nucleation in aqueous humor outflow pathway, the effects of Wiskostatin, a selective pharmacological inhibitor of N-WASP, on aqueous humor outflow facility were evaluated using enucleated porcine eyes and a constant pressure perfusion system. Further, drug induced effects on actin cytoskeletal organization, cell adhesions, myosin II phosphorylation, matrix metalloproteinase (MMP) activity, and cytoskeletal protein profile in porcine trabecular meshwork (TM) cells were determined by immunofluorescence, zymography, and mass spectrometry. Aqueous humor outflow facility was increased significantly and progressively in the Wiskostatin perfused porcine eyes. The Wiskostatin perfused eyes appear to exhibit increased giant vacuoles in the inner wall of aqueous plexi and deformation of aqueous plexi. The Wiskostatin treated TM cells demonstrated extensive vacuoles in their cytosol, and both actin stress fibers and focal adhesions were decreased in a reversible manner. The drug treated TM cells also revealed decreased myosin II and actin in the cytoskeletal enriched triton insoluble fraction but did not affect myosin II phosphorylation or MMP-2 activity. These data demonstrate that the chemical inhibition of N-WASP increases aqueous humor outflow facility in association with decreased actomyosin interaction and cell adhesive interactions revealing the importance of N-WASP in homeostasis of aqueous humor outflow. PMID:19961849

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

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

    SciTech Connect

    FRYE JM; KUNKEL JM

    2009-03-05

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

  9. 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.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  12. Consequence analysis of aqueous ammonia spills using an improved liquid pool evaporation model

    E-print Network

    Raghunathan, Vijay

    2005-02-17

    for aqueous ammonia spills was then checked to aid in the offsite consequence analysis of aqueous ammonia spills. The behavior of the chemical released depends on its various inherent properties, ambient conditions and the spill scenario. The different... ..............................................................64 6.6 Applicability of the Model Under Different Meteorological Conditions67 6.7 Limitations of the Model.........................................................................69 VII MODELING SOFTWARE...

  13. Chemically and biologically modified activated carbon sorbents for the removal of lead ions from aqueous media

    Microsoft Academic Search

    Mohamed E. Mahmoud; Tarek M. Abdel-Fattah; Maher M. Osman; Somia B. Ahmed

    2012-01-01

    A method is described for hybridization of the adsorption and biosorption characteristics of chemically treated commercial activated carbon and baker's yeast, respectively, for the formation of environmental friendly multifunctional sorbents. Activated carbon was loaded with baker's yeast after acid-base treatment. Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy were used to characterize these sorbents. Moreover, the sorption capabilities

  14. 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%.

  15. Copper(II) removal from aqueous solutions by adsorption on non-treated and chemically modified cactus fibres.

    PubMed

    Prodromou, M; Pashalidis, I

    2013-01-01

    The adsorption efficiency of a biomass by-product (cactus fibres) regarding the removal of copper(II) from aqueous solutions has been investigated before and after its chemical treatment. The chemical treatment of the biomass by-product included phosphorylation and MnO2-coating. The separation/removal efficiency has been studied as a function of pH, Cu(II) concentration, ionic strength, temperature and contact time. Evaluation of the experimental data shows that the MnO2-coated product presents the highest adsorption capacity, followed by the non-treated and phosphorylated material. Regarding the effect of ionic strength/salinity on the adsorption, in contrast to the removal efficiency of the phosphorylated product, which is significantly affected, the MnO2-coated and non-treated material don't show any effect, indicating the formation of inner-sphere surface complexes. The adsorption reaction is in all cases endothermic and relatively fast, particularly the adsorption on the MnO2-coated product. The results of the present study indicate that for the removal of bivalent metal-ions from contaminated waters the MnO2-coated material is expected to be the most effective adsorbent and an alternative to MnO2 resins for the treatment of environmentally relevant waters. PMID:24334902

  16. '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...

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

    Microsoft Academic Search

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

    1985-01-01

    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.

  18. 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.

  19. SH-SAW Sensor Platform for Chemical Detection in Aqueous Solutions

    SciTech Connect

    Casalnuovo, Steve; Cernosek, Richard; Josse, Fabien; Ricco, Antonio; Zhou, Rongnong

    1999-07-20

    Chemically sensitive polymers coated on delay lines utilizing shear horizontal surface acoustic wave (SH-SAW) sensors are investigated for the detection of organic analytes in liquid environments. The SH-SAW sensor platform was designed and fabricated on 36{degree} rotated Y-cut LiTaO{sub 3}. By depositing a SiO{sub 2} dielectric layer over the entire device prior to applying the polymer film, partial electrical passivation of the interdigital transducers (IDT) is obtained while increasing the mass sensitivity of the device. Changes in the mechanical properties of the chemically sensitive polymer materials were clearly detectable through a frequency shift at least one order of magnitude larger than that of a coated-quartz crystal resonator (QCR) in a similar experiment.

  20. Molecular dynamics simulations of a chemical reaction; conditions for local equilibrium in a temperature gradient

    E-print Network

    Kjelstrup, Signe

    Molecular dynamics simulations of a chemical reaction; conditions for local equilibrium have examined a simple chemical reaction in a temperature gradient; 2F $ F2. A mechanical model molecular dynamics simulations showed that the chemical reaction is in local thermodynamic as well

  1. 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.

  2. Charting the known chemical space for non-aqueous Lithium-air battery electrolyte solvents

    E-print Network

    Husch, Tamara

    2015-01-01

    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 compoun...

  3. Development of an aminocarboxylic acid-modified infrared chemical sensor for selective determination of copper ions in aqueous solutions.

    PubMed

    Lin, Huei-Chi; Chou, Yi-Hsin; Yang, Jyisy

    2008-03-17

    An evanescent wave infrared chemical sensor for the sensitive and selective detection of copper ions in aqueous solutions is described. Because copper ions have no vibrational features, a band-shifting technique was utilized to produce the analytical signal. To enhance the sensitivity of the detection process, a three-step procedure was employed to prepare acidified tris(2-aminoethyl)amine (ATAA) phase on an evanescent wave sensing element. This sensing phase has a chemical structure similar to that of ethylenediamine tetraacetic acid (EDTA), a common chelating agent for metal ions. After formation of complex with copper ions, the shifts in the absorption bands of the ATAA phase were used for quantitation. An additional four sensing phases having chemical structures related to that of EDTA were synthesized to compare their performances for detection of copper ions. The synthetic sensing phases are highly stable in water and insensitive to changes in solutions at pH greater than 4. ATAA was the most sensitive of the phases tested, probably because of the accessibility and flexibility of the functional groups in the ATAA phase. To explore these systems in greater detail and to optimize detection, the effects of parameters such as the buffer concentration, the pH of the sample solution, and the matrix effect on response time and linearity of detection were examined. The analytical signals for copper ions were similar - and highly selective - when the pH of the solution was between 5 and 6.5. For a detection time of 5min, these signals were linear for concentrations up to 200microM with a detection limit ca. 3microM. PMID:18298972

  4. Chemical Enrichment and Physical Conditions in IZw18*

    NASA Technical Reports Server (NTRS)

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

    2013-01-01

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

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

    SciTech Connect

    Boukis, N.; Kritzer, P. [Forschungszentrum Karlsruhe (Germany)

    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.

  6. Fe(III)-oxalate complexes mediated photolysis of aqueous alkylphenol ethoxylates under simulated sunlight conditions.

    PubMed

    Liu, Guangming; Zheng, Shourong; Xing, Xiaoli; Li, Yifan; Yin, Daqiang; Ding, Yongsheng; Pang, Weihai

    2010-01-01

    Photolysis of octylphenol ethoxylates Triton X-100 (TX) in water under simulated sunlight conditions was investigated in the presence of Fe(III)-oxalate complexes. The results showed that Fe(III)-oxalate complexes mediated TX degradation followed the first-order kinetics and the photolysis efficiency was dependent on the pH, Fe(III) concentration, Fe(III)/oxalate ratio and initial TX concentration. The active oxygen species generated by photolysis of Fe(III)-oxalate complexes were monitored by electron paramagnetic resonance (EPR) method using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the spin-trapping reagent. The steady-state concentration of OH radicals was 8.33x10(-14)M and the rate constant of TX reaction with OH radical was 1.29x10(9)M(-1)s(-1) under our experimental conditions. The degradation products were analyzed by the high-performance liquid chromatography-electrospray ionisation-mass spectrometry and the degradation mechanisms of TX in the presence of Fe(III)-oxalate complexes was proposed. The OH radical can react with the alkyl chain, ethoxy (EO) chain and the aromatic ring of TX molecule during TX photolysis process. The main degradation pathway of TX involves the OH radical addition to the aromatic ring and the cleavage of the alkyl chain followed by combination with OH radical. The OH radical also attacks the polyethoxylated chain to generate short polyethoxylated chains or formyl ethoxylates. PMID:19945734

  7. 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...

  8. CHEMICAL SPECIATION OF INORGANIC COMPOUNDS UNDER HYDROTHERMAL CONDITIONS

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  10. Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

    NASA Technical Reports Server (NTRS)

    Barkatt, Aaron; Saad, E. E.; Adiga, R. B.; Sousanpour, W.; Barkatt, AL.; Feng, X.; O'Keefe, J. A.; Alterescu, S.

    1988-01-01

    This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

  11. 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/.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  13. Chemical reactions in viscous liquids under space conditions

    Microsoft Academic Search

    A. Kondyurin; B. Lauke; E. Richter

    2004-01-01

    A long-term human flight needs a large-size space ships with artificial self-regulating ecological life-support system. The best way for creation of large-size space ship is a synthesis of light construction on Earth orbit, that does not need a high energy transportation carriers from Earth surface. The construction can be created by the way of chemical polymerisation reaction under space environment.

  14. Passivation of Zn{sub 3}P{sub 2} substrates by aqueous chemical etching and air oxidation

    SciTech Connect

    Kimball, Gregory M.; Bosco, Jeffrey P.; Mueller, Astrid M.; Tajdar, Syed F.; Brunschwig, Bruce S.; Atwater, Harry A.; Lewis, Nathan S. [Noyes Laboratory, Watson Laboratory, and Beckman Institute, California Institute of Technology, Pasadena, California 91125 (United States)

    2012-11-15

    Surface recombination velocities measured by time-resolved photoluminescence and compositions of Zn{sub 3}P{sub 2} surfaces measured by x-ray photoelectron spectroscopy (XPS) have been correlated for a series of wet chemical etches of Zn{sub 3}P{sub 2} substrates. Zn{sub 3}P{sub 2} substrates that were etched with Br{sub 2} in methanol exhibited surface recombination velocity values of 2.8 Multiplication-Sign 10{sup 4} cm s{sup -1}, whereas substrates that were further treated by aqueous HF-H{sub 2}O{sub 2} exhibited surface recombination velocity values of 1.0 Multiplication-Sign 10{sup 4} cm s{sup -1}. Zn{sub 3}P{sub 2} substrates that were etched with Br{sub 2} in methanol and exposed to air for 1 week exhibited surface recombination velocity values of 1.8 Multiplication-Sign 10{sup 3} cm s{sup -1}, as well as improved ideality in metal/insulator/semiconductor devices.

  15. Chemically exfoliated MoS? nanosheets as an efficient catalyst for reduction reactions in the aqueous phase.

    PubMed

    Guardia, Laura; Paredes, Juan I; Munuera, José M; Villar-Rodil, Silvia; Ayán-Varela, Miguel; Martínez-Alonso, Amelia; Tascón, Juan M D

    2014-12-10

    Chemically exfoliated MoS2 (ce-MoS2) nanosheets that incorporate a large fraction of metallic 1T phase have been recently shown to possess a high electrocatalytic activity in the hydrogen evolution reaction, but the potential of this two-dimensional material as a catalyst has otherwise remained mostly uncharted. Here, we demonstrate that ce-MoS2 nanosheets are efficient catalysts for a number of model reduction reactions (namely, those of 4-nitrophenol, 4-nitroaniline, methyl orange, and [Fe(CN)6](3-)) carried out in aqueous medium using NaBH4 as a reductant. The performance of the nanosheets in these reactions is found to be comparable to that of many noble metal-based catalysts. The possible reaction pathways involving ce-MoS2 as a catalyst are also discussed and investigated. Overall, the present results expand the scope of this two-dimensional material as a competitive, inexpensive, and earth-abundant catalyst. PMID:25405770

  16. Chemical properties of positive singly charged astatine ion in aqueous solution

    Microsoft Academic Search

    M. Milanov; V. Doberenz; V. A. Khalkin; A. Marinov

    1984-01-01

    The mobility of oxidized astatine in solutions H(Na)ClO4 (=0.4 M) – 1·10–4M K2Cr2O7 has been measured at 25°C in the interval 0.63pH1.68. Under these conditions astatine migrates to the cathode only. The speed of the migration depends upon the concentration of hydrogen ions in solution: pH 1.68 Uc = 1.17 · 10-4 cm2 V-1 s-1 pH 0.63 Uc = 2.67

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

    SciTech Connect

    Clark, D.L.; Conradson, S.D.; Donohoe, R.J.; Keogh, D.W.; Morris, D.E.; Palmer, P.D.; Tait, C.D. [Los Alamos National Lab., NM (United States)] [Los Alamos National Lab., NM (United States); Rogers, R.D. [Los Alamos National Lab., NM (United States)] [Los Alamos National Lab., NM (United States); [Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry

    1999-04-05

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

  18. 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

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

    USGS Publications Warehouse

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

    1999-01-01

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

  20. The use of chemically modified and unmodified cassava waste for the removal of Cd, Cu and Zn ions from aqueous solution

    Microsoft Academic Search

    A. A. Abia; M. Horsfall; O. Didi

    2003-01-01

    The use of different chemically modified cassava waste biomass for the enhancement of the adsorption of three metal ions Cd, Cu and Zn from aqueous solution is reported in this paper. Treating with different concentrations of thioglycollic acid modified the cassava waste biomass.The sorption rates of the three metals were 0.2303 min?1 (Cd2+), 0.0051 min?1 (Cu2+), 0.0040 min?1 (Zn2+) and

  1. THE INFLUENCE OF THE CHEMICAL NATURE OF SOLID PARTICLES ON THEIR CATAPHORETIC P.D. IN AQUEOUS SOLUTIONS

    PubMed Central

    Loeb, Jacques

    1923-01-01

    1. The effect of eight salts, NaCl, Na2SO4, Na4Fe(CN)6, CaCl2, LaCl3, ThCl4, and basic and acid fuchsin on the cataphoretic P.D. between solid particles and aqueous solutions was measured near the point of neutrality of water (pH 5.8). It was found that without the addition of electrolyte the cataphoretic P.D. between particles and water is very minute near the point of neutrality (pH 5.8), often less than 10 millivolts, if care is taken that the solutions are free from impurities. Particles which in the absence of salts have a positive charge in water near the point of neutrality (pH 5.8) are termed positive colloids and particles which have a negative charge under these conditions are termed negative colloids. 2. If care is taken that the addition of the salt does not change the hydrogen ion concentration of the solution (which in these experiments was generally pH 5.8) it can be said in general, that as long as the concentration of salts is not too high, the anions of the salt have the tendency to make the particles more negative (or less positive) and that cations have the opposite effect; and that both effects increase with the increasing valency of the ions. As soon as a maximal P.D. is reached, which varies for each salt and for each type of particles, a further addition of salt depresses the P.D. again. Aside from this general tendency the effects of salts on the P.D. are typically different for positive and negative colloids. 3. Negative colloids (collodion, mastic, Acheson's graphite, gold, and metal proteinates) are rendered more negative by low concentrations of salts with monovalent cation (e.g. Na) the higher the valency of the anion, though the difference in the maximal P.D. is slight for the monovalent Cl and the tetravalent Fe(CN)6 ions. Low concentrations of CaCl2 also make negative colloids more negative but the maximal P.D. is less than for NaCl; even LaCl3 increases the P.D. of negative particles slightly in low concentrations. ThCl4 and basic fuchsin, however, seem to make the negative particles positive even in very low concentrations. 4. Positive colloids (ferric hydroxide, calcium oxalate, casein chloride—the latter at pH 4.0) are practically not affected by NaCl, are rendered slightly negative by high concentrations of Na2SO4, and are rendered more negative by Na4Fe(CN)6 and acid dyes. Low concentrations of CaCl2 and LaCl3 increase the positive charge of the particles until a maximum is reached after which the addition of more salt depresses the P.D. again. 5. It is shown that alkalies (NaOH) act on the cataphoretic P.D. of both negative and positive particles as Na4Fe(CN)6 does at the point of neutrality. 6. Low concentrations of HCl raise the cataphoretic P.D. of particles of collodion, mastic, graphite, and gold until a maximum is reached, after which the P.D. is depressed by a further increase in the concentration of the acid. No reversal in the sign of charge of the particle occurs in the case of collodion, while if a reversal occurs in the case of mastic, gold, and graphite, the P.D. is never more than a few millivolts. When HCl changes the chemical nature of the colloid, e.g. when HCl is added to particles of amphoteric electrolytes like sodium gelatinate, a marked reversal will occur, on account of the transformation of the metal proteinate into a protein-acid salt. 7. A real reversal in the sign of charge of positive particles occurs, however, at neutrality if Na4Fe(CN)6 or an acid dye is added; and in the case of negative colloids when low concentrations of basic dyes or minute traces of ThCl4 are added. 8. Flocculation of the suspensions by salts occurs when the cataphoretic P.D. reaches a critical value which is about 14 millivolts for particles of graphite, gold, or mastic or denatured egg albumin; while for collodion particles it was about 16 millivolts. A critical P.D. of about 15 millivolts was also observed by Northrop and De Kruif for the flocculation of certain bacteria. PMID:19872064

  2. 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...

  3. Cerium: A chemical tracer of paleo-oceanic redox conditions

    Microsoft Academic Search

    T. G. Liu; M. R. U. Miah; R. A. Schmitt

    1988-01-01

    The Ce anomalies found in marine carbonates provide a sensitive indicator for the study of paleo-oceanic redox conditions. The dependency of C{sub Ce} and a{sub CePOâ°} to the P{sub Oâ}, pH and P{sub COâ} of seawater can be used for deciphering some aspects of the paleo-ocean chemistry. The pH, which is related to P{sub COâ}, and P{sub Oâ} are major

  4. 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.

  5. 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...

  6. Production of chemical alarm cues in convict cichlids: the effects of diet, body condition and ontogeny

    Microsoft Academic Search

    Grant E. Brown; Patricia E. Foam; Hilary E. Cowell; Palestina Guevara Fiore; Douglas P. Chivers

    While much is known regarding the role of chemical alarm cues in the mediation of predator-prey dynamics within aquatic ecosystems, little is known regarding the production of these critically important information sources. In a series of labora- tory experiments, we tested the possible effects of diet, body condition and ontogeny on the production of chemical alarm cues in juvenile convict

  7. The Chemical Impact of Physical Conditions in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Rimmer, Paul Brandon

    2012-09-01

    We examine the role cosmic rays, X-rays and ultra-violet (UV) photons play in the chemical evolution of the interstellar medium, and how astrophysical processes like massive star formation can change the fluxes of these energetic particles. We connect star formation rates to interstellar chemistry. We first explore the basic effects of cosmic-ray and X-ray ionization and UV photodissociation on the chemistry. For cosmic-ray and X-ray ionization, increasing the ionization rates enriches the chemistry, up to a value of 10 -14 s-1, whereupon molecules and ions are quickly destroyed due to the high electron fraction. Isolated from other effects, the UV field tends to dissociate species much more efficiently than ionizing them, and generally reduces molecular abundances, especially those of complex molecules. The combination of a high ionization rate and a high UV field can enhance the production of some molecular species, such as small hydrocarbons. We investigate the role of cosmic rays and UV photons in the Horsehead Nebula, and determine the impact a column-dependent cosmic ray ionization rate makes on photodissociation region (PDR) chemistry. The column-dependence of cosmic rays is solved using a three-dimensional two-fluid magnetohydrodynamics model, treating the cosmic rays as a fluid governed by the relativistic Boltzmann Transport Equation, and treating the interstellar medium as a second fluid, governed by the standard non-relativistic magnetohydrodynamics equations. We then utilize a modified version of the Morata-Herbst time-dependent PDR model, incorporating our function for cosmic ray ionization. Our results help solve a chemical mystery concerning high abundances of small hydrocarbons at the edge of the nebula. We discuss predictions the model makes for species currently unobserved in the Horsehead Nebula. Finally, we examine the role of star formation on interstellar astrochemistry in the Orion KL region. We develop a new astrochemical gas-grain PDR model with a time-dependent UV radiation field and X-ray and cosmic ray flux, scaled to the star formation rate and radiative contributions of different spectral-type stars. The results provide an explanation for OH+, H2O + and water observations, and H3O+ non-detection in the region, as well as make unique predictions for HCO+ and other molecules. These results allow us to constrain the age of the Orion KL region. We predict an age for Orion KL of one hundred thousand to one million years after OB star formation.

  8. The Chemical Impact of Physical Conditions in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Rimmer, Paul B.

    2012-03-01

    We examine the role cosmic rays, X-rays and ultra-violet (UV) photons play in the chemical evolution of the interstellar medium, and how astrophysical processes like massive star formation can change the fluxes of these energetic particles. We connect star formation rates to interstellar chemistry. We first explore the basic effects of cosmic-ray and X-ray ionization and UV photodissociation on the chemistry. For cosmic-ray and X-ray ionization, increasing the ionization rates enriches the chemistry, up to a value of 10(-14) s-1, whereupon molecules and ions are quickly destroyed due to the high electron fraction. Isolated from other effects, the UV field tends to dissociate species much more efficiently than ionizing them, and generally reduces molecular abundances, especially those of complex molecules. The combination of a high ionization rate and a high UV field can enhance the production of some molecular species, such as small hydrocarbons. We investigate the role of cosmic rays and UV photons in the Horsehead Nebula, and determine the impact a column-dependent cosmic ray ionization rate makes on photodissociation region (PDR) chemistry. The column-dependence of cosmic rays is solved using a three-dimensional two-fluid magnetohydrodynamics model, treating the cosmic rays as a fluid governed by the relativistic Boltzmann Transport Equation, and treating the interstellar medium as a second fluid, governed by the standard non-relativistic magnetohydrodynamics equations. We then utilize a modified version of the Morata-Herbst time-dependent PDR model, incorporating our function for cosmic ray ionization. Our results help solve a chemical mystery concerning high abundances of small hydrocarbons at the edge of the nebula. We discuss predictions the model makes for species currently unobserved in the Horsehead Nebula. Finally, we examine the role of star formation on interstellar astrochemistry in the Orion KL region. We develop a new astrochemical gas-grain PDR model with a time-dependent UV radiation field and X-ray and cosmic ray flux, scaled to the star formation rate and radiative contributions of different spectral-type stars. The results provide an explanation for OH+, H2O+ and water observations, and H3O+ non-detection in the region, as well as make unique predictions for HCO+ and other molecules. These results allow us to constrain the age of the Orion KL region. We predict an age for Orion KL of one hundred thousand to one million years after OB star formation.

  9. 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.

  10. 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.

  11. Characterization of chemically modified corncobs and its application in the removal of metal ions from aqueous solution.

    PubMed

    Nasiruddin Khan, M; Farooq Wahab, M

    2007-03-01

    The objective of this work was to convert corncobs to activated carbon by low temperature chemical treatment for removing copper from wastewater. The parameters for developing a new adsorbent i.e. sorption capacity, selectivity, regenerability, suspension test, and kinetics were investigated. All studies were performed in batch experiments. Removal of copper from aqueous solutions varied with the amount of adsorbent, metal ion concentration, agitation time, solution pH and the species of copper present. It was found that the effect of temperature was very small. The Langmuir model was found to best fit the equilibrium isotherm data. Kinetics of copper removal at two different temperatures obeyed Lagergren pseudo-first-order equation. Effect of water hardness, other cations (Pb(2+) and Zn(2+)) on copper removal was also studied. Experiments with anionic and cationic complexes of copper showed that anionic copper species are not removed at all by the prepared material. To observe the nature of surface and pore structure scanning electron microscope (SEM) images of modified corncobs were used. To study the interaction forces between the adsorbent and the metal ion functional group analysis with infrared spectroscopy and proximate analysis were carried out. In addition, recovery of the metals ion and regeneration of spent adsorbent was possible by acidified hydrogen peroxide. Since the uptake capacity of the prepared adsorbent is 26mg Cu/g for copper, it can be a potential adsorbent for removing and recovering other heavy metal ions from contaminated wastewaters. The sorption capacity of the treated corncobs for copper was better than the reported capacity of other activated carbons prepared from agricultural sources. PMID:16911857

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  13. Chemical Etching of CdTe in Aqueous Solutions of H2O2-HI-Citric Acid

    NASA Astrophysics Data System (ADS)

    Ivanits'ka, V. G.; Moravec, P.; Franc, J.; Tomashik, Z. F.; Feychuk, P. I.; Tomashik, V. M.; Shcherbak, L. P.; Mašek, K.; Höschl, P.

    2007-08-01

    An iodine-based etching system, H2O2-HI-citric acid, has been developed and tested on CdTe samples with orientations (111)A, (111)B, (110), and (100). The etching velocity of CdTe was shown to depend on sample orientation and other etching conditions. The surface roughness was comparable with that of the surfaces after Br-methanol treatment. A comparative study of the chemical composition of the (211)B CdZnTe surfaces etched under different conditions was performed. X-ray photoelectron spectroscopy (XPS) measurements showed that all treated surfaces of CdZnTe samples are enriched with Te. The HI-based treatment seems to be more acceptable than the Br-methanol treatment in terms of elimination of Te oxides from the surface, however.

  14. Ion-pair formation in aqueous strontium chloride and strontium hydroxide solutions under hydrothermal conditions by AC conductivity measurements.

    PubMed

    Arcis, H; Zimmerman, G H; Tremaine, P R

    2014-09-01

    Frequency-dependent electrical conductivities of solutions of aqueous strontium hydroxide and strontium chloride have been measured from T = 295 K to T = 625 K at p = 20 MPa, over a very wide range of ionic strength (3 × 10(-5) to 0.2 mol kg(-1)), using a high-precision flow AC conductivity instrument. Experimental values for the concentration-dependent equivalent conductivity, ?, of the two electrolytes were fitted with the Turq-Blum-Bernard-Kunz ("TBBK") ionic conductivity model, to determine ionic association constants, K(A,m). The TBBK fits yielded statistically significant formation constants for the species SrOH(+) and SrCl(+) at all temperatures, and for Sr(OH)2(0) and SrCl2(0) at temperatures above 446 K. The first and second stepwise association constants for the ion pairs followed the order K(A1)(SrOH(+)) > K(A1)(SrCl(+)) > K(A2)[Sr(OH)2(0)] > K(A2)[SrCl2(0)], consistent with long-range solvent polarization effects associated with the lower static dielectric constant and high compressibility of water at elevated temperatures. The stepwise association constants to form SrCl(+) agree with previously reported values for CaCl(+) to within the combined experimental error at high temperatures and, at temperatures below ?375 K, the values of log10?KA1 for strontium are lower than those for calcium by up to ?0.3-0.4 units. The association constants for the species SrOH(+) and Sr(OH)2(0) are the first accurate values to be reported for hydroxide ion pairs with any divalent cation under these conditions. PMID:25031185

  15. Fabrication of core-shell structured nanoparticle layer substrate for excitation of localized surface plasmon resonance and its optical response for DNA in aqueous conditions

    Microsoft Academic Search

    Tatsuro Endo; Daisuke Ikeda; Yukari Kawakami; Yasuko Yanagida; Takeshi Hatsuzawa

    2010-01-01

    LSPR from nanostructured noble metals such as gold and silver offers great potential for biosensing applications. In this study, a core-shell structured nanoparticle layer substrate was fabricated and the localized surface plasmon resonance (LSPR) optical characteristics were investigated for DNA in aqueous conditions. Factors such as DNA length dependence, concentration dependence, and the monitoring of DNA aspects (ssDNA or dsDNA)

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  17. CO-conditioning and dewatering of chemical sludge and waste activated sludge

    Microsoft Academic Search

    G. R Chang; J. C Liu; D. J Lee

    2001-01-01

    The conditioning and dewatering behaviors of chemical and waste activated sludges from a tannery were studied. Capillary suction time (CST), specific resistance to filtration (SRF), and bound water content were used to evaluate the sludge dewatering behaviors. Zeta potentials were also measured. Experiments were conducted on each sludge conditioned and dewatered separately, and on the sludge mixed at various ratios.

  18. 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 (?ex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the ?ex 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-?ex 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 ?ex 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-?ex 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

  19. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models.

    PubMed

    Liberman, M A; Kiverin, A D; Ivanov, M F

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation. PMID:23004867

  20. Regimes of chemical reaction waves initiated by nonuniform initial conditions for detailed chemical reaction models

    NASA Astrophysics Data System (ADS)

    Liberman, M. A.; Kiverin, A. D.; Ivanov, M. F.

    2012-05-01

    Regimes of chemical reaction wave propagation initiated by initial temperature nonuniformity in gaseous mixtures, whose chemistry is governed by chain-branching kinetics, are studied using a multispecies transport model and a detailed chemical model. Possible regimes of reaction wave propagation are identified for stoichiometric hydrogen-oxygen and hydrogen-air mixtures in a wide range of initial pressures and temperature levels, depending on the initial non-uniformity steepness. The limits of the regimes of reaction wave propagation depend upon the values of the spontaneous wave speed and the characteristic velocities of the problem. It is shown that one-step kinetics cannot reproduce either quantitative neither qualitative features of the ignition process in real gaseous mixtures because the difference between the induction time and the time when the exothermic reaction begins significantly affects the ignition, evolution, and coupling of the spontaneous reaction wave and the pressure wave, especially at lower temperatures. We show that all the regimes initiated by the temperature gradient occur for much shallower temperature gradients than predicted by a one-step model. The difference is very large for lower initial pressures and for slowly reacting mixtures. In this way the paper provides an answer to questions, important in practice, about the ignition energy, its distribution, and the scale of the initial nonuniformity required for ignition in one or another regime of combustion wave propagation.

  1. The selective peptide reactivity of chemical respiratory allergens under competitive and non-competitive conditions.

    PubMed

    Lalko, Jon F; Kimber, Ian; Dearman, Rebecca J; Api, Anne Marie; Gerberick, G Frank

    2013-01-01

    It is well established that certain chemicals cause respiratory allergy. In common with contact allergens, chemicals that induce sensitization of the respiratory tract must form stable associations with host proteins to elicit an immune response. Measurement of the reactivity of chemical allergens to single nucleophilic peptides is increasingly well-described, and standardized assays have been developed for use in hazard assessment. This study employed standard and modified peptide reactivity assays to investigate the selectivity of chemical respiratory allergens for individual amino acids under competitive and non-competitive conditions. The reactivity of 20 known chemical respiratory sensitizers (including diisocyanates, anhydrides, and reactive dyes) were evaluated for reactivity towards individual peptides containing cysteine, lysine, histidine, arginine, or tyrosine. Respiratory allergens exhibited the common ability to deplete both lysine and cysteine peptides; however, reactivity for histidine, arginine, and tyrosine varied between chemicals, indicating differences in relative binding affinity toward each nucleophile. To evaluate amino acid selectivity for cysteine and lysine under competitive conditions a modified assay was used in which reaction mixtures contained different relative concentrations of the target peptides. Under these reaction conditions, the binding preferences of reference respiratory and contact allergens (dinitrochlorobenzene, dinitrofluorobenzene) were evaluated. Discrete patterns of reactivity were observed showing various levels of competitive selectivity between the two allergen classes. PMID:23050863

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

    NASA Technical Reports Server (NTRS)

    Tyree, S. Y., Jr.

    1975-01-01

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

  3. Computer simulation of structure and mobility of water hydrogen bonds net in aqueous solutions of some chemical compounds

    NASA Astrophysics Data System (ADS)

    Kuznetsov, Pavel E.; Rogacheva, Svetlana M.; Popyhova, Era B.; Simonova, Zoya A.; Pylaev, Timophey E.

    2005-06-01

    Computer simulation of aqueous solutions of some biological active and inactive compounds has been carried out. Molecular dynamics method and TIP3P potential were used. The parameters of hydrogen bonds net were calculated by using the developed computer program. The simulation showed that relatively large clusters of water molecules appeared and the average number of hydrogen bonds decreased in the aqueous solutions of biological active compounds. It points to the fact that these compounds may induce the phase k-transition in the surrounding water. Molecular mechanisms ofthese effects are discussed.

  4. A general synthesis for PEDOT-coated nonconductive materials and PEDOT hollow particles by aqueous chemical polymerization.

    PubMed

    Luo, Shyh-Chyang; Yu, Hsiao-hua; Wan, Andrew C A; Han, Yu; Ying, Jackie Y

    2008-11-01

    A method for coating functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) on nonconductive substrates in aqueous solution allows the deposition of PEDOT thin layers on various substrates, including silica and polystyrene (PS) nanoparticles, siliceous mesocellular foam, and chitosan-alginate fibers. The surface property is tuned by controlling the monomer composition in the aqueous solutions. Using appropriate organic solvents to remove the PS cores of PEDOT-coated PS nanoparticles, hollow PEDOT particles with single holes and PEDOT capsules can be formed. PMID:18949792

  5. Chemical Composition and Antimicrobial Potential of Aqueous Distillate Volatiles of Indian Peppermint (Mentha piperita) and Spearmint (Mentha spicata)

    Microsoft Academic Search

    Ram Swaroop Verma; Vandana Pandey; Rajendra Chandra Padalia; Dharmendra Saikia; Binay Krishna

    2011-01-01

    During the process of distillation, the hydrophilic part of the essential oil dissolves in the aqueous distillate that is generally considered waste and discarded. The decanted (main essential oil) and hydrophilic (recovered essential oil) fractions of peppermint (Mentha piperita cv Kukrail) and spearmint (Mentha spicata cv MSS-5) essential oils were investigated by gas chromatography and gas chromatography–mass spectrometry. The decanted

  6. Stochastic Models for Pad Structure and Pad Conditioning Used in Chemical-Mechanical Polishing

    Microsoft Academic Search

    Susanne Wiegand; Dietrich Stoyan

    2006-01-01

    Stochastic models are presented for the structure and conditioning of pads used in chemical-mechanical polishing of wafers.\\u000a First the one-dimensional distribution function of surface depth in the case of a conditioned solid pad is described. Then,\\u000a for characterizing the structure of a foamed pad, the theory of random closed sets is applied. An important distributional\\u000a characteristic of a random closed

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

    EPA Science Inventory

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

  8. Surface studies of niobium chemically polished under conditions for superconducting radio frequency (SRF) cavity production

    Microsoft Academic Search

    Hui Tian; Charles E. Reece; Michael J. Kelley; Shancai Wang; Lukasz Plucinski; Kevin E. Smith; Matthew M. Nowell

    2006-01-01

    The performance of niobium superconducting radiofrequency (SRF) accelerator cavities is strongly impacted by the topmost several nanometers of the active (interior) surface, especially as influenced by the final surface conditioning treatments. We examined the effect of the most commonly employed treatment, buffered chemical polishing (BCP), on polycrystalline niobium sheet over a range of realistic solution flow rates using electron back

  9. A system dynamics model for behavioral analysis of safety conditions in a chemical storage unit

    E-print Network

    Paris-Sud XI, Université de

    Mode Effect Analysis; Nicolet-Monnier, 1996), FTA (Fault Tree Analysis; Khan & Abbasi, 1998), FMECAA system dynamics model for behavioral analysis of safety conditions in a chemical storage unit.guarnieri@mines-paristech.fr Abstract This paper aims to develop a system dynamics model in order to formalize causal interdependencies

  10. Aqueous precursors for electrochromic tungsten oxide hydrates

    Microsoft Academic Search

    J. Livage; G. Guzman

    1996-01-01

    Tungsten oxide hydrates WO3 · nH2O are formed upon the acidification of tungstate aqueous solutions. Different amorphous or crystalline phases can be obtained depending on the experimental conditions (pH, concentration, temperature). The chemical mechanisms for the formation of these hydrates are discussed and the electrochromic properties of thin films deposited from these solutions are described. Hydrogen peroxide H2O2 reacts with

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

    USGS Publications Warehouse

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

    2003-01-01

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

  12. Adsorption studies of lead on lateritic minerals from aqueous media

    Microsoft Academic Search

    Shujaat Ahmad; Nasir Khalid; Muhammad Daud

    2002-01-01

    Minerals produced by lateritic weathering have been exploited to evaluate their potential for the decontamination of lead ions from aqueous solutions and for understanding decontamination mechanism in nature. Various physico-chemical parameters such as selection of appropriate electrolyte, equilibration time, amount of adsorbent, concentration of adsorbate, effect of diverse ions and temperature were studied in order to simulate the best conditions

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

    PubMed

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

    2013-05-01

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

  14. Poliovirus retention in soil columns after application of chemical- and polyelectrolyte-conditioned dewatered sludges.

    PubMed Central

    Pancorbo, O C; Bitton, G; Farrah, S R; Gifford, G E; Overman, A R

    1988-01-01

    The transport of poliovirus type 1 (strain LSc) was studied in Red Bay sandy loam columns that were treated with chemical- or polyelectrolyte-conditioned dewatered sludges and then leached with natural rainwater under saturated flow conditions. Poliovirus was concentrated in the alum and ferric chloride sludges that were produced following the flocculation of virus-seeded raw sewage. Virtually complete inactivation of the virus was observed following the flocculation of raw sewage or the stabilization of alum and ferric chloride sludges with lime at pH 11.5. Poliovirus was also concentrated in polyelectrolyte-conditioned dewatered sludge that was produced from virus-seeded, anaerobically digested sludge. Despite the saturated flow conditions for a sustained period, no viruses were detected in the leachates of the soil columns that were treated with these chemical and chemically treated sludges. Since the viruses were mostly associated with the solids in these sludge samples, it is believed that they were immobilized along with the sludge solids in the top portion of the soil columns. PMID:2830848

  15. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers observed during aqueous phase processing.

  16. APPLICATION OF THE TRADESCANTIA MICRONUCLEUS ASSAY FOR THE GENETIC EVALUATION OF CHEMICAL MIXTURES IN SOIL AND AQUEOUS MEDIA

    EPA Science Inventory

    Genotoxic evaluation of nine binary and one tertiary mixtures of arsenic trioxide, dieldrin, and lead tetraacetate were performed using the Tradescantia micronucleus (Trad-MN) assay. he chemical mixtures were either (I) mixed into soil, and chemical exposure to the target cells w...

  17. Corrosion phenomena of alloy 625 in aqueous solutions containing sulfuric acid and oxygen under subcritical and supercritical conditions

    SciTech Connect

    Kritzer, P.; Boukis, N.; Dinjus, E. [Forschungszentrum Karlsruhe (Germany)

    1998-12-31

    Corrosion phenomena of alloy 625 pressure tubes were investigated in aqueous solutions containing up to 0.2 mol/kg sulfuric acid and up to 1.44 mol/kg oxygen. Applied maximum temperatures and pressures were 500 C, and 38 MPa, respectively. Corrosion started at temperatures around 150 C with intergranular attack. Above 250 C, the whole surface of the alloy was attacked, shallow pits and deep intergranular attack appeared. This behavior can be explained by transpassive dissolution of the protecting Cr(III) oxide layer and leads to severe material loss. The upper temperature limit of severe corrosion at an experimental pressure of 24 MPa was about 390 C. As temperature was increased further and the density of the solution dropped to low values, only slight corrosion was detected.

  18. 117 I. A. Aksay, 6.E. Hoge, andd. A. Pask Wetting under Chemical Equilibrium and Nonequilibrium Conditions

    E-print Network

    Aksay, Ilhan A.

    117 I. A. Aksay, 6.E. Hoge, andd. A. Pask Wetting under Chemical Equilibrium and Nonequilibrium equilibrium and nonequilibri- um conditions, based on the model of Gibbs, is discussed. Under chemical of mechanical equilibrium, the sysitem was assumed to be at chemical equilibrium, E 17 I no mass transport

  19. On the performance of quantum chemical methods to predict solvatochromic effects: The case of acrolein in aqueous solution

    NASA Astrophysics Data System (ADS)

    Aidas, Kestutis; Møgelhøj, Andreas; Nilsson, Elna J. K.; Johnson, Matthew S.; Mikkelsen, Kurt V.; Christiansen, Ove; Söderhjelm, Pär; Kongsted, Jacob

    2008-05-01

    The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n ??* and ? ??* electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n ??* excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the ? ??* electronic transition in solution, whereas the recent CAM-B3LYP functional performs well also in this case. The ? ??* excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental data.

  20. What Hydra can teach us about chemical ecology -how a simple, soft organism survives in a hostile aqueous environment.

    PubMed

    Rachamim, Tamar; Sher, Daniel

    2012-01-01

    Hydra and its fellow cnidarians - sea anemones, corals and jellyfish - are simple, mostly sessile animals that depend on bioactive chemicals for survival. In this review, we briefly describe what is known about the chemical armament of Hydra, and detail future research directions where Hydra can help illuminate major questions in chemical ecology, pharmacology, developmental biology and evolution. Focusing on two groups of putative toxins from Hydra - phospholipase A2s and proteins containing ShK and zinc metalloprotease domains, we ask: how do different venom components act together during prey paralysis? How is a venom arsenal created and how does it evolve? How is the chemical arsenal delivered to its target? To what extent does a chemical and biotic coupling exist between an organism and its environment? We propose a model whereby in Hydra and other cnidarians, bioactive compounds are secreted both as localized point sources (nematocyte discharges) and across extensive body surfaces, likely combining to create complex "chemical landscapes". We speculate that these cnidarian-derived chemical landscapes may affect the surrounding community on scales from microns to, in the case of coral reefs, hundreds of kilometers. PMID:22689366

  1. Chemical conditioning of electrode reservoirs during electrokinetic soil flushing of Pb-contaminated silt loam

    Microsoft Academic Search

    Brian E. Reed; Mitchell T. Berg; J. H. Hatfield; J. C. Thompson

    1995-01-01

    The in-situ remediation of a lead-contaminated soil (silt loam, K{sub H} = 5 à 10⁻⁸ cm\\/s, soil Pb = 1,000 mg\\/kg) by electrokinetic (EK) soil flushing [60 V (DC)] was studied. Research focused on the chemical conditioning of the electrode reservoirs with either 500 μS\\/cm (as NaNOâ, baseline behavior), acetic acid (HAc), HCl, or EDTA. For baseline tests there were

  2. Differentiation of Human Embryonic Stem Cells to Regional Specific Neural Precursors in Chemically Defined Medium Conditions

    Microsoft Academic Search

    Slaven Erceg; Sergio Laínez; Mohammad Ronaghi; Petra Stojkovic; Maria Amparo Pérez-Aragó; Victoria Moreno-Manzano; Rubén Moreno-Palanques; Rosa Planells-Cases; Miodrag Stojkovic; Joseph Najbauer

    2008-01-01

    BackgroundHuman embryonic stem cells (hESC) provide a unique model to study early events in human development. The hESC-derived cells can potentially be used to replace or restore different tissues including neuronal that have been damaged by disease or injury.Methodology and Principal FindingsThe cells of two different hESC lines were converted to neural rosettes using adherent and chemically defined conditions. The

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

    DOEpatents

    Hames, Bonnie R. (Westminster, CO); Sluiter, Amie D. (Arvada, CO); Hayward, Tammy K. (Broomfield, CO); Nagle, Nicholas J. (Broomfield, CO)

    2004-05-18

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

  4. X-ray Absorption Spectroscopy Study of Solvation and Ion-Pairing in Aqueous Gallium Bromide Solutions at Supercritical Conditions

    E-print Network

    Paris-Sud XI, Université de

    Solutions at Supercritical Conditions Cécile Da Silvaa , Olivier Prouxb , Jean-Louis Hazemanna , Julianne.proux@grenoble.cnrs.fr Keywords: gallium bromide solution; ion solvation, ion pairing; supercritical fluids Abstract X at ambient conditions, supercritical water (SCW) is unique in that it exhibits both gas-like and liquid

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

    PubMed

    Kröger, Robert; Moore, Matthew T

    2011-01-01

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

  6. Mercury removal from aqueous and organo-aqueous solutions by natural Mexican erionite

    Microsoft Academic Search

    B. Y. Moreno-Gutiérrez; M. T. Olguín

    2003-01-01

    The sorption of Hg(II) from aqueous and organo aqueous solutions was investigated by Mexican natural erionite. The mercury chemical species (anionic, cationic or neutral) were determined by high voltage electrophoresis, and the mercury chemical species present in the aqueous media were simulated by a program MEDUSA. The mercury sorption process was monitored during 48 hours. The mercury content was determined

  7. Stability of an Aqueous Quadrupole Micro-Trap

    PubMed Central

    Park, Jae Hyun; Krsti?, Predrag S.

    2011-01-01

    Recently demonstrated functionality of an aqueous quadrupole micro- or nano-trap opens a new avenue for applications of the Paul traps, like is confinement of a charged biomolecule which requires water environment for its chemical stability. Besides strong viscosity forces, motion of a charged particle in the aqueous trap is subject to dielectrophoretic and electrophoretic forces. In this study, we describe the general conditions for stability of a charged particle in an aqueous quadrupole trap. We find that for the typical micro-trap parameters, effects of both dielectrophoresis and electrophoresis significantly influence the trap stability. In particular, the aqueous quadrupole trap could play of a role of a synthetic virtual nanopore for the 3rd generation of DNA sequencing technology. PMID:22466254

  8. Metabolism and dissipation kinetics of a novel protoporphyrinogen IX oxidase herbicide [oxadiargyl] in various buffered aqueous system under laboratory-simulated condition.

    PubMed

    Sanyal, Nilanjan; Alam, Samsul; Pradhan, Saswati; Banerjee, Kaushik; Chowdhury, Ashim; Aktar, Md Wasim

    2015-07-01

    Present investigation was carried out using two commercial products Raft (oxadiargyl 6 % EC) and Topstar (oxadiargyl 80 % WP) of Oxadiargyl {5-tert-butyl-3[2,4-dichloro-5-(prop-2-ynyloxy)phenyl]-1,3,4-oxadiazol-2 (3H)-one} to investigate the persistence behavior and metabolism of the herbicide in various aqueous system under different pH condition. Half-life values revealed that alkaline hydrolysis played a dominant role in hydrolytic degradation of this compound. Q-ToF micromass study with the alkaline fractions of oxadiargyl indicated the formation of five metabolites, which was further characterized from their mass fragmentation data. The nature of metabolites formed indicated that heterocyclic oxadiazoline ring cleavage was found to be the main pathway of hydrolytic transformation of oxadiargyl. PMID:26077021

  9. Chemical erosion of different carbon composites under ITER-relevant plasma conditions

    NASA Astrophysics Data System (ADS)

    Westerhout, J.; Borodin, D.; Al, R. S.; Brezinsek, S.; 't Hoen, M. H. J.; Kirschner, A.; Lisgo, S.; van der Meiden, H. J.; Philipps, V.; van de Pol, M. J.; Shumack, A. E.; De Temmerman, G.; Vijvers, W. A. J.; Wright, G. M.; Lopes Cardozo, N. J.; Rapp, J.; van Rooij, G. J.

    2009-12-01

    We have studied the chemical erosion of different carbon composites in Pilot-PSI at ITER-relevant hydrogen plasma fluxes (~1024 m-2 s-1) and low electron temperatures (Te~1 eV). Optical emission spectroscopy on the CH A-X band was used to characterize the chemical sputtering. Fine grain graphite (R 6650, SGL Carbon Group), ITER-reference carbon fiber composite material (SNECMA NB31 and NB41; Dunlop 3D), nano- and micro-crystalline diamond coatings on molybdenum and SiC (Silit® SKD Reaction-Bonded, Saint-Gobain Ceramics) were compared. The chemical sputtering was similar for the different composites under comparable plasma conditions, except for SiC, which produced a ten times lower rate. The CH emission was constant at electron temperatures Te>1 eV and ion fluxes ranging between 1023 and 1024 m- 2 s-1, but decreased at lower temperatures. This decrease is possibly due to changes in the excitation of CH and not due to a change in the chemical erosion rate.

  10. Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions

    Microsoft Academic Search

    Katherine M. MullaughGeorge; George W. Luther

    2011-01-01

    The ubiquity of naturally occurring nanoparticles in the aquatic environment is now widely accepted, but a better understanding\\u000a of the conditions that promote their formation and persistence is needed. Using cadmium sulfide (CdS) as a model metal sulfide\\u000a species, thiolate-capped CdS nanoparticles were prepared in the laboratory to evaluate how aquatic conditions influence metal\\u000a sulfide nanoparticle growth and stability. This

  11. Chemical changes during anaerobic decomposition of hardwood, softwood, and old newsprint under mesophilic and thermophilic conditions.

    PubMed

    De la Cruz, Florentino B; Yelle, Daniel J; Gracz, Hanna S; Barlaz, Morton A

    2014-07-01

    The anaerobic decomposition of plant biomass is an important aspect of global organic carbon cycling. While the anaerobic metabolism of cellulose and hemicelluloses to methane and carbon dioxide are well-understood, evidence for the initial stages of lignin decomposition is fragmentary. The objective of this study was to look for evidence of chemical transformations of lignin in woody tissues [hardwood (HW), softwood (SW), and old newsprint (ONP)] after anaerobic decomposition using Klason and acid-soluble lignin, CuO oxidation, and 2D NMR. Tests were conducted under mesophilic and thermophilic conditions, and lignin associations with structural carbohydrates are retained. For HW and ONP, the carbon losses could be attributed to cellulose and hemicelluloses, while carbon loss in SW was attributable to an uncharacterized fraction (e.g., extractives etc.). The 2D NMR and chemical degradation methods revealed slight reductions in ?-O-4 linkages for HW and ONP, with no depolymerization of lignin in any substrate. PMID:24967726

  12. Chemical immobilization of crested porcupines with tiletamine HCl and zolazepam HCl (Zoletil) under field conditions.

    PubMed

    Massolo, Alessandro; Sforzi, Andrea; Lovari, Sandro

    2003-07-01

    The combination of tiletamine HCl and zolazepam HCl has been used on many species of wild mammals. Short induction time, low dosage, satisfactory safety margins, relatively constant immobilization time, and smooth recovery are benefits reported. This combination (Zoletil 100) was used during a study on behavioural ecology of the crested porcupine (Hystrix cristata) in a Mediterranean coastal area (Maremma Regional Park, Tuscany, Italy). We used this mixture 42 times on 31 individuals. Mean adult dose was (+/- SE) 7.24 +/- 0.37 mg/kg (74.0 +/- 3.0 mg/individual). Average adult induction time was 5.3 min (+/- 1.1) and average adult immobilization time was 22.6 min (+/- 6.0). One adult male porcupine died after chemical restraints. The use of tiletamine-zolazepam seems adequate for chemical immobilization of crested porcupines under field conditions, mainly because of its short induction time, small volume to be injected and wide safety margin. PMID:14567239

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

    SciTech Connect

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

    1990-10-04

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

  14. Nitrosation of Nigerian medicinal plant preparations under 'chemical' and 'simulated' gastric conditions.

    PubMed

    Atawodi, S E; Lamorde, A G; Spiegelhalder, B; Preussmann, R

    1995-01-01

    Preparations of some tropical plants of medicinal importance, collected from the savannah vegetational belt of Nigeria, were nitrosated and analysed for volatile N-nitrosamines formed under chemical and simulated gastric conditions. N-Nitrosamines were determined on a Thermal Energy Analyser following gas chromatographic separation. Mean concentrations of N-nitrosodimethylamine (NDMA) in the range of 7 to 58 ppb and N-nitrosodiethylamine (NDEA) in the range of 23 to 26 ppb were formed in 31 and 7%, respectively, of the preparations using artificial gastric juice (simulated gastric condition). Under chemically optimal conditions, relatively high levels of NDMA (72-2008 ppb), NDEA (23-1528 ppb) and N-nitrosopyrrolidine (20-405 ppb) were formed in 100, 75 and 32% of the preparations, respectively; N-nitrosomethylethylamine, N-nitrosodibutylamine and N-nitrosomorpholine were formed in fewer preparations. These findings suggest that the endogenous formation of N-nitroso compounds from precursors present in medicinal plants might be another source of human exposure to environmental carcinogens in Nigeria and other developing countries. PMID:7821876

  15. Radiation-induced degradation of carboxymethylated chitosan in aqueous solution

    Microsoft Academic Search

    Ling Huang; Maolin Zhai; Jing Peng; Jiuqiang Li; Genshuan Wei

    2007-01-01

    Aqueous solutions of carboxymethylated chitosan (CM-chitosan) were radiated with ?-ray in various conditions. The degradations of CM-chitosan were faster in the presence of nitrous oxide or hydrogen peroxide, but it was inhibited obviously after adding isopropanol because of the changes of the concentration of hydroxyl radicals in above different conditions. The radiation chemical yields of CM-chitosan degradation were found to

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

    PubMed

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

    2014-02-01

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

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

    PubMed Central

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

    2014-01-01

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

  18. Adsorption of Procion Blue MX-R dye from aqueous solutions by lignin chemically modified with aluminium and manganese.

    PubMed

    Adebayo, Matthew A; Prola, Lizie D T; Lima, Eder C; Puchana-Rosero, M J; Cataluña, Renato; Saucier, Caroline; Umpierres, Cibele S; Vaghetti, Julio C P; da Silva, Leandro G; Ruggiero, Reinaldo

    2014-03-15

    A macromolecule, CML, was obtained by purifying and carboxy-methylating the lignin generated from acid hydrolysis of sugarcane bagasse during bioethanol production from biomass. The CMLs complexed with Al(3+) (CML-Al) and Mn(2+) (CML-Mn) were utilised for the removal of a textile dye, Procion Blue MX-R (PB), from aqueous solutions. CML-Al and CML-Mn were characterised using Fourier transform infrared spectroscopy (FTIR), scanning differential calorimetry (SDC), scanning electron microscopy (SEM) and pHPZC. The established optimum pH and contact time were 2.0 and 5h, respectively. The kinetic and equilibrium data fit into the general order kinetic model and Liu isotherm model, respectively. The CML-Al and CML-Mn have respective values of maximum adsorption capacities of 73.52 and 55.16mgg(-1) at 298K. Four cycles of adsorption/desorption experiments were performed attaining regenerations of up to 98.33% (CML-Al) and 98.08% (CML-Mn) from dye-loaded adsorbents, using 50% acetone+50% of 0.05molL(-1) NaOH. The CML-Al removed ca. 93.97% while CML-Mn removed ca. 75.91% of simulated dye house effluents. PMID:24462989

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

    NASA Technical Reports Server (NTRS)

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

  3. A nondestructive electrochemical method to detect and quantify graphite fiber\\/polymer matrix disbondment in aqueous and cathodically polarized conditions

    Microsoft Academic Search

    S. R. Taylor

    1994-01-01

    In certain engineering applications, graphite fiber polymer matrix composites may be exposed to both moisture and electrochemical polarization. The combined effect to these environmental conditions can cause fiber\\/matrix interfacial breakdown and matrix degradation. In previous research, electrochemical impedance spectroscopy (EIS) was used to examine the effects of electrochemical polarization on bismaleimide (BMI)\\/graphite fiber (GF) composites, and revealed changes in the

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

    PubMed

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

    2013-07-01

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

  5. Assessment of existing H2/O2 chemical reaction mechanisms at reheat gas turbine conditions

    E-print Network

    Weydahl, Torleif; Seljeskog, Morten; Haugen, Nils Erland L

    2011-01-01

    This paper provides detailed comparisons of chemical reaction mechanisms of H2 applicable at high preheat temperatures and pressures relevant to gas turbine and particularly Alstom's reheat gas turbine conditions. It is shown that the available reaction mechanisms exhibit large differences in several important elementary reaction coefficients. The reaction mechanisms are assessed by comparing ignition delay and laminar flame speed results obtained from CHEMKIN with available data, however, the amount of data at these conditions is scarce and a recommended candidate among the mechanisms can presently not be selected. Generally, the results with the GRI-Mech and Leeds mechanisms deviate from the Davis, Li, O'Conaire, Konnov and San Diego mechanisms, but there are also significant deviations between the latter five mechanisms that altogether are better adapted to hydrogen. The differences in ignition delay times between the dedicated hydrogen mechanisms (O'Conaire, Li and Konnov) range from approximately a maxim...

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

    PubMed

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

    2015-03-01

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

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

    PubMed Central

    2015-01-01

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

  8. DETERMINATION OF PHTHALATES IN WATER AND SOIL BY TANDEM MASS SPECTROMETRY UNDER CHEMICAL IONIZATION CONDITIONS WITH ISOBUTANE AS REAGENT GAS

    EPA Science Inventory

    Phthalate determination is important because phthalates often are major impurities in samples and can have significant health effects. Tandem mass spectrometry under chemical ionization mass spectrometry conditions with isobutane as the reagent gas was used to determine 11 phthal...

  9. Physico-chemical characterization of steel slag. Study of its behavior under simulated environmental conditions.

    PubMed

    Navarro, Carla; Díaz, Mario; Villa-García, María A

    2010-07-15

    The chemical and mineralogical composition of steel slag produced in two ArcelorMittal steel plants located in the North of Spain, as well as the study of the influence of simulated environmental conditions on the properties of the slag stored in disposal areas, was carried out by elemental chemical analysis, XRF, X-ray diffraction, thermal analysis, and scanning electron microscopy with EDS analyzer. Spectroscopic characterization of the slag was also performed by using FTIR spectroscopy. Due to the potential uses of the slag as low cost adsorbent for water treatment and pollutants removal, its detailed textural characterization was carried out by nitrogen adsorption-desorption at 77 K and mercury intrusion porosimetry. The results show that the slag is a crystalline heterogeneous material whose main components are iron oxides, calcium (magnesium) compounds (hydroxide, oxide, silicates, and carbonate), elemental iron, and quartz. The slags are porous materials with specific surface area of 11 m(2)g(-1), containing both mesopores and macropores. Slag exposure to simulated environmental conditions lead to the formation of carbonate phases. Carbonation reduces the leaching of alkaline earth elements as well as the release of the harmful trace elements Cr (VI) and V. Steel slags with high contents of portlandite and calcium silicates are potential raw materials for CO(2) long-term storage. PMID:20568743

  10. Photoelectrochemical (PEC) characterization of chemically deposited Bi 2S 3 thin films from non-aqueous medium

    Microsoft Academic Search

    R. S Mane; B. R Sankapal; C. D Lokhande

    1999-01-01

    Bi2S3 thin films have been prepared by chemical bath deposition method using bismuth nitrate, Bi(NO3)3 and sodium thiosulphate (Na2S2O3) dissolved in acetic acid and formaldehyde respectively. Films were deposited onto flourine doped tin oxide coated (FTO) glass substrates. The photoelectrochemical (PEC) cell configuration was n-Bi2S3\\/0.25MNaOH–0.25MNa2S–0.25M S\\/C. From the current–voltage characteristics (I–V) and capacitance–voltage (C–V) plots, it is concluded that the

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

    SciTech Connect

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

    1991-03-01

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

  12. Greener Syntheses and Chemical Transformations: Sustainable Alternative Methods and Applications of Nano-Catalysts. (Florence, Italy)

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions. The synthesis of heterocyclic compounds, coupling reactions, and a vari...

  13. Sustainable 'Greener' Methods for Chemical Transformations and Applications of Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 Synthesis of heterocyclic compounds, coupling reactions, and name reac...

  14. Greener Syntheses and Chemical Transformations Using SustainableAlternative Methods and Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, namely greener reaction medium in aqueous or solventfree conditions and using alternative activation via microwave or photocatalytic activation. Eco-friendly synthesis of nanoma...

  15. Greener Synthesis and Chemical transformations Using Sustainable Alternative Methods and Applications of Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, namely greener reaction medium in aqueous or solventfree conditions and using alternative activation via microwave or photocatalytic activation. Eco-friendly synthesis of nanoma...

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

    PubMed

    Lalhmunsiama; Tiwari, Diwakar; Lee, Seung-Mok

    2015-09-01

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

  17. Application of Zero-Valent Iron Nanoparticles for the Removal of Aqueous Zinc Ions under Various Experimental Conditions

    PubMed Central

    Liang, Wen; Dai, Chaomeng; Zhou, Xuefei; Zhang, Yalei

    2014-01-01

    Application of zero-valent iron nanoparticles (nZVI) for Zn2+ removal and its mechanism were discussed. It demonstrated that the uptake of Zn2+ by nZVI was efficient. With the solids concentration of 1 g/L nZVI, more than 85% of Zn2+ could be removed within 2 h. The pH value and dissolved oxygen (DO) were the important factors of Zn2+ removal by nZVI. The DO enhanced the removal efficiency of Zn2+. Under the oxygen-contained condition, oxygen corrosion gave the nZVI surface a shell of iron (oxy)hydroxide, which could show high adsorption affinity. The removal efficiency of Zn2+ increased with the increasing of the pH. Acidic condition reduced the removal efficiency of Zn2+ by nZVI because the existing H+ inhibited the formation of iron (oxy)hydroxide. Adsorption and co-precipitation were the most likely mechanism of Zn2+ removal by nZVI. The FeOOH-shell could enhance the adsorption efficiency of nZVI. The removal efficiency and selectivity of nZVI particles for Zn2+ were higher than Cd2+. Furthermore, a continuous flow reactor for engineering application of nZVI was designed and exhibited high removal efficiency for Zn2+. PMID:24416439

  18. [Adsorption of calcium ion from aqueous solution using Na(+)-conditioned clinoptilolite for hot-water softening].

    PubMed

    Zhang, Shuo; Wang, Dong; Chen, Yuan-Chao; Zhang, Xing-Wen; Chen, Gui-Jun

    2015-02-01

    This work investigated adsorptive removal of calcium ion (Ca2+) by virtue of Na(+) -conditioned clinoptilolite simulating the process of softening for industrial hot-water system. Influential factors such as the activation/regeneration of sorbent and solution pH were tested. The kinetics/thermodynamics for adsorption of Ca2+ were analyzed and discussed. Results showed that: (1) The adsorption rate was in good agreement with the pseudo-second order kinetic models, and the process of adsorption better followed the Langmuir model; (2) Higher solution temperature allowed an enhanced efficiency on Ca2+ removal, albeit the maximum adsorption capacity of Na(+)-conditioned clinoptilolite was hardly affected; (3) The process of adsorption was dominated by chemisorption, and also characterized by entropy increase with spontaneous/endothermic nature; (4) Solution temperature was suggested to be controlled within the range of 6 to 10, and more than 9 times of sorbent regeneration could be ensured for an effective adsorption towards Ca2+ with initial concentration less than 20 mg x L(-1). It was demonstrated that the activated clinoptilolite should be a promising alternative adsorbent for industrial hot-water softening. PMID:26031107

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

    SciTech Connect

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I-Ming (SMSU); (Cornell); (SFX); (USGS)

    2008-09-25

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500 C and at pressures up to 480 MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L{sub 3}-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO{sub 3} aqueous solution at temperatures up to 500 C and at pressures up to 260 MPa shows that the Gd-O distance of the Gd{sup 3+} aqua ion decreases steadily at a rate of {approx} 0.007 {angstrom}/100 C whereas the number of coordinated H{sub 2}O molecules decreases from 9.0 {+-} 0.5 to 7.0 {+-} 0.4. The loss of water molecules in the Gd{sup 3+} aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb{sup 3+} aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd{sup 3+} aqua ion relative to other REEs. Gd L{sub 3}-edge XAFS measurements of 0.006m and 0.1m GdCl{sub 3} aqueous solutions at temperatures up to 500 C and pressures up to 480 MPa reveal that the onset of significant Gd{sup 3+}-Cl{sup -} association occurs around 300 C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} occur in the chloride solutions at higher temperatures, where {delta} {approx} 8 at 300 C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500 C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb{sup 3+} aquo ion and chloro complexes in aqueous solutions at up to 500 C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 {+-} 0.2 to 1.7 {+-} 0.3 in the 0.006m chloride solution and from 0.9 {+-} 0.7 to 1.8 {+-} 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500 C range. Conversely, the number of H{sub 2}O ligands of Gd(H{sub 2}O){sub {delta}-n}Cl{sub n}{sup +3-n} complexes decreases steadily from 8.9 {+-} 0.4 to 5.8 {+-} 0.7 in the 0.006m GdCl{sub 3} aqueous solution and from 9.0 {+-} 0.5 to 5.3 {+-} 1.0 in the 0.1m GdCl{sub 3} aqueous solution at temperatures from 25 to 500 C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH{sub 2} bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction ({approx} 0.005 {angstrom}/100 C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids.

  20. Use of chemically derivatized n-type silicon photoelectrodes in aqueous media: photooxidation of iodide, hexacyanoiron(II), and hexaammineruthenium(II) at ferrocene-derivatized photoanodes

    Microsoft Academic Search

    Andrew B. Bocarsly; Erick G. Walton; Mark S. Wrighton

    1980-01-01

    A procedure is described for the chemical derivatization of the surface of n-type semiconductor photoanodes to yield photosensitive interfaces for use in a large number of thermodynamically uphill oxidation processes. (1,1'-ferrocenediyl)dichlorosilane was used to derivatize n-type Si to yield a photoanode that can be used under conditions where the naked (nonderivatized) n-type Si undergoes photoanodic corrosion yielding an insulating SiO\\/sub

  1. Chitosan use in chemical conditioning for dewatering municipal-activated sludge.

    PubMed

    Zemmouri, H; Mameri, N; Lounici, H

    2015-01-01

    This work aims to evaluate the potential use of chitosan as an eco-friendly flocculant in chemical conditioning of municipal-activated sludge. Chitosan effectiveness was compared with synthetic cationic polyelectrolyte Sedipur CF802 (Sed CF802) and ferric chloride (FeCl3). In this context, raw sludge samples from Beni-Messous wastewater treatment plant (WWTP) were tested. The classic jar test method was used to condition sludge samples. Capillary suction time (CST), specific resistance to filtration (SRF), cakes dry solid content and filtrate turbidity were analyzed to determine filterability, dewatering capacity of conditioned sludge and the optimum dose of each conditioner. Data exhibit that chitosan, FeCl3 and Sed CF802 improve sludge dewatering. Optimum dosages of chitosan, Sed CF802 and FeCl3 allowing CST values of 6, 5 and 9 s, were found, respectively, between 2-3, 1.5-3 and 6 kg/t ds. Both polymers have shown faster water removal with more permeable sludge. SRF values were 0.634 × 10(12), 0.932 × 10(12) and 2 × 10(12) m/kg for Sed CF802, chitosan and FeCl3 respectively. A reduction of 94.68 and 87.85% of the filtrate turbidity was obtained with optimal dosage of chitosan and Sed CF802, respectively. In contrast, 54.18% of turbidity abatement has been obtained using optimal dosage of FeCl3. PMID:25812088

  2. Experimental investigation and planetary implications of the stability of clathrate hydrates in aqueous solution at icy satellite conditions

    NASA Astrophysics Data System (ADS)

    Dunham, M.; Choukroun, M.; Barmatz, M.; Hodyss, R. P.; Smythe, W. D.

    2012-12-01

    Clathrate hydrates consist of hydrogen-bonded water molecules forming cages in which gas molecules are trapped individually. They are among the favored volatile reservoirs in solar system bodies, and are expected to play an important role in many processes: accretion of volatiles in planetesimals, outgassing on Titan, Enceladus, and comets. Their insulating thermal properties and high mechanical strength also bear important implications for understanding the evolution of icy satellites like Europa. However, the conditions allowing for their formation and/or their dissociation and the release of volatiles to the atmosphere (Titan) or the plumes (Enceladus) are still poorly understood. This is mainly because of a lack of knowledge on the stability of mixed clathrate hydrates in presence of anti-freeze agents such as ammonia. We have developed a high-pressure cryogenic calorimeter to address this deficiency in the literature. This liquid nitrogen - cooled Setaram BT2.15 calorimeter is located at the JPL Ice Physics Laboratory. The temperature range achievable with this instrument is 77-473 K. This calorimeter uses Calvet elements (3D arrays of thermocouples) to measure the heat flow required to follow a predefined heating rate within a sample and a reference cell with a resolution of 0.1 ?W. A gas handling system has been designed and fabricated in house to reach pressures up to 100 bars, corresponding to several km depth in icy satellites. The thermodynamic properties of CO2 and CH4 clathrates with ammonia are under investigation, and the results will be used to constrain a statistical thermodynamic model of clathrates for applications to planetary environments. Preliminary results will be shown at the meeting. This work has been conducted at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Support from the Minnesota Space Grant Consortium, the NASA Outer Planets Research program, and government sponsorship are gratefully acknowledged.

  3. Soil structure, colloids, and chemical transport as affected by short-term reducing conditions: a laboratory study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Upland soils in the Midwestern US often undergo reducing conditions when soils are temporally flooded during the spring and remain water saturated for days or weeks. Short-term reducing conditions change the chemistry of the soil and may affect soil structure and solution chemical transport. The eff...

  4. Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

    NASA Technical Reports Server (NTRS)

    Johnson, R. E.

    1986-01-01

    Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

  5. A Molecular Dynamics Study of Chemical Reactions of Solid Pentaerythritol Tetranitrate at Extreme Conditions

    SciTech Connect

    Wu, C J; Manaa, M R; Fried, L E

    2006-05-30

    We have carried out density functional based tight binding (DFTB) molecular dynamics (MD) simulation to study energetic reactions of solid Pentaerythritol Tetranitrate (PETN) at conditions approximating the Chapman-Jouguet (CJ) detonation state. We found that the initial decomposition of PETN molecular solid is characterized by uni-molecular dissociation of the NO{sub 2}groups. Interestingly, energy release from this powerful high explosive was found to proceed in several stages. The large portion of early stage energy release was found to be associated with the formation of H{sub 2}O molecules within a few picoseconds of reaction. It took nearly four times as long for majority of CO{sub 2} products to form, accompanied by a slow oscillatory conversion between CO and CO{sub 2}. The production of N{sub 2} starts after NO{sub 2} loses its oxygen atoms to hydrogen or carbon atoms to form H{sub 2}O or CO. We identified many intermediate species that emerge and contribute to reaction kinetics, and compared our simulation with a thermo-chemical equilibrium calculation. In addition, a detailed chemical kinetics of formation of H{sub 2}O, CO, and CO{sub 2} were developed. Rate constants of formations of H{sub 2}O, CO{sub 2} and N{sub 2} were reported.

  6. Efficient and selective chemical transformations under flow conditions: The combination of supported catalysts and supercritical fluids

    PubMed Central

    Burguete, M Isabel; García-Verdugo, Eduardo

    2011-01-01

    Summary This paper reviews the current trends in the combined use of supported catalytic systems, either on solid supports or in liquid phases and supercritical fluids (scFs), to develop selective and enantioselective chemical transformations under continuous and semi-continuous flow conditions. The results presented have been selected to highlight how the combined use of those two elements can contribute to: (i) Significant improvements in productivity as a result of the enhanced diffusion of substrates and reagents through the interfaces favored by the scF phase; (ii) the long term stability of the catalytic systems, which also contributes to the improvement of the final productivity, as the use of an appropriate immobilization strategy facilitates catalyst isolation and reuse; (iii) the development of highly efficient selective or, when applicable, enantioselective chemical transformations. Although the examples reported in the literature and considered in this review are currently confined to a limited number of fields, a significant development in this area can be envisaged for the near future due to the clear advantages of these systems over the conventional ones. PMID:22043246

  7. Chemical and toxicological evaluation of an emerging pollutant (enrofloxacin) by catalytic wet air oxidation and ozonation in aqueous solution.

    PubMed

    Li, Yan; Zhang, Feifang; Liang, Xinmiao; Yediler, Ayfer

    2013-01-01

    This study evaluates the degradation efficiency of enrofloxacin (ENR) by catalytic wet air oxidation (CWAO) and ozonation. Results obtained by CWAO experiments show that 99.5% degradation, 37.0% chemical oxidation demand (COD) removal and 51.0% total organic carbon (TOC) conversion were obtained when 100 mol% FeCl(3) and 25 mol% NaNO(2) at 150 °C under 0.5 MPa oxygen pressure after 120 min are used. The degradation products are identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC). The oxidation end products, F(-), NO(3)(-) and NH(4)(+) were determined by IC. The BOD(5)/COD ratio as a measure of the biodegradability of the parent compound increased from 0.01 to 0.12 after 120 min of reaction time, indicating an improved biodegradability of the parent compound. The inhibition of bioluminescence of the marine bacteria V. fischeri decreased from 43% to 12% demonstrating a loss in toxicity of ENR during CWAO. Ozonation of 0.2 mM ENR was carried out with an ozone concentration of 7.3 g m(-3) at pH 7. ENR decomposition with a degradation rate of 87% was obtained corresponding to the reaction time. Moderate changes in COD (18%) and TOC (17%) removal has been observed. The bioluminescence inhibition increased from 8% to 50%, due to the generation of toxic degradation products during ozonation. In comparison to the widely use of well developed method of ozonation CWAO exhibits better performance in terms of COD, TOC removals and generates less toxic products. PMID:22858256

  8. Application of high resolution Chemical Ionization Mass Spectrometry (CI-ToFMS) to study SOA composition: focus on formation of oxygenated species via aqueous phase processing

    NASA Astrophysics Data System (ADS)

    Aljawhary, D.; Lee, A. K. Y.; Abbatt, J. P. D.

    2013-07-01

    This paper demonstrates the capabilities of Chemical Ionization Mass Spectrometry (CIMS) to study secondary organic aerosol (SOA) composition with a high resolution (HR) time-of-flight mass analyzer (aerosol-CI-ToFMS). In particular, by studying aqueous oxidation of Water Soluble Organic Compounds (WSOC) extracted from ?-pinene ozonolysis SOA, we assess the capabilities of three common CIMS reagent ions: (a) protonated water clusters (H2O)nH+, (b) acetate CH3C(O)O- and (c) iodide water clusters I(H2O)n- to monitor SOA composition. As well, we report the relative sensitivity of these reagent ions to a wide range of common organic aerosol constituents. We find that (H2O)nH+ is more selective to the detection of less oxidized species, so that the range of O/C and OSC (carbon oxidation state) in the SOA spectra is considerably lower than those measured using CH3C(O)O- and I(H2O)n-. Specifically, (H2O)nH+ ionizes organic compounds with OSC ? 1.3, whereas CH3C(O)O- and I(H2O)n- both ionize highly oxygenated organics with OSC up to 4 with I(H2O)n- being more selective towards multi-functional organic compounds. In the bulk O/C and H/C space, i.e. in a Van Krevelen plot, there is a remarkable agreement in both absolute magnitude and oxidation trajectory between CI-ToFMS data and those from a high resolution aerosol mass spectrometer (HR-AMS). This indicates that the CI-ToFMS data captures much of the chemical change occurring in the particle and that gas phase species, which are not detected by the HR-AMS, do not dominate the overall ion signal. Finally, the data illustrate the capability of aerosol-CI-ToFMS to monitor specific chemical change, including the fragmentation and functionalization reactions that occur during organic oxidation, and the oxidative conversion of dimeric SOA species into monomers. Overall, aerosol-CI-ToFMS is a valuable, selective complement to some common SOA characterization methods, such as AMS and spectroscopic techniques. Both laboratory and ambient SOA samples can be analyzed using the techniques illustrated in the paper.

  9. Atomistic Simulations of Chemical Reactivity of TATB Under Thermal and Shock Conditions

    SciTech Connect

    Manaa, M R; Reed, E J; Fried, L E

    2009-09-23

    The study of chemical transformations that occur at the reactive shock front of energetic materials provides important information for the development of predictive models at the grain-and continuum scales. A major shortcoming of current high explosives models is the lack of chemical kinetics data of the reacting explosive in the high pressure and temperature regimes. In the absence of experimental data, long-time scale atomistic molecular dynamics simulations with reactive chemistry become a viable recourse to provide an insight into the decomposition mechanism of explosives, and to obtain effective reaction rate laws. These rates can then be incorporated into thermo-chemical-hydro codes (such as Cheetah linked to ALE3D) for accurate description of the grain and macro scales dynamics of reacting explosives. In this talk, I will present quantum simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals under thermal decomposition (high density and temperature) and shock compression conditions. This is the first time that condensed phase quantum methods have been used to study the chemistry of insensitive high explosives. We used the quantum-based, self-consistent charge density functional tight binding method (SCC{_}DFTB) to calculate the interatomic forces for reliable predictions of chemical reactions, and to examine electronic properties at detonation conditions for a relatively long time-scale on the order of several hundreds of picoseconds. For thermal decomposition of TATB, we conducted constant volume-temperature simulations, ranging from 0.35 to 2 nanoseconds, at {rho} = 2.87 g/cm{sup 3} at T = 3500, 3000, 2500, and 1500 K, and {rho} = 2.9 g/cm{sup 3} and 2.72 g/cm{sup 3}, at T = 3000 K. We also simulated crystal TATB's reactivity under steady overdriven shock compression using the multi-scale shock technique. We conducted shock simulations with specified shock speeds of 8, 9, and 10 km/s for up to 0.43 ns duration, enabling us to track the reactivity of TATB well into the formation of several stable gas products, such as H{sub 2}O, N{sub 2}, and CO{sub 2}. Although complex chemical transformations are occurring continuously in the dynamical, high temperature, reactive environment of our simulations, a simple overall scheme for the decomposition of TATB emerges: Water is the earliest decomposition products to form, followed by a polymerization (or condensation) process in which several TATB remaining fragments are joined together, initiating the early step in the formation of high-nitrogen clusters, along with stable products such as N{sub 2} and CO{sub 2}. Remarkably, these clusters with high concentration of carbon and nitrogen (and little oxygen) remain dynamically stable for the remaining period of the simulations. Our simulations, thus, reveal a hitherto unidentified region of high concentrations of nitrogen-rich heterocyclic clusters in reacting TATB, whose persistence impede further reactivity towards final products of fluid N{sub 2} and solid carbon. These simulations also predict significant populations of charged species such as NCO{sup -}, H{sup +}, OH{sup -}, H{sub 3}O{sup +}, and O{sup -2}, the first such observation in a reacting explosive. Finally, A reduced four steps, global reaction mechanism with Arrhenius kinetic rates for the decomposition of TATB, along with comparative Cheetah decomposition kinetics at various temperatures has been constructed and will be discussed.

  10. Surface Studies of Niobium Chemically Polished Under Conditions for Superconducting Radio Frequency (SRF) Cavity Production

    SciTech Connect

    Tian,H.; Reece, C.; Kelley, M.; Wang, S.; Plucinski, L.; Smith, K.; Nowell, M.

    2006-01-01

    The performance of niobium superconducting radiofrequency (SRF) accelerator cavities is strongly impacted by the topmost several nanometers of the active (interior) surface, especially as influenced by the final surface conditioning treatments. We examined the effect of the most commonly employed treatment, buffered chemical polishing (BCP), on polycrystalline niobium sheet over a range of realistic solution flow rates using electron back scatter diffraction (EBSD), stylus profilometry, atomic force microscopy, laboratory XPS and synchrotron (variable photon energy) XPS, seeking to collect statistically significant datasets. We found that the predominant general surface orientation is (1 0 0), but others are also present and at the atomic-level details of surface plane orientation are more complex. The post-etch surface exhibits micron-scale roughness, whose extent does not change with treatment conditions. The outermost surface consists of a few-nm thick layer of niobium pentoxide, whose thickness increases with solution flow rate to a maximum of 1.3-1.4 times that resulting from static solution. The standard deviation of the roughness measurements is {+-}30% and that of the surface composition is {+-}5%.

  11. Discrimination of conspecific sex and reproductive condition using chemical cues in axolotls ( Ambystoma mexicanum).

    PubMed

    Park, D; McGuire, J M; Majchrzak, A L; Ziobro, J M; Eisthen, H L

    2004-05-01

    Chemosensory cues play an important role in the daily lives of salamanders, mediating foraging, conspecific recognition, and territorial advertising. We investigated the behavioral effects of conspecific whole-body odorants in axolotls, Ambystoma mexicanum, a salamander species that is fully aquatic. We found that males increased general activity when exposed to female odorants, but that activity levels in females were not affected by conspecific odorants. Although males showed no difference in courtship displays across testing conditions, females performed courtship displays only in response to male odorants. We also found that electro-olfactogram responses from the olfactory and vomeronasal epithelia were larger in response to whole-body odorants from the opposite sex than from the same sex. In males, odorants from gravid and recently spawned females evoked different electro-olfactogram responses at some locations in the olfactory and vomeronasal epithelia; in general, however, few consistent differences between the olfactory and vomeronasal epithelia were observed. Finally, post hoc analyses indicate that experience with opposite-sex conspecifics affects some behavioral and electrophysiological responses. Overall, our data indicate that chemical cues from conspecifics affect general activity and courtship behavior in axolotls, and that both the olfactory and vomeronasal systems may be involved in discriminating the sex and reproductive condition of conspecifics. PMID:15034733

  12. Molecules in interstellar clouds. [physical and chemical conditions of star formation and biological evolution

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Hjalmarson, A.; Rydbeck, O. E. H.

    1981-01-01

    The physical conditions and chemical compositions of the gas in interstellar clouds are reviewed in light of the importance of interstellar clouds for star formation and the origin of life. The Orion A region is discussed as an example of a giant molecular cloud where massive stars are being formed, and it is pointed out that conditions in the core of the cloud, with a kinetic temperature of about 75 K and a density of 100,000-1,000,000 molecules/cu cm, may support gas phase ion-molecule chemistry. The Taurus Molecular Clouds are then considered as examples of cold, dark, relatively dense interstellar clouds which may be the birthplaces of solar-type stars and which have been found to contain the heaviest interstellar molecules yet discovered. The molecular species identified in each of these regions are tabulated, including such building blocks of biological monomers as H2O, NH3, H2CO, CO, H2S, CH3CN and H2, and more complex species such as HCOOCH3 and CH3CH2CN.

  13. Sustainable Applications of Nano-Catalysts and Alternative Methods in the Greener Synthesis and Transformations of Chemical

    EPA Science Inventory

    The presentation summarizes our sustainable chemical synthesis activity involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a var...

  14. Evaluation of meat and bone meal combustion residue as lead immobilizing material for in situ remediation of polluted aqueous solutions and soils: "chemical and ecotoxicological studies".

    PubMed

    Deydier, E; Guilet, R; Cren, S; Pereas, V; Mouchet, F; Gauthier, L

    2007-07-19

    As a result of bovine spongiform encephalopathy (BSE) crisis, meat and bone meal (MBM) production can no longer be used to feed cattle and must be safely disposed of or transformed. MBM specific incineration remains an alternative that could offer the opportunity to achieve both thermal valorization and solid waste recovery as ashes are calcium phosphate-rich material. The aim of this work is to evaluate ashes efficiency for in situ remediation of lead-contaminated aqueous solutions and soils, and to assess the bioavailability of lead using two biological models, amphibian Xenopus laevis larvae and Nicotiana tabaccum tobacco plant. With the amphibian model, no toxic or genotoxic effects of ashes are observed with concentrations from 0.1 to 5 g of ashes/L. If toxic and genotoxic effects of lead appear at concentration higher than 1 mg Pb/L (1 ppm), addition of only 100 mg of ashes/L neutralizes lead toxicity even with lead concentration up to 10 ppm. Chemical investigations (kinetics and X-ray diffraction (XRD) analysis) reveals that lead is quickly immobilized as pyromorphite [Pb10(PO4)6(OH)2] and lead carbonate dihydrate [PbCO(3).2H2O]. Tobacco experiments are realized on contaminated soils with 50, 100, 2000 and 10000 ppm of lead with and without ashes amendment (35.3g ashes/kg of soil). Tobacco measurements show that plant elongation is bigger in an ashes-amended soil contaminated with 10000 ppm of lead than on the reference soil alone. Tobacco model points out that ashes present two beneficial actions as they do not only neutralize lead toxicity but also act as a fertilizer. PMID:17240054

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

    Microsoft Academic Search

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

    2007-01-01

    Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500 °C and at pressures up to 480 MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd\\/0.16m HNO3 aqueous solution at temperatures up to

  16. Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

    NASA Astrophysics Data System (ADS)

    Sulyma, Christopher Michael

    This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated he

  17. EMERGING TECHNOLOGY BULLETIN: REMOVAL OF PHENOL FROM AQUEOUS SOLUTIONS USING HIGH ENERGY ELECTRON BEAM IRRADIATION

    EPA Science Inventory

    Irradiation of aqueous solutions with high-energy electrons results in the formation of the aqueous electron, hydrogen radical, H-, and the hydroxyl radical, OH-. These reactive transient species initiate chemical reactions capable of destroying organic compounds in aqueous solut...

  18. Unusual atmospheric pressure chemical ionization conditions for detection of organic peroxides.

    PubMed

    Rondeau, David; Vogel, René; Tabet, Jean-Claude

    2003-09-01

    Organic peroxides such as the cumene hydroperoxide I (M(r) = 152 u), the di-tert-butyl peroxide II (M(r) = 146 u) and the tert-butyl peroxybenzoate III (M(r) = 194 u) were analyzed by atmospheric pressure chemical ionization mass spectrometry using a water-methanol mixture as solvent with a low flow-rate of mobile phase and unusual conditions of the source temperature (< or =50 degrees C) and probe temperature (70-200 degrees C). The mass spectra of these compounds show the formation of (i) an [M + H](+) ion (m/z 153) for the hydroperoxide I, (ii) a stable adduct [M + CH(3)OH(2)](+) ion (m/z 179) for the dialkyl peroxide II and (iii) several protonated adduct species such as protonated molecules (m/z 195) and different protonated adduct ions (m/z 227, 389 and 421) for the peroxyester III. Tandem mass spectrometric experiments, exact mass measurements and theoretical calculations were performed for characterize these gas-phase ionic species. Using the double-well energy potential model illustrating a gas-phase bimolecular reaction, three important factors are taken into account to propose a qualitative interpretation of peroxide behavior toward the CH(3)OH(2) (+), i.e. thermochemical parameters (DeltaHdegrees(reaction)) and two kinetic factors such as the capture constant of the initial stable ion-dipole and the magnitude of the rate constant of proton transfer reaction into the loose proton bond cluster. PMID:14505320

  19. Particle emissions from a marine engine: chemical composition and aromatic emission profiles under various operating conditions.

    PubMed

    Sippula, O; Stengel, B; Sklorz, M; Streibel, T; Rabe, R; Orasche, J; Lintelmann, J; Michalke, B; Abbaszade, G; Radischat, C; Gröger, T; Schnelle-Kreis, J; Harndorf, H; Zimmermann, R

    2014-10-01

    The chemical composition of particulate matter (PM) emissions from a medium-speed four-stroke marine engine, operated on both heavy fuel oil (HFO) and distillate fuel (DF), was studied under various operating conditions. PM emission factors for organic matter, elemental carbon (soot), inorganic species and a variety of organic compounds were determined. In addition, the molecular composition of aromatic organic matter was analyzed using a novel coupling of a thermal-optical carbon analyzer with a resonance-enhanced multiphoton ionization (REMPI) mass spectrometer. The polycyclic aromatic hydrocarbons (PAHs) were predominantly present in an alkylated form, and the composition of the aromatic organic matter in emissions clearly resembled that of fuel. The emissions of species known to be hazardous to health (PAH, Oxy-PAH, N-PAH, transition metals) were significantly higher from HFO than from DF operation, at all engine loads. In contrast, DF usage generated higher elemental carbon emissions than HFO at typical load points (50% and 75%) for marine operation. Thus, according to this study, the sulfur emission regulations that force the usage of low-sulfur distillate fuels will also substantially decrease the emissions of currently unregulated hazardous species. However, the emissions of soot may even increase if the fuel injection system is optimized for HFO operation. PMID:25202837

  20. Polar organic chemical integrative samplers for pesticides monitoring: impacts of field exposure conditions.

    PubMed

    Lissalde, Sophie; Mazzella, Nicolas; Mazellier, Patrick

    2014-08-01

    This study focuses on how Polar Organic Chemical Integrative Samplers (POCIS) work in real environmental conditions. A selection of 23 polar pesticides and 8 metabolites were investigated by exposure of triplicates of integrative samplers in two rivers in France for successive 14-day periods. The pesticides and metabolites were trapped not only in Oasis HLB sorbent but also in the polyethersulfone (PES) membrane of the POCIS. The distribution of pesticides depended on the molecular structure. The use of the Performance Reference Compound (PRC) is also discussed here. The impact of some environmental parameters and exposure setup on the transfer of pesticides in POCIS sorbent was studied: river flow rate, biofouling on membranes, sampler holding design and position in the stream. Results show a significant impact of river flow velocity on PRC desorption, especially for values higher than 4 cm·s(-1). Some fouling was observed on the PES membrane which could potentially have an impact on molecule accumulation in the POCIS. Finally, the positioning of the sampler in the river did not have significant effects on pesticide accumulation, when perpendicular exposures were used (sampler positioning in front of the water flow). The POCIS with PRC correction seems to be a suitable tool for estimating time-weighted average (TWA) concentrations, for all the molecules except for one of the nine pesticides analyzed in these two French rivers. PMID:24830931

  1. Chemical Peels

    MedlinePLUS

    ... to Choose the Best Skin Care Products Chemical Peels Uses for Chemical Peels Learn more about specific conditions where chemical peels ... skin Sagging skin Wrinkles What is a chemical peel? A chemical peel is a technique used to ...

  2. Modelling chemistry in aircraft plumes 2: the chemical conversion of NO x to reservoir species under different conditions

    Microsoft Academic Search

    Anne Gunn Kraabøl; Frode Stordal

    2000-01-01

    An expanding plume model with chemistry has been used to study the chemical conversion of nitrogen oxides to reservoir species in aircraft plumes under various conditions. A plume from a B747 was studied, where the NOx emission index was 26.1gkg?1. Several sensitivity tests were performed for emissions at 07 UT at 50°N under summer conditions. The amount of NOx remaining

  3. Changes in the Condition Index and Chemical Contents of Venerupis (decussata decussate L.) from the Egyptian Coastal Waters

    Microsoft Academic Search

    F. E. El-Nady

    1997-01-01

    Changes in the condition index and chemical contents of adult and young aged exotic Manila Venerupis (decussata decussata L.) have been studied. Animals were collected monthly from El-Mex Bay during the period from April 1993 to April 1994. Monthly variations in total lipid, phospholipid, triglyceride, free fatty acids (FFA), phosphorus, potassium and magnesium were determined in animals of different sizes.

  4. Changes in the condition index and chemical contents of venerupis (decussate decussata l.) from the Egyptian coastal waters

    Microsoft Academic Search

    1996-01-01

    Changes in the condition index and chemical contents of adult and young aged exotic Manila Venerupis (decussata decussata L.) have been studied. Animals were collected monthly from El?Mex Bay during the period from April 1993 to April 1994. Monthly variations in total lipid, phospholipid , triglyceride, free fatty acids (FFA), phosphorus, potassium and magnesium were determined in animals of different

  5. THE JOURNAL OF CHEMICAL PHYSICS 135, 204704 (2011) Molecular diffusion and slip boundary conditions at smooth surfaces

    E-print Network

    Priezjev, Nikolai V.

    2011-01-01

    THE JOURNAL OF CHEMICAL PHYSICS 135, 204704 (2011) Molecular diffusion and slip boundary conditions on the flow structure and effective slip length in Newtonian fluids is investigated by molecular dynamics (MD with hydrodynamic predictions provided that the stripe width is larger than several molecular diameters. We found

  6. Chemical and Physical Environmental Conditions Underneath Mat and Canopy-Forming Macroalgae, and Their Effects on Understorey Corals

    Microsoft Academic Search

    Claudine Hauri; Katharina E. Fabricius; Britta Schaffelke; Craig Humphrey; Stuart Humphries

    2010-01-01

    Disturbed coral reefs are often dominated by dense mat- or canopy-forming assemblages of macroalgae. This study investigated how such dense macroalgal assemblages change the chemical and physical microenvironment for understorey corals, and how the altered environmental conditions affect the physiological performance of corals. Field measurements were conducted on macroalgal-dominated inshore reefs in the Great Barrier Reef in quadrats with macroalgal

  7. The Effect of Cooperative Learning Approach Based on Conceptual Change Condition on Students' Understanding of Chemical Equilibrium Concepts

    ERIC Educational Resources Information Center

    Bilgin, Ibrahim; Geban, Omer

    2006-01-01

    The purpose of this study is to investigate the effects of the cooperative learning approach based on conceptual change conditions over traditional instruction on 10th grade students' conceptual understanding and achievement of computational problems related to chemical equilibrium concepts. The subjects of this study consisted of 87 tenth grade…

  8. Thermo-chemical ablation of heat shields under Earth reentry conditions

    NASA Astrophysics Data System (ADS)

    Keenan, James Anthony

    1994-04-01

    The process of ablation for earth atmospheric entry is modeled. The flowfield surrounding the ablator is modeled by an extended set of Navier-Stokes equations that include the effects of thermochemical nonequilibrium. This set of equations encompasses the conservation of mass for each chemical species, conservation of momentum, the conservation of vibrational energy, and the conservation of total energy. The heat conduction into the ablator material is modeled by using Fourier's Law of heat conduction and the heat equation. The flowfield and ablator are coupled by a thermochemical ablation model that includes a surface mass balance and a surface energy balance. The ablation model takes into account chemical reactions of the flowfield species with the surface material, surface material acting as a catalytic surface, and sublimation of the surface material. To solve the governing equations for the model, a computational fluid dynamics approach is used where the flowfield is solved using a modified Steger-Warming flux vector splitting scheme and the solid is solved using a centrally differenced scheme. A Gauss-Seidel line relaxation technique is implemented to speed numerical convergence. The flowfield model is verified by comparing to flowfield computations of other researchers and to experimental data. The ablator/heat shield model is validated by a direct comparison between an exact analytical solution and a numerical solution. The thermochemical ablation model is verified by comparing to the experimental results of the Passive Nosetip Technology (PANT) program. The model is used to calculate steady-state ablation data for sphere-cone reentry bodies. Two bodies with nose radii of 0.0127 m and 0.1270 m are tested at a velocity of 8 km/s. The ablator material is selected to be a commercial grade graphite. Due to the ablator selection, the flowfield is limited to 11 chemical species and two internal energy modes. A standard earth atmosphere is selected at altitudes ranging from 40 km to 80 km. The major results concern the thermochemical ablation model. Both oxidation and sublimation mechanisms are evident and are dependent on freestream conditions and the reentry body shape.

  9. Simulations of Chemical Reactivity of Insensitive Energetic Materials Under Thermal and Shock Conditions

    NASA Astrophysics Data System (ADS)

    Manaa, Riad; Reed, Evan; Fried, Laurence; Goldman, Nir

    2011-06-01

    Results of quantum based simulations of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) crystals under thermal decomposition (high density and temperature) and shock compression conditions are presented. We conducted constant volume-temperature simulations, ranging from 0.35 to 2 nanoseconds, at ? = 2.87 g/cm3 at T= 3500, 3000, 2500, and 1500 K, and ? = 2.9 g/cm3and 2.72 g/cm3, at T = 3000 K. We also simulated crystal TATB's reactivity under steady overdriven shock compression at shock speeds of 8, 9, and 10 km/s for up to 0.43 ns duration. These simulations have enabled us to track the reactivity of TATB well into the formation of several stable gas products, such as H2O, N2, and CO2. Our simulations revealed a hitherto unidentified region of high concentrations of nitrogen-rich heterocyclic clusters in reacting TATB, whose persistence impede further reactivity towards final products of fluid N2 and solid carbon. Our simulations also predict significant populations of charged species such as NCO-, H+, OH-, H3O+, and O-2, the first such observation in a reacting explosive. A reduced four steps, global reaction mechanism with Arrhenius kinetic rates for the decomposition of TATB, along with comparative thermo-chemical decomposition kinetics has been constructed and will be discussed. This work performed under the auspices of the U.S. DoE Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  10. Chemical bath deposition of ZnO nanowires at near-neutral pH conditions without hexamethylenetetramine (HMTA): understanding the role of HMTA in ZnO nanowire growth.

    PubMed

    McPeak, Kevin M; Le, Thinh P; Britton, Nathan G; Nickolov, Zhorro S; Elabd, Yossef A; Baxter, Jason B

    2011-04-01

    Chemical bath deposition (CBD) is an inexpensive and reproducible method for depositing ZnO nanowire arrays over large areas. The aqueous Zn(NO(3))(2)-hexamethylenetetramine (HMTA) chemistry is one of the most common CBD chemistries for ZnO nanowire synthesis, but some details of the reaction mechanism are still not well-understood. Here, we report the use of in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy to study HMTA adsorption from aqueous solutions onto ZnO nanoparticle films and show that HMTA does not adsorb on ZnO. This result refutes earlier claims that the anisotropic morphology arises from HMTA adsorbing onto and capping the ZnO {10 1 0} faces. We conclude that the role of HMTA in the CBD of ZnO nanowires is only to control the saturation index of ZnO. Furthermore, we demonstrate the first deposition of ZnO nanowire arrays at 90 °C and near-neutral pH conditions without HMTA. Nanowires were grown using the pH buffer 2-(N-morpholino)ethanesulfonic acid (MES) and continuous titratation with KOH to maintain the same pH conditions where growth with HMTA occurs. This semi-batch synthetic method opens many new opportunities to tailor the ZnO morphology and properties by independently controlling temperature and pH. PMID:21361384

  11. Chemical Control of Water Loss in Growing Plants

    Microsoft Academic Search

    E. M. Stoddard; P. M. Miller

    1962-01-01

    Immersing the roots of growing strawberry plants in aqueous solutions of 8-hydroxyquinoline sulfate closes the stomata, reduces water loss, and increases the time before complete wilting under drought conditions. Under such drought conditions plant survival and vigor are increased. Prolonged closing of the stomata seems to be the principal mode of action of the chemical.

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

    SciTech Connect

    Vijayan, S.; Wong, Chi Fun; Buckley, L.P.

    1992-12-31

    It is an object of the claimed invention to combine chemical treatment with microfiltration process to treat groundwater, leachate from contaminated soil washing, surface and run-off waters contaminated with toxic metals, radionuclides and trace amounts of organics from variety of sources. The process can also be used to treat effluents from industrial processes such as discharges associated with smelting, mining and refining operations. Influent contaminants amenable to treatment are from a few mg/L to hundreds of mg/L. By selecting appropriate precipitation, ion exchange and adsorption agents and conditions, efficiencies greater than 99.9 percent can be achieved for removal of contaminants. The filtered water for discharge can be targeted with either an order of magnitude greater or lower than contaminant levels for drinking water.

  13. Journal of Chemical Ecology, Vol. 25, No. 12, 1999 CONDITIONED ALARM BEHAVIOR IN FATHEAD

    E-print Network

    Wisenden, Brian D.

    (Pimephales promelas) RESULTING FROM ASSOCIATION OF CHEMICAL ALARM PHEROMONE WITH A NONBIOLOGICAL VISUAL--Fathead minnows (Pimephales promelas) adopt antipredator (alarm) behavior when they detect alarm pheromone, Pimephales promelas, alarm pheromone, Schreckstoff, learned recognition of predation risk, red light. #12

  14. A Study on the Aqueous Formation of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sinclair, K.; Tsigaridis, K.

    2013-12-01

    The effect aerosols have on radiative forcing in the atmosphere is recognized as one of the largest uncertainties in the radiation budget. About 80% of organic aerosol mass in the atmosphere is estimated to be created though secondary processes. Recently, the aqueous formation of secondary organic aerosols (SOA) has become recognized as important when considering the source, transformation and radiative impacts of SOA. This work focuses on implementing a mechanism for aqueous SOA formation that can be used in atmospheric chemistry and models of all scales, from box to global. A box model containing a simplified chemical mechanism for the aqueous production of precursors of aqueous SOA (Myriokefalitakis et al. (2011) is coupled to gas-phase chemistry which uses the carbon bond mechanism (CBM) IV is presented. The model implements aqueous chemistry of soluble gases, both in-cloud and aerosol water, including organic compounds such as glyoxal and methylglyoxal, which have been shown as potentially significant sources for dissolved secondary organic aerosols. This mechanism implements aqueous phase mass transfer and molecular dissociation. The model's performance is evaluated against previous box model studies from the literature. A comparison is conducted between the detailed GAMMA model (McNeill et al., 2012), which is constrained with chamber experiments and the one developed here. The model output under different atmospheric conditions is explored and differences and sensitivities are assessed. The objective of this work is to create a robust framework for simulating aqueous phase formation of SOA and maximizing the computational efficiency of the model, while maintaining accuracy, in order to later use the exact mechanism in global climate simulations.

  15. THE JOURNAL OF CHEMICAL PHYSICS 134, 154503 (2011) pH-dependent x-ray absorption spectra of aqueous boron oxides

    E-print Network

    Cohen, Ronald C.

    2011-01-01

    -ray absorption fine structure (NEXAFS) spectra at the boron K-edge were measured for aqueous boric acid, borate reveal that water is arranged nearly isotrop- ically around boric acid and sodium borate) spectroscopy ex- periments to probe boric acid, borate, and polyborate ions in solution. We also compare

  16. Microfluidic image cytometry for quantitative single-cell profiling of human pluripotent stem cells in chemically defined conditions†

    PubMed Central

    Ohashi, Minori; Gschweng, Eric; Ho, Quinn; Suh, Jane; Tang, Jinghua; Yu, Zeta Tak For; Clark, Amander T.; Pyle, April D.; Teitell, Michael A.; Lee, Ki-Bum.; Witte, Owen N.

    2010-01-01

    Microfluidic image cytometry (MIC) has been developed to study phenotypes of various hPSC lines by screening several chemically defined serum/feeder-free conditions. A chemically defined hPSC culture was established using 20 ng mL?1 of bFGF on 20 ?g mL?1 of Matrigel to grow hPSCs over a week in an undifferentiated state. Following hPSC culture, we conducted quantitative MIC to perform a single cell profiling of simultaneously detected protein expression (OCT4 and SSEA1). Using clustering analysis, we were able to systematically compare the characteristics of various hPSC lines in different conditions. PMID:20390128

  17. Rapid screening procedures for the hydrolysis products of chemical warfare agents using positive and negative ion liquid chromatography–mass spectrometry with atmospheric pressure chemical ionisation

    Microsoft Academic Search

    Robert W Read; Robin M Black

    1999-01-01

    Qualitative screening procedures have been developed for the rapid detection and identification of the hydrolysis products of chemical warfare agents in aqueous samples and extracts, using liquid chromatography–mass spectrometry with positive and negative atmospheric pressure chemical ionisation (APCI). Previously reported screening procedures, which used positive APCI or electrospray ionisation (ESI), were modified by using LC conditions that allowed acquisition of

  18. Low temperature nanostructured zinc titanate by an aqueous particulate sol–gel route: Optimisation of heat treatment condition based on Zn:Ti molar ratio

    Microsoft Academic Search

    M. R. Mohammadi; D. J. Fray

    2010-01-01

    Nanocrystalline zinc titanate (ZnTiO3) thin films and powders with purity of 94% were produced at the low sintering temperature of 500°C and the short sintering time of 1h by a straightforward aqueous particulate sol–gel route. The effect of Zn:Ti molar ratio was studied on the crystallisation behaviour of zinc titanates. The prepared sols showed a narrow particle size distribution in

  19. Influence of cultivation conditions on the production of cellulolytic enzymes with Trichoderma reesei Rutgers C30 in aqueous two-phase systems

    Microsoft Academic Search

    Ingrid Persson; Folke Tjerneld; Bärbel Hähn-Hagerdal

    1991-01-01

    Cellulolytic enzyme production in aqueous two-phase systems withTrichoderma reesei Rutgers C30 has been investigated. The influ ence of different phase systems, as well as addition of media compo nents and\\u000a substrate on enzyme production have been studied. Extractive enzyme production in fed-batch cultivations was per formed in\\u000a a phase system composed of PEG 8000 5%-Dextran T500 7% with 1% Solka-Floc

  20. Optimization of Cultural Conditions for the Production of Xylanase by Chemically Mutated Strain of Aspergillus niger GCBCX-20

    Microsoft Academic Search

    IKRAM-UL HAQ; KOUKAB RAANA; AYESHA KHAN; HAMID MUKHTAR

    Present investigation deals with the studies on the cultural conditions for enhanced biosynthesis of xylanase by a chemically mutated strain of Aspergillus niger GCBCX-20. The effects of time course, incubation temperature, medium pH and volume of fermentation medium on the production of xylanase were studied. The maximum xylanase production (250 U mL-1) was observed at an incubation temperature of 30

  1. Diurnal fluctuations in the physico-chemical conditions of the Shatt al-Arab and the Ashar Canal

    Microsoft Academic Search

    A L Sarker; S K Al-Nasiri; S A Hussein

    1980-01-01

    Diel fluctuations of temperature, dissolved oxygen, carbon dioxide, pH, total alkalinity and chlorosity in the Shatt al-Arab\\u000a River and the Ashar Canal at Basrah, Iraq were studied. The study covered three 24-hour periods in three different months.\\u000a Appreciable diurnal changes in the physico-chemical conditions and considerable heterogeneity were noted at the three stations\\u000a selected. The ranges of diurnal differences between

  2. Chemical reactions involved in the deep fat frying of foods. I. A laboratory apparatus for frying under simulated restaurant conditions

    Microsoft Academic Search

    R. G. Krishnamurthy; Tsukasa Kawada; S. S. Chang

    1965-01-01

    A laboratory apparatus has been designed which can be used to quantitatively collect the volatile decomposition products produced\\u000a during deep fat frying under simulated restaurant conditions. In order to study the chemical reactions of frying fat without\\u000a any inter-reaction with the food fried, moist cotton balls were fried in corn oil.\\u000a \\u000a The oil used for frying was shown to differ

  3. Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions

    Microsoft Academic Search

    Eleonora So?o; Jan Kalembkiewicz

    2007-01-01

    The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of

  4. DOI: 10.1002/adem.200900122 Influence of Treatment Conditions on the Chemical Oxidative

    E-print Network

    is the rational design of a material's surface properties. Several physical and chemical methods have been adopted to modify, at different scales, the surface properties of widely used biomaterials toward an improved response. The modified submicron and nanotextured surfaces were characterized by scanning electron (SEM

  5. THE INSTABILITY OF ESTROGENIC CHEMICALS DURING LABORATORY STATIC EXPOSURE CONDITIONS WITH MALE FATHEAD MINNOWS

    EPA Science Inventory

    Endocrine disrupting chemicals (EDCs) such as Para-nonylphenol (NP), estradiol (E2), estrone (E1), estriol (E3) and ethynylestradiol (EE2) are shown to be ubiquitous in surface waters, sediments and sludge. These EDCs are known to induce vitellogenin gene (Vg) expression in male...

  6. Physical and chemical stability of expired fixed dose combination artemether-lumefantrine in uncontrolled tropical conditions

    Microsoft Academic Search

    Roger Bate; Richard Tren; Kimberly Hess; Amir Attaran

    2009-01-01

    BACKGROUND: New artemisinin combination therapies pose difficulties of implementation in developing and tropical settings because they have a short shelf-life (two years) relative to the medicines they replace. This limits the reliability and cost of treatment, and the acceptability of this treatment to health care workers. A multi-pronged investigation was made into the chemical and physical stability of fixed dose

  7. Influence of coal briquetting conditions on the chemical composition of the products of thermal degradation

    SciTech Connect

    Turenko, F.P.

    1984-01-01

    A spectro-statistical method was used to examine the chemical composition of liquid non-volatile constituents from a mixture of Donbass coals (gas, fat, lean, caking). The thermal destruction products obtained by thermal filtration in a centrifugal field from both briquetted and non-briquetted charges differ in terms of their structural group content.

  8. Numerical simulation of the middle atmosphere chemical composition and temperature under changing solar conditions

    NASA Technical Reports Server (NTRS)

    Zadorozhny, A. M.; Dyominov, I. G.; Tuchkov, G. A.

    1989-01-01

    There are given results of the numerical experiments on modelling the influence of solar activity on chemical composition and temperature of the middle atmosphere. The consideration is made for peculiarities of solar activity impact under different values of antropogenic pollution of the atmosphere with chlorofluorocarbons and other stuff.

  9. Low-thrust chemical propulsion system propellant expulsion and thermal conditioning study. Executive summary

    NASA Technical Reports Server (NTRS)

    Merino, F.; Wakabayashi, I.; Pleasant, R. L.; Hill, M.

    1982-01-01

    Preferred techniques for providing abort pressurization and engine feed system net positive suction pressure (NPSP) for low thrust chemical propulsion systems (LTPS) were determined. A representative LTPS vehicle configuration is presented. Analysis tasks include: propellant heating analysis; pressurant requirements for abort propellant dump; and comparative analysis of pressurization techniques and thermal subcoolers.

  10. Aqueous chemical growth of free standing vertical ZnO nanoprisms, nanorods and nanodiskettes with improved texture co-efficient and tunable size uniformity

    NASA Astrophysics Data System (ADS)

    Ram, S. D. Gopal; Ravi, G.; Athimoolam, A.; Mahalingam, T.; Kulandainathan, M. Anbu

    2011-12-01

    Tuning the morphology, size and aspect ratio of free standing ZnO nanostructured arrays by a simple hydrothermal method is reported. Pre-coated ZnO seed layers of two different thicknesses (?350 nm or 550 nm) were used as substrates to grow ZnO nanostructures for the study. Various parameters such as chemical ambience, pH of the solution, strength of the Zn2+ atoms and thickness of seed bed are varied to analyze their effects on the resultant ZnO nanostructures. Vertically oriented hexagonal nanorods, multi-angular nanorods, hexagonal diskette and popcorn-like nanostructures are obtained by altering the experimental parameters. All the produced nanostructures were analysed by X-ray powder diffraction analysis and found to be grown in the (002) orientation of wurtzite ZnO. The texture co-efficient of ZnO layer was improved by combining a thick seed layer with higher cationic strength. Surface morphological studies reveal various nanostructures such as nanorods, diskettes and popcorn-like structures based on various preparation conditions. The optical property of the closest packed nanorods array was recorded by UV-VIS spectrometry, and the band gap value simulated from the results reflect the near characteristic band gap of ZnO. The surface roughness profile taken from the Atomic Force Microscopy reveals a roughness of less than 320 nm.

  11. In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: A new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions

    USGS Publications Warehouse

    Lu, W.J.; Chou, I.-Ming; Burruss, R.C.; Yang, M.Z.

    2006-01-01

    A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition. ?? 2006 Society for Applied Spectroscopy.

  12. Parenteral Peptide Formulations: Chemical and Physical Properties of Native Luteinizing Hormone-Releasing Hormone (LHRH) and Hydrophobic Analogues in Aqueous Solution

    Microsoft Academic Search

    Michael F. Powell; Lynda M. Sanders; Alan Rogerson; Vicki Si

    1991-01-01

    The degradation of native LHRH in aqueous buffers of pH ~1–10 obeyed the rate equation, kobs = kH+aH+ + ko + kHO-(aHO-)x, where x at 60–100°C was ~0.64 and temperature independent. Extrapolation to 25°C using the Arrhenius equation and secondary rate constants showed that native LHRH is reasonably stable at pH 5.4, giving a shelf life (t90) of approximately 5

  13. ADVANCED CHEMICAL OXIDATION OF 2,4,6 TRICHLOROPHENOL IN AQUEOUS PHASE BY FENTON'S REAGENT-PART II: EFFECTS OF VARIOUS REACTION PARAMETERS ON THE TREATMENT REACTION

    Microsoft Academic Search

    SOMNATH BASU; IRVINE W. WEI

    1998-01-01

    Part I of this paper examined the effects of the amounts of oxidant and catalyst on the rates and extents of oxidation of 2,4,6-Trichlorophenol (TCP), in aqueous phase, by Fenton's Reagent. In this part the effects of various reaction parameters, e.g. temperature, pH, oxidation state of catalyst (ferrous versus ferric), mode of addition of oxidant to the reactor (single batch

  14. Conditions?

    Microsoft Academic Search

    A. Christy Wyckoff; Scott E. Henke; Kurt C. VerCauteren

    Research interests in feral hogs typically involve their negative impacts on ecosystems or their potential as a disease reservoir, especially with disease transmission to domestic swine. Authors within scientific literature state that feral hogs were captured as part of their research, but usually fail to mention specific conditions in which hogs were captured. Novice researchers of feral hogs must rely

  15. Electronic structure of DNA polynucleotides under the chemical-doping condition investigated by PES and NEXAFS

    NASA Astrophysics Data System (ADS)

    Furukawa, Masashi; Kato, H. S.; Taniguchi, M.; Hatsui, T.; Kosugi, N.; Komeda, T.; Kawai, Maki; Kawai, T.

    2003-03-01

    During the last several years, the carrier transport through DNA between nm- spaced electrodes has been discussed without the understanding of their intrinsic electronic structures. As a result, its 'scattered' results in the controversial magnitude of conductivity, from a good conductor to an insulator, which is also assumed to be dependent on the chemical species surrounding DNA (H^+, counterion, etc.)@[ref.]. In this talk, we show electronic structures of the occupied- and unoccupied-states near the Fermi level. Systems exhibited here are well-defined sequence of DNA polynucleotides, Poly(dG)-poly(dC) and Poly(dA)-poly(dT), with- and without- chemical-doping (carrier-doping), in order to evaluate such an effect into DNA and also to propose the carrier conduction mechanism through DNA. [ref.] M. Taniguchi et al., submitted to JACS.

  16. Monte Carlo simulation study on the flow conditions of a vacuum chemical epitaxy system

    NASA Astrophysics Data System (ADS)

    Cotta, M. A.; de Carvalho, M. M. G.

    1992-07-01

    This work presents a numerical simulation, using Monte Carlo method, of the gas phase behavior in a vacuum chemical epitaxy (VCE) system, without hydride cracker. From this simulation, it is shown that the growth rate depends on the gas - mainly hydride —pressure in the growth chamber. This dependence is stronger for pressures above 10 -3 Torr, where the growth rate decreases almost linearly with increasing pressure. The slope of this curve decreases with the sticking coefficient of the organometallic molecules, that is, when growth temperature increases. Experimental results agree well with the predicted results which can, qualitatively, explain the growth rate behavior with the hydride flows used in VCE, and show that gas phase collisions should not be neglected even in chemical beam epitaxy (CBE) systems.

  17. Boundary conditions for the paleoenvironment: Chemical and Physical Processes in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Schloerb, F. P.; Ziurys, L. M.

    1986-01-01

    The present research includes searches for important new interstellar constituents; observations relevant to differentiating between different models for the chemical processes that are important in the interstellar environment; and coordinated studies of the chemistry, physics, and dynamics of molecular clouds which are the sites or possible future sites of star formation. Recent research has included the detection and study of four new interstellar molecules; searches which have placed upper limits on the abundance of several other potential constituents of interstellar clouds; quantitative studies of comparative molecular abundances in different types of interstellar clouds; investigation of reaction pathways for astrochemistry from a comparison of theory and the observed abundance of related species such as isomers and isotopic variants; studies of possible tracers of energenic events related to star formation, including silicon and sulfur containing molecules; and mapping of physical, chemical, and dynamical properties over extended regions of nearby cold molecular clouds.

  18. Conditions of early chemical processing of matter - Explosive exhalations of supernovae

    NASA Technical Reports Server (NTRS)

    Heymann, D.

    1983-01-01

    The chemical and isotopic stratifications of supernova exhalations are discussed, with reference to a number of theoretical estimates. Particular attention is given to the theoretical models of the major chemical zones of explosive exhalation of isotopes of Mg, Si, and Ti in intermediate size supernovae. The contribution of supernova exhalations to oxygen anomalies in the solar system is also discussed within the framework of the theoretical models of Clayton et al. (1977, 1978, 1979, 1981). The initial stratigraphy of the major elements in the explosive exhalation of a progenitor star of 25 solar mass is illustrated in a graph, on the basis of the theoretical estimates of Waver et al. (1978), and Weaver and Woolsey (1980).

  19. Chemically defined conditions for human iPSC derivation and culture

    Microsoft Academic Search

    Guokai Chen; Daniel R Gulbranson; Zhonggang Hou; Jennifer M Bolin; Victor Ruotti; Mitchell D Probasco; Kimberly Smuga-Otto; Sara E Howden; Nicole R Diol; Nicholas E Propson; Ryan Wagner; Garrett O Lee; Jessica Antosiewicz-Bourget; Joyce M C Teng; James A Thomson

    2011-01-01

    We re-examine the individual components for human embryonic stem cell (ESC) and induced pluripotent stem cell (iPSC) culture and formulate a cell culture system in which all protein reagents for liquid media, attachment surfaces and splitting are chemically defined. A major improvement is the lack of a serum albumin component, as variations in either animal- or human-sourced albumin batches have

  20. [Elemental chemical composition of Scolelepis fuliginosa (Annelida, Polychaeta): effect of growth conditions].

    PubMed

    Guerin, J P; Kerambrum, P

    1976-09-27

    The elemental chemical composition of Scolelepis fuliginosa was comparatively with specimens reared in laboratory and from a natural population. The carbon-nitrogen ratio variations show a certain homogeneity of composition in juveniles and young sexed and a sexual dimorphism in adults. C/N ratio of the laboratory specimens is not significantly different from that of the ones from natural surroundings. But, when these are kept several weeks in captivity, this ratio considerably decreases. PMID:825314

  1. Effect of outdoor conditions on growth rate and chemical composition of Gelidium crinale in culture

    Microsoft Academic Search

    Areen Boulus; Ehud Spaneir; Michael Friedlander

    2007-01-01

    A comprehensive study of the major environmental factors affecting growth and chemical composition of Gelidium crinale is presented here for the first time. The purpose of this study was to analyze the significance of the major growth factors\\u000a and to formulate them into regression models. For this purpose summer and winter experiments were conducted in small aerated\\u000a seawater tanks under

  2. Size-resolved aerosol chemical composition over the Italian Peninsula during typical summer and winter conditions

    Microsoft Academic Search

    C. Carbone; S. Decesari; M. Mircea; L. Giulianelli; E. Finessi; M. Rinaldi; S. Fuzzi; A. Marinoni; R. Duchi; C. Perrino; T. Sargolini; M. Vardè; F. Sprovieri; G. P. Gobbi; F. Angelini; M. C. Facchini

    2010-01-01

    In the frame of the MIUR-AEROCLOUDS project (Study of Direct and Indirect Aerosol Effects on Climate), night-time and daytime size-segregated aerosol samples were collected concurrently at five different sites (near-city, urban, rural, marine and mountain background sites). The paper reports on the daily evolution of the main aerosol chemical characteristics as a function of particle size in different environments over

  3. Chemical aspects of deposition\\/corrosion from coal-water fuels under gas turbine conditions

    Microsoft Academic Search

    R. A. Wenglarz; R. G. Jr. Fox

    1990-01-01

    This patent describes a staged, subscale turbine combustor based on a promising rich-quench-lean combustion approach to reduce NOâ emissions used to evaluate deposition, erosion, and corrosion (DEC) from coal-water fuels (CWF). This combustor was operated with three CWF at conditions of a recuperated turbine. Specimens were exposed in two test sections at temperature conditions of the first stator vanes and

  4. Mars aqueous chemistry experiment

    NASA Technical Reports Server (NTRS)

    Clark, Benton C.; Mason, Larry W.

    1994-01-01

    Mars Aqueous Chemistry Experiment (MACE) is designed to conduct a variety of measurements on regolith samples, encompassing mineral phase analyses, chemical interactions with H2O, and physical properties determinations. From these data, much can be learned or inferred regarding the past weathering environment, the contemporaneous soil micro-environments, and the general chemical and physical state of the Martian regolith. By analyzing both soil and duricrust samples, the nature of the latter may become more apparent. Sites may be characterized for comparative purposes and criteria could be set for selection of high priority materials on future sample return missions. The second year of the MACE project has shown significant progress in two major areas. MACE Instrument concept definition is a baseline design that has been generated for the complete MACE instrument, including definition of analysis modes, mass estimates and thermal model. The design includes multiple reagent reservoirs, 10 discrete analysis cells, sample manipulation capability, and thermal control. The MACE Measurement subsystems development progress is reported regarding measurement capabilities for aqueous ion sensing, evolved gas sensing, solution conductivity measurement, reagent addition (titration) capabilities, and optical sensing of suspended particles.

  5. Influence of Aqueous-Salt Conditions on the Structure and Dynamics of the Monomeric and Novel Dimeric forms of the Alzheimer s ABeta21-30 protein fragment

    NASA Astrophysics Data System (ADS)

    Smith, Micholas Dean

    The behavior of the Alzheimer's related peptide Abeta is the subject of much study. In typical computational studies the environment local to the peptide is assumed to be pure water; however, in vivo the peptide is found in the extracellular space near the plasma membrane which is rich in ionic species. In this thesis, the hypothesis that the presence of group I/IIA salts will result in increased sampling of disordered structures as well as modify the dynamics of meta-stable structural motifs in the small folding nucleus of the Abeta peptide (Abeta21-30) is examined under a variety of ionic environments and was shown that of the tested salts, CaCl2 (and MgCl2, to a much lesser degree) did increase the propensity for disordered states; while, the group IA salts, KCl and NaCl, had little effect on the secondary structure of the peptide. Further, study of three familial mutations of this peptide region is also performed under aqueous salt-environments to elucidate further mechanistic details of how aqueous salts modify the region's behavior. Finally, as experimental results have highlighted that aggregation rates of the full-length peptide are modified by the presence of CaCl2, this work examines novel dimers states of Abeta21-30 and their stabilities when exposed to CaCl2.

  6. An evaluation of a river health using the index of biological integrity along with relations to chemical and habitat conditions.

    PubMed

    An, Kwang-Guk; Park, Seok Soon; Shin, Joung-Yi

    2002-11-01

    We evaluated the health condition of a temperate river during June-November 1999 through applications of the index of biological integrity (IBI) using fish assemblages and qualitative habitat evaluation index (QHEI) as well as chemical analyses. Overall IBI values ranged from 13 to 37 and averaged 23 (n = 25, standard error = 1.16), indicating a "poor" or "very poor" condition according to the criteria of modified Karr [Fisheries 6 (1981) 21]. The values of mean IBI declined at a rate of 0.22 km(-1) (R2 = 0.91, p < 0.05) along the longitudinal distance from the headwaters to the downstream sites. Reduced IBI values at downstream sites reflected low forest cover, high population density and high nutrient enrichments. Ecotoxicity tests using the river water also showed that toxic impacts were evident in the downriver sites. These factors resulted in decreases of riffle benthic species and insectivores and increases of tolerant species, anormalies and exotic species in the river. Spatial pattern in IBI agreed with QHEI values, which showed a linear relation (R2 = 0.998, p < 0.001) with species richness. Field measurements of conductivity and pH, an indicators for variation of conservative ions, showed that the river water was diluted by 40% fold by summer monsoon rain and surface run-off from the watershed, resulting in a physical and chemical instability during the monsoon. For these reasons, average IBI values during the monsoon and postmonsoon decreased >20% compared to the premonsoon, indicating that IBI values were also affected by flow regime. Based on the overall physico-chemical data and IBI values, the river health is rapidly degrading due to the combined effect of chemical contaminations and habitat modifications. PMID:12437291

  7. Chemical and microbiological changes in fluid milk as affected by packaging conditions

    Microsoft Academic Search

    Evangelia Vassila; Anastasia Badeka; Efthymia Kondyli; Ioannis Savvaidis; Michael G Kontominas

    2002-01-01

    Changes in chemical and microbiological quality parameters of whole pasteurized milk stored under fluorescent light at 4°C in pouches made of (a) low density polyethylene (LDPE, clear and TiO2 pigmented, 60?m in thickness), (b) coextruded (LDPE\\/polyamide\\/LDPE, clear and TiO2 pigmented, 60?m in thickness) and (c) coextruded (LDPE+2% TiO2\\/LDPE+2% TiO2\\/LDPE+4% carbon black pigment\\/LDPE+2% TiO2\\/LDPE+2% TiO2), 60 and 110?m in thickness were

  8. Constant-trace anomaly as a universal condition for the chemical freeze-out

    NASA Astrophysics Data System (ADS)

    Tawfik, A.

    2013-09-01

    Finding out the universal conditions describing the freeze-out parameters has been the subject of various phenomenological studies. In the present work, we introduce a new condition based on constant-trace anomaly (or interaction measure) calculated in the hadron resonance gas (HRG) model. Various extensions to the ideal HRG which are conjectured to take into consideration different types of interactions have been analyzed. When comparing HRG thermodynamics to that of lattice quantum chromodynamics, we conclude that the hard-core radii are practically irrelevant, especially when HRG includes all resonances with masses less than 2 GeV. It is found that the constant-trace anomaly (or interaction measure) agrees well with most previous conditions.

  9. Chemical Soil Physics Phenomena for Chemical Sensing of Buried UXO

    SciTech Connect

    Phelan, James, M.; Webb, Stephen W.

    1999-06-14

    Technology development efforts are under way to apply chemical sensors to discriminate inert ordnance and clutter from live munitions that remain a threat to reutilization of military ranges. However, the chemical signature is affected by multiple environmental phenomena that can enhance or reduce its presence and transport behavior, and can affect the distribution of the chemical signature in the environment. For example, the chemical can be present in the vapor, aqueous, and solid phases. The distribution of the chemical among these phases, including the spatial distribution, is key in designing appropriate detectors, e.g., gas, aqueous or solid phase sampling instruments. A fundamental understanding of the environmental conditions that affect the chemical signature is needed to describe the favorable and unfavorable conditions of a chemical detector based survey to minimize the consequences of a false negative. UXO source emission measurements are being made to estimate the chemical flux from a limited set of ordnance items. Phase partitioning analysis has been completed to show what the expected concentrations of chemical analytes would be fi-om total concentrations measured in the soil. The soil moisture content in the dry region has been shown to be critical in the attenuation of soil gas concentrations by increased sorption to soil particles. Numerical simulation tools have been adapted to include surface boundary conditions such as solar radiation, surface boundary layer (which is a function of wind speed), precipitation and evaporation, and plant cover/root density to allow transport modeling and evaluate long term processes. Results of this work will provide performance targets for sensor developers and support operational decisions regarding field deployments.

  10. Synthesis Under 'Greener' Conditions: Role of Sustainable Nano-Catalysts

    EPA Science Inventory

    The presentation summarizes our recent activity in chemical synthesis involving benign alternatives, such as the use of supported reagents, and greener reaction medium in aqueous or solvent-free conditions.1 The synthesis of heterocyclic compounds, coupling reactions, and a varie...

  11. Emission characteristics of nitrogen- and sulfur-containing odorous compounds during different sewage sludge chemical conditioning processes.

    PubMed

    Liu, Huan; Luo, Guang-Qian; Hu, Hong-Yun; Zhang, Qiang; Yang, Jia-Kuan; Yao, Hong

    2012-10-15

    Chemical conditioners are often used to enhance sewage sludge dewaterability through altering sludge properties and flocs structure, both affect odorous compounds emissions not only during sludge conditioning but also in subsequent sludge disposal. This study was to investigate emission characteristics of ammonia (NH(3)), sulfur dioxide (SO(2)), hydrogen sulfide (H(2)S) and carbonyl sulfide (COS) generated from sewage sludge conditioned by three representative conditioners, i.e., organic polymers, iron salts and skeleton builders, F-S (Fenton's reagent and skeleton builders) composite conditioner. The results demonstrate that polyacrylamide (PAM) has an insignificant effect on emission characteristics of nitrogen- and sulfur-containing odorous compounds, because the properties, sulfur and nitrogen speciations are similar in PAM-conditioned sludge and raw sludge (RS). Significant increases of SO(2) and H(2)S emissions in the H(2)SO(4) conditioning process were observed due to the accelerated decomposition of sulfur-containing amino acids in acidic environment. Fenton peroxidation facilitates the formation of COS. CaO can reduce sulfur-containing gases emission via generation of calcium sulfate. However, under strong alkaline conditions, free ammonia or protonated amine in sludge can be easily converted to volatile ammonia, resulting in a significant release of NH(3). PMID:22902143

  12. Monitoring and physical-chemical modeling of conditions of natural surface and underground waters forming in the Kola North.

    PubMed

    Mazukhina, Svetlana I; Masloboev, Vladimir A; Chudnenko, Konstantin V; Bychinsky, Valeriy A; Svetlov, Anton V; Muraviev, Sergey V

    2012-01-01

    Processes of surface and underground water forming in the Khibiny massif have been studied using a physical-chemical model of the "water-rock-atmosphere-organic substance" system. The obtained model solutions are indicative of the fact that formation of surface and underground water of the Khibiny massif takes place on the whole in the framework of the considered system without attracting a hypothetical outside source of pollutants. The results are of practical and methodological importance for assessment of prediction of the man-induced impact on water systems in conditions of Subarctic. PMID:22416860

  13. Is Vanadate Reduced by Thiols under Biological Conditions?: Changing The Redox Potential of V(V)/V(IV) by Complexation in Aqueous solution

    PubMed Central

    Crans, Debbie C.; Zhang, Boyan; Gaidamauskas, Ernestas; Keramidas, Anastasios D.; Willsky, Gail R.; Roberts, Chris R.

    2010-01-01

    Although dogma states that vanadate is readily reduced by glutathione, cysteine and other thiols, there are several examples documenting that vanadium(V)-sulfur complexes can form and be observed. This conundrum has impacted life scientists for more than two decades. Investigation of this problem requires an understanding of both the complexes that form from vanadium(IV) and (V) and a representative thiol in aqueous solution. The reactions of vanadate and hydrated vanadyl cation with 2-mercaptoethanol have been investigated using multinuclear NMR, EPR and UV-vis spectroscopy. Vanadate forms a stable complex of 2:2 stoichiometry with 2-mercaptoethanol at neutral and alkaline pH. In contrast, vanadate can oxidize 2-mercaptoethanol; this process is favored at low pH and high solute concentrations. The complex that forms between aqueous vanadium(IV) and 2-mercaptoethanol has a 1:2 stoichiometry and can be observed at high pH and high 2-mercaptoethanol concentration. The solution structures have been deduced and speciation diagrams prepared. This work demonstrates that both vanadium(IV) and (V)-thiol complexes form and that redox chemistry also takes place. Whether reduction of vanadate takes place is governed by a combination of parameters: pH, solute- and vanadate-concentrations and the presence of other complexing ligands. Based on these results it is now possible to understand the distribution of vanadium in oxidation states (IV) and (V) in the presence of glutathione, cysteine and other thiols and begin to evaluate the forms of the vanadium compounds that exert a particular biological effect including the insulin-enhancing agents, anti-amoebic agents and interactions with vanadium binding proteins. PMID:20359175

  14. Effects of metalorganic chemical vapor deposition growth conditions on the GaAs/Ge solar cell properties

    SciTech Connect

    Chen, J.C.; Ristow, M.L.; Cubbage, J.I.; Werthen, J.G. (Varian Research Center, 611 Hansen Way, Palo Alto, California 94303 (US))

    1991-05-20

    We have studied the effects of metalorganic chemical vapor deposition (MOCVD) growth conditions on the properties of GaAs solar cells grown upon Ge substrates, and in particular the GaAs/Ge interface. The interface properties were found to strongly depend on growth conditions. By small changes in the growth temperature, the GaAs/Ge interface was altered from active to passive. Only a narrow temperature window (600--630 {degree}C) for the initial GaAs layer growth gave the passive-Ge junction together with good surface morphology. Accordingly, a high efficiency (19%, AM0) GaAs solar cell was grown by atmospheric pressure MOCVD on a Ge substrate without any junction in the Ge.

  15. Exhaust emissions from gasoline-fuelled light duty vehicles operated in different driving conditions: A chemical and biological characterization

    NASA Astrophysics Data System (ADS)

    Westerholm, Roger; Almén, Jacob; Li, Hang; Rannug, Ulf; Rosén, Åke

    Chemical analysis and mutagenicity tests on Salmonella typtimurium strains TA 98 and TA 100 (Ames test) of exhaust emissions from five passengers vehicles, with or without a three-way catalyst, have been carried out to obtain emission factors and to characterize exhaust emissions. Both constant cruising speeds and transient driving conditions were investigated, regulated CO, HC, NO x and particulates, as well as unregulated pollutants, were analysed. The following unregulated pollutants were measured: particle-associated polycyclic aromatic hydrocarbons (PAH), 1-nitropyrene, light aromatics and light oxygenates. In total, 39 individual compounds were assayed. Emissions from catalyst-equipped vehicles showed a dramatic decrease compared with those from the vehicle without a catalyst. An emission dependency of both regulated and unregulated pollutants and biological activity on driving conditions were determined. An increased emission of PAH, 1-nitropyrene, particulates and mutagenic activity was found with a higher cruising speed.

  16. Chemical and Physical Environmental Conditions Underneath Mat- and Canopy-Forming Macroalgae, and Their Effects on Understorey Corals

    PubMed Central

    Hauri, Claudine; Fabricius, Katharina E.; Schaffelke, Britta; Humphrey, Craig

    2010-01-01

    Disturbed coral reefs are often dominated by dense mat- or canopy-forming assemblages of macroalgae. This study investigated how such dense macroalgal assemblages change the chemical and physical microenvironment for understorey corals, and how the altered environmental conditions affect the physiological performance of corals. Field measurements were conducted on macroalgal-dominated inshore reefs in the Great Barrier Reef in quadrats with macroalgal biomass ranging from 235 to 1029 g DW m?2 dry weight. Underneath mat-forming assemblages, the mean concentration of dissolved oxygen was reduced by 26% and irradiance by 96% compared with conditions above the mat, while concentrations of dissolved organic carbon and soluble reactive phosphorous increased by 26% and 267%, respectively. The difference was significant but less pronounced under canopy-forming assemblages. Dissolved oxygen declined and dissolved inorganic carbon and alkalinity increased with increasing algal biomass underneath mat-forming but not under canopy-forming assemblages. The responses of corals to conditions similar to those found underneath algal assemblages were investigated in an aquarium experiment. Coral nubbins of the species Acropora millepora showed reduced photosynthetic yields and increased RNA/DNA ratios when exposed to conditions simulating those underneath assemblages (pre-incubating seawater with macroalgae, and shading). The magnitude of these stress responses increased with increasing proportion of pre-incubated algal water. Our study shows that mat-forming and, to a lesser extent, canopy-forming macroalgal assemblages alter the physical and chemical microenvironment sufficiently to directly and detrimentally affect the metabolism of corals, potentially impeding reef recovery from algal to coral-dominated states after disturbance. Macroalgal dominance on coral reefs therefore simultaneously represents a consequence and cause of coral reef degradation. PMID:20856882

  17. Chemical and physical environmental conditions underneath mat- and canopy-forming macroalgae, and their effects on understorey corals.

    PubMed

    Hauri, Claudine; Fabricius, Katharina E; Schaffelke, Britta; Humphrey, Craig

    2010-01-01

    Disturbed coral reefs are often dominated by dense mat- or canopy-forming assemblages of macroalgae. This study investigated how such dense macroalgal assemblages change the chemical and physical microenvironment for understorey corals, and how the altered environmental conditions affect the physiological performance of corals. Field measurements were conducted on macroalgal-dominated inshore reefs in the Great Barrier Reef in quadrats with macroalgal biomass ranging from 235 to 1029 g DW m(-2) dry weight. Underneath mat-forming assemblages, the mean concentration of dissolved oxygen was reduced by 26% and irradiance by 96% compared with conditions above the mat, while concentrations of dissolved organic carbon and soluble reactive phosphorous increased by 26% and 267%, respectively. The difference was significant but less pronounced under canopy-forming assemblages. Dissolved oxygen declined and dissolved inorganic carbon and alkalinity increased with increasing algal biomass underneath mat-forming but not under canopy-forming assemblages. The responses of corals to conditions similar to those found underneath algal assemblages were investigated in an aquarium experiment. Coral nubbins of the species Acropora millepora showed reduced photosynthetic yields and increased RNA/DNA ratios when exposed to conditions simulating those underneath assemblages (pre-incubating seawater with macroalgae, and shading). The magnitude of these stress responses increased with increasing proportion of pre-incubated algal water. Our study shows that mat-forming and, to a lesser extent, canopy-forming macroalgal assemblages alter the physical and chemical microenvironment sufficiently to directly and detrimentally affect the metabolism of corals, potentially impeding reef recovery from algal to coral-dominated states after disturbance. Macroalgal dominance on coral reefs therefore simultaneously represents a consequence and cause of coral reef degradation. PMID:20856882

  18. Effect of chemical composition and sintering conditions on the mechanical properties of sintered duplex stainless steels

    Microsoft Academic Search

    F. Martín; C. García; Y. Blanco

    2011-01-01

    Duplex stainless steels were obtained through powder metallurgy technology from austenitic AISI 316L and ferritic AISI 430L powders mixed in different amounts to obtain ratios of austenite\\/ferrite of 25\\/75, 50\\/50 and 75\\/25. Prepared powder mixes were compacted at 650 or 750MPa and sintered in N2–H2 atmosphere (95%-5%) at several sintering conditions and with three sintering cooling rates (furnace, gas and

  19. Fretting-wear prediction in heat exchanger tubes: The effect of chemical cleaning and modelling ill-defined support conditions

    SciTech Connect

    Yetisir, M.; Fisher, N.J. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada). Chalk River Labs.

    1996-12-01

    Chemical cleaning of heat exchangers increases the clearances between tubes and their supports, which may lead to increased fretting-wear damage. This paper presents the results of a fretting-wear damage analysis of a U-bend tube at nominal and post-cleaning conditions. In multi-span heat exchanger tubes, the boundary conditions at the supports are ill-defined due to tube-support clearances. The fretting-wear rate at a support is a function of the gap (the distance between the tube and the support if the tube is not contacting the support) and preload (the contact force between the tube and the support if the tube is contacting the support). The configurations of gap/preload for a typical multi-span tube are numerous and not all possibilities can be analyzed. Instead, a randomly selected group of tube-to-support configurations that is representative of the whole set needs to be used. In this paper, results of simulations for 40 randomly chosen tube-to-support configurations are presented. These indicate that when random vibration is considered, on the average no significant increase in fretting-wear damage will occur after chemical cleaning.

  20. Physical properties, chemical composition, and cloud forming potential of particulate emissions from a marine diesel engine at various load conditions.

    PubMed

    Petzold, A; Weingartner, E; Hasselbach, J; Lauer, P; Kurok, C; Fleischer, F

    2010-05-15

    Particulate matter (PM) emissions from one serial 4-stroke medium-speed marine diesel engine were measured for load conditions from 10% to 110% in test rig studies using heavy fuel oil (HFO). Testing the engine across its entire load range permitted the scaling of exhaust PM properties with load. Emission factors for particle number, particle mass, and chemical compounds were determined. The potential of particles to form cloud droplets (cloud condensation nuclei, CCN) was calculated from chemical composition and particle size. Number emission factors are (3.43 +/- 1.26) x 10(16) (kg fuel)(-1) at 85-110% load and (1.06 +/- 0.10) x 10(16) (kg fuel)(-1) at 10% load. CCN emission factors of 1-6 x 10(14) (kg fuel)(-1) are at the lower bound of data reported in the literature. From combined thermal and optical methods, black carbon (BC) emission factors of 40-60 mg/(kg fuel) were determined for 85-100% load and 370 mg/(kg fuel) for 10% load. The engine load dependence of the conversion efficiency for fuel sulfur into sulfate of (1.08 +/- 0.15)% at engine idle to (3.85 +/- 0.41)% at cruise may serve as input to global emission calculations for various load conditions. PMID:20402501

  1. Investigations of chemical fraction of Co and Ni in industrial fly ash and mobility of metals in environmental conditions.

    PubMed

    Soco, Eleonora; Kalembkiewicz, Jan

    2007-02-01

    The quantitative evaluation of chemical fraction of Co and Ni in the industrial fly ash by methods of five step sequential extraction was carried out in order to characterize metal mobility in environmental conditions. The research involved (i) water-soluble (pH=7), (ii) acid-soluble (pH=5), (iii) oxide, (iv) sulfide and (v) residue metal fractions. It was discovered, that the total extraction of the studied metals from fly ash to solutions take place in the following quantities Co - 35.5 and Ni - 153.0mgkg(-1). The investigations of chemical fractions proved that the subject metals occur mainly in fly ash as: oxide (Co - 7.0, Ni - 28.5mgkg(-1)) and residue (Co - 11.5, Ni - 42.5mgkg(-1)) as well as sulfide (Co - 8.5, Ni - 46.5mgkg(-1)). Low concentrations of metals for water-soluble fraction (Co - 0.7, Ni - 1.2mgkg(-1)) and acid-soluble fraction (Co - 4.5, Ni - 23.5mgkg(-1)) were observed. The fractions of Co and Ni leachable from the ash in environmental conditions contain: 24.0% (Co) and 23.3% (Ni) of metal total amount in the industrial fly ash. The obtained mobility parameter of Co and Ni can be applied to estimate the concentration increase of mobile and hardly mobile forms of these metals in soil polluted with the ash. PMID:17150241

  2. Dynamics-based selective 2D (1)H/(1)H chemical shift correlation spectroscopy under ultrafast MAS conditions.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of (1)H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of (1)H/(1)H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  3. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  4. Coulometric investigation of the drying conditions of high-grade iron ores for chemical analysis.

    PubMed

    Yoshimori, T; Asano, Y; Harada, T

    1978-03-01

    Drying conditions for several iron ores have been investigated by the coulometric microdetermination of water. Samples, which were heated in an atmosphere of dry argon at 110 degrees for 3-4 hr and cooled, usually evolved less than 0.015% of water during a further 1 hr of heating. Therefore the difference in water content of the sample thus treated did not significantly influence the analytical results for total iron. Some magnetites and sintered pellet could be dried readily by heating for 2 hr in dry argon. Heating of samples of high water content for too long is not advisable as they may evolve some combined water. PMID:18962233

  5. Hematite Spherules in Basaltic Tephra Altered Under Aqueous, Acid-Sulfate Conditions on Mauna Kea Volcano, Hawaii: Possible Clues for the Occurrence of Hematite-Rich Spherules in the Burns Formation at Meridiani Planum, Mars

    NASA Technical Reports Server (NTRS)

    Morris, R. V.; Ming, D. W.; Graff, T. G.; Arvidson, R. E.; Bell, J. F., III; Squyres, S. W.; Mertzman, S. A.; Gruener, J. E.; Golden, D. C.; Robinson, G. A.

    2005-01-01

    Iron-rich spherules (>90% Fe2O3 from electron microprobe analyses) approx.10-100 microns in diameter are found within sulfate-rich rocks formed by aqueous, acid-sulfate alteration of basaltic tephra on Mauna Kea volcano, Hawaii. Although some spherules are nearly pure Fe, most have two concentric compositional zones, with the core having a higher Fe/Al ratio than the rim. Oxide totals less than 100% (93-99%) suggest structural H2O and/or /OH. The transmission Moessbauer spectrum of a spherule-rich separate is dominated by a hematite (alpha-Fe2O3) sextet whose peaks are skewed toward zero velocity. Skewing is consistent with Al(3+) for Fe(3+) substitution and structural H2O and/or /OH. The grey color of the spherules implies specular hematite. Whole-rock powder X-ray diffraction spectra are dominated by peaks from smectite and the hydroxy sulfate mineral natroalunite as alteration products and plagioclase feldspar that was present in the precursor basaltic tephra. Whether spherule formation proceeded directly from basaltic material in one event (dissolution of basaltic material and precipitation of hematite spherules) or whether spherule formation required more than one event (formation of Fe-bearing sulfate rock and subsequent hydrolysis to hematite) is not currently constrained. By analogy, a formation pathway for the hematite spherules in sulfate-rich outcrops at Meridiani Planum on Mars (the Burns formation) is aqueous alteration of basaltic precursor material under acid-sulfate conditions. Although hydrothermal conditions are present on Mauna Kea, such conditions may not be required for spherule formation on Mars if the time interval for hydrolysis at lower temperatures is sufficiently long.

  6. Physico-chemical conditions for plankton in Lake Timsah, a saline lake on the Suez Canal

    NASA Astrophysics Data System (ADS)

    El-Serehy, H. A. H.; Sleigh, M. A.

    1992-02-01

    Lake Timsah receives high salinity water from the Suez Canal, mainly from the south, and freshwater from a Nile canal and other sources, producing a salinity stratification with surface salinities of 20-40‰ and over 40‰ in deeper water. Water temperature at a depth of 50-70 cm fell to below 20 °C in winter and rose to above 30 °C in summer; oxygen concentration at the same depth ranged between 6-10 mg l -1 and the pH was 8·1-8·3, and at mid-day this water was supersaturated with oxygen through 6-8 months of the year. The main chemical nutrients reached their highest levels in winter (December-February) and their lowest levels in summer (May-August), silicate varying between 1-7 ? M, phosphate between 0·1 and 0·8 ? M and nitrate between 4-10 ? M; nitrite varied in a more complex manner, usually between 0·25 and 0·4 ? M. The atomic ratio of N/P was generally well above the Redfield ratio level, except for a few months in midwinter. These nutrient concentrations are high in comparison with those of unpolluted seas of the region, but are typical of the more eutrophic coastal waters in most parts of the world.

  7. Chemical interaction of aqueous solutions with epidote-feldspar mineral assemblages in geologic systems. II. Equilibrium constraints in metamorphic/geothermal processes

    SciTech Connect

    Bird, D.K.; Helgeson, H.C.

    1981-05-01

    Thermodynamic analysis of the system Na/sub 2/O-K/sub 2/O-CaO-FeO-Fe/sub 2/O/sub 3/-Al/sub 2/O/sub 3/-SiO/sub 2/-H/sub 2/O-HCl-CO/sub 2/ at pressures and temperatures to 5 kb and 600/sup 0/C affords quantitative description and interpretation of phase relations among epidote, garnet, plagioclase, and alkali feldspar solid solutions in hydrothermal systems. Comparison of computed and observed compositions of these minerals and coexisting fluids suggests that the calculations afford close approximation of equilibrium and mass transfer in metamorphic/geothermal processes. The standard molal enthalpies of decomposition reactions for plagioclase are of the order of -4 to -50 kcal mole/sup -1/, which requires the activity of the anorthite component of plagioclase coexisting with epidote solid solutions to increase with increasing temperature at constant pressure. In contrast, because the standard molal volumes of these reactions are also negative, a/sub CaAl/sub 2/Si/sub 2/O/sub 8// decreases with increasing pressure at constant temperature. Either stoichiometric epidote or clinozoisite is compatible with plagioclase, quartz, calcite, and an aqueous phase, but only at X/sub CO/sub 2// less than or equal to 0.2. The complex zoning commonly exhibited by both plagioclase and epidote solid solutions in geologic systems can be attributed to minor isothermal/isobaric changes in the composition of coexisting aqueous solutions. Logarithmic activity and fugacity diagrams constructed with provision for solid solution permit documentation of such changes and facilitate thermodynamic interpretation of mineral and fluid compositions in metamorphic/geothermal systems.

  8. Effects of Atmospheric Conditions and the Land/Atmospheric Interface on Transport of Chemical Vapors from Subsurface Sources

    NASA Astrophysics Data System (ADS)

    Rice, A. K.; Smits, K. M.; Cihan, A.; Howington, S. E.; Illangasekare, T. H.

    2013-12-01

    Understanding the movement of chemical vapors and gas through variably saturated soil subjected to atmospheric thermal and mass flux boundary conditions at the land/atmospheric interface is important to many applications, including landmine detection, methane leakage during natural gas production from shale and CO2 leakage from deep geologic storage. New, advanced technologies exist to sense chemical signatures and gas leakage at the land/atmosphere interface, but interpretation of sensor signals remains a challenge. Chemical vapors are subject to numerous interactions while migrating through the soil environment, masking source conditions. The process governing movement of gases through porous media is often assumed to be Fickian diffusion through the air phase with minimal quantification of other processes, such as convective gas flow and temporal or spatial variation in soil moisture. Vapor migration is affected by atmospheric conditions (e.g. humidity, temperature, wind velocity), soil thermal and hydraulic properties and contaminant properties, all of which are physically and thermodynamically coupled. The complex coupling of two drastically different flow regimes in the subsurface and atmosphere is commonly ignored in modeling efforts, or simplifying assumptions are made to treat the systems as de-coupled. Experimental data under controlled laboratory settings are lacking to refine the theory for proper coupling and complex treatment of vapor migration through porous media in conversation with atmospheric flow and climate variations. Improving fundamental understanding and accurate quantification of these processes is not feasible in field settings due to lack of controlled initial and boundary conditions and inability to fully characterize the subsurface at all relevant scales. The goal of this work is to understand the influence of changes in atmospheric conditions to transport of vapors through variably saturated soil. We have developed a tank apparatus with a network of soil and atmospheric sensors and a head space for air flow to simulate the atmospheric boundary layer. Experiments were performed under varying temperature values at the soil surface bounded by the atmospheric boundary layer. The model of Smits et al. [2011], accounting for non-equilibrium phase change and coupled heat, water vapor and liquid water flux through soil, was amended to include organic vapor in the gas phase and migration mechanisms often overlooked in models (thermal and Knudsen diffusion, density driven advection). Experimental results show increased vapor mass flux across the soil/atmospheric interface due to heat applied from the atmosphere and coupling of heat and mass transfer in the shallow subsurface for both steady and diurnal temperature patterns. Comparison of model results to experimental data shows dynamic interactions between transport in porous media and boundary conditions. Results demonstrate the value of considering interactions of the atmosphere and subsurface to better understand chemical gas transport through unsaturated soils and the land/atmospheric interface.

  9. Corrosion problems with aqueous coolants, final report

    SciTech Connect

    Diegle, R B; Beavers, J A; Clifford, J E

    1980-04-11

    The results of a one year program to characterize corrosion of solar collector alloys in aqueous heat-transfer media are summarized. The program involved a literature review and a laboratory investigation of corrosion in uninhibited solutions. It consisted of three separate tasks, as follows: review of the state-of-the-art of solar collector corrosion processes; study of corrosion in multimetallic systems; and determination of interaction between different waters and chemical antifreeze additives. Task 1 involved a comprehensive review of published literature concerning corrosion under solar collector operating conditions. The reivew also incorporated data from related technologies, specifically, from research performed on automotive cooling systems, cooling towers, and heat exchangers. Task 2 consisted of determining the corrosion behavior of candidate alloys of construction for solar collectors in different types of aqueous coolants containing various concentrations of corrosive ionic species. Task 3 involved measuring the degradation rates of glycol-based heat-transfer media, and also evaluating the effects of degradation on the corrosion behavior of metallic collector materials.

  10. Removal of Indigo Carmine and Pb(II) Ion from Aqueous Solution by Polyaniline

    Microsoft Academic Search

    Murat Ya?ar; Hüseyin Deligöz; Gamze Güçlü

    2011-01-01

    In this work, we report the synthesis of polyaniline emaraldine salt (PAni-ES) by a chemical oxidative polymerization method. The obtained PAni-ES samples prepared under different conditions were used for the removal of indigo carmine anionic dye and Pb(II) ion from aqueous solutions. The results also showed that the pseudo–second-order kinetic model fitted better than the data obtained from pseudo–first-order model

  11. Chemical Profiling of Jatropha Tissues under Different Torrefaction Conditions: Application to Biomass Waste Recovery

    PubMed Central

    Watanabe, Taiji; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

    2014-01-01

    Gradual depletion of the world petroleum reserves and the impact of environmental pollution highlight the importance of developing alternative energy resources such as plant biomass. To address these issues, intensive research has focused on the plant Jatropha curcas, which serves as a rich source of biodiesel because of its high seed oil content. However, producing biodiesel from Jatropha generates large amounts of biomass waste that are difficult to use. Therefore, the objective of our research was to analyze the effects of different conditions of torrefaction on Jatropha biomass. Six different types of Jatropha tissues (seed coat, kernel, stem, xylem, bark, and leaf) were torrefied at four different temperature conditions (200°C, 250°C, 300°C, and 350°C), and changes in the metabolite composition of the torrefied products were determined by Fourier transform-infrared spectroscopy and nuclear magnetic resonance analyses. Cellulose was gradually converted to oligosaccharides in the temperature range of 200°C–300°C and completely degraded at 350°C. Hemicellulose residues showed different degradation patterns depending on the tissue, whereas glucuronoxylan efficiently decomposed between 300°C and 350°C. Heat-induced depolymerization of starch to maltodextrin started between 200°C and 250°C, and oligomer sugar structure degradation occurred at higher temperatures. Lignin degraded at each temperature, e.g., syringyl (S) degraded at lower temperatures than guaiacyl (G). Finally, the toxic compound phorbol ester degraded gradually starting at 235°C and efficiently just below 300°C. These results suggest that torrefaction is a feasible treatment for further processing of residual biomass to biorefinery stock or fertilizer. PMID:25191879

  12. Chemical profiling of Jatropha tissues under different torrefaction conditions: application to biomass waste recovery.

    PubMed

    Watanabe, Taiji; Shino, Amiu; Akashi, Kinya; Kikuchi, Jun

    2014-01-01

    Gradual depletion of the world petroleum reserves and the impact of environmental pollution highlight the importance of developing alternative energy resources such as plant biomass. To address these issues, intensive research has focused on the plant Jatropha curcas, which serves as a rich source of biodiesel because of its high seed oil content. However, producing biodiesel from Jatropha generates large amounts of biomass waste that are difficult to use. Therefore, the objective of our research was to analyze the effects of different conditions of torrefaction on Jatropha biomass. Six different types of Jatropha tissues (seed coat, kernel, stem, xylem, bark, and leaf) were torrefied at four different temperature conditions (200°C, 250°C, 300°C, and 350°C), and changes in the metabolite composition of the torrefied products were determined by Fourier transform-infrared spectroscopy and nuclear magnetic resonance analyses. Cellulose was gradually converted to oligosaccharides in the temperature range of 200°C-300°C and completely degraded at 350°C. Hemicellulose residues showed different degradation patterns depending on the tissue, whereas glucuronoxylan efficiently decomposed between 300°C and 350°C. Heat-induced depolymerization of starch to maltodextrin started between 200°C and 250°C, and oligomer sugar structure degradation occurred at higher temperatures. Lignin degraded at each temperature, e.g., syringyl (S) degraded at lower temperatures than guaiacyl (G). Finally, the toxic compound phorbol ester degraded gradually starting at 235°C and efficiently just below 300°C. These results suggest that torrefaction is a feasible treatment for further processing of residual biomass to biorefinery stock or fertilizer. PMID:25191879

  13. Chemical repair of base lesions, AP-sites, and strand breaks on plasmid DNA in dilute aqueous solution by ascorbic acid

    SciTech Connect

    Hata, Kuniki [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan) [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Urushibara, Ayumi; Yamashita, Shinichi; Shikazono, Naoya; Yokoya, Akinari [Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan)] [Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 (Japan); Katsumura, Yosuke, E-mail: katsu@n.t.u-tokyo.ac.jp [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan) [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan); Nuclear Professional School, School of Engineering, The University of Tokyo, 2-22 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1188 (Japan)

    2013-05-03

    Highlights: •We report a novel mechanism of radiation protection of DNA by chemical activity of ascorbic acid. •The “chemical repair” of DNA damage was revealed using biochemical assay and chemical kinetics analysis. •We found that ascorbic acid significantly repairs precursors of nucleobase lesions and abasic sites. •However, ascorbic acid seldom repairs precursors of DNA-strand breaks. -- Abstract: We quantified the damage yields produced in plasmid DNA by ?-irradiation in the presence of low concentrations (10–100 ?M) of ascorbic acid, which is a major antioxidant in living systems, to clarify whether it chemically repairs radiation damage in DNA. The yield of DNA single strand breaks induced by irradiation was analyzed with agarose gel electrophoresis as conformational changes in closed circular plasmids. Base lesions and abasic sites were also observed as additional conformational changes by treating irradiated samples with glycosylase proteins. By comparing the suppression efficiencies to the induction of each DNA lesion, in addition to scavenging of the OH radicals derived from water radiolysis, it was found that ascorbic acid promotes the chemical repair of precursors of AP-sites and base lesions more effectively than those of single strand breaks. We estimated the efficiency of the chemical repair of each lesion using a kinetic model. Approximately 50–60% of base lesions and AP-sites were repaired by 10 ?M ascorbic acid, although strand breaks were largely unrepaired by ascorbic acid at low concentrations. The methods in this study will provide a route to understanding the mechanistic aspects of antioxidant activity in living systems.

  14. Deposition and reentrainment of Brownian particles in porous media under unfavorable chemical conditions: some concepts and applications.

    PubMed

    Hahn, Melinda W; O'Meliae, Charles R

    2004-01-01

    The deposition and reentrainment of particles in porous media have been examined theoretically and experimentally. A Brownian Dynamics/Monte Carlo (MC/BD) model has been developed that simulates the movement of Brownian particles near a collector under "unfavorable" chemical conditions and allows deposition in primary and secondary minima. A simple Maxwell approach has been used to estimate particle attachment efficiency by assuming deposition in the secondary minimum and calculating the probability of reentrainment. The MC/BD simulations and the Maxwell calculations support an alternative view of the deposition and reentrainment of Brownian particles under unfavorable chemical conditions. These calculations indicate that deposition into and subsequent release from secondary minima can explain reported discrepancies between classic model predictions that assume irreversible deposition in a primary well and experimentally determined deposition efficiencies that are orders of magnitude larger than Interaction Force Boundary Layer (IFBL) predictions. The commonly used IFBL model, for example, is based on the notion of transport over an energy barrier into the primary well and does not address contributions of secondary minimum deposition. A simple Maxwell model based on deposition into and reentrainment from secondary minima is much more accurate in predicting deposition rates for column experiments at low ionic strengths. It also greatly reduces the substantial particle size effects inherent in IFBL models, wherein particle attachment rates are predicted to decrease significantly with increasing particle size. This view is consistent with recent work by others addressing the composition and structure of the first few nanometers at solid-water interfaces including research on modeling water at solid-liquid interfaces, surface speciation, interfacial force measurements, and the rheological properties of concentrated suspensions. It follows that deposition under these conditions will depend on the depth of the secondary minimum and that some transition between secondary and primary depositions should occur when the height of the energy barrier is on the order of several kT. When deposition in secondary minima predominates, observed deposition should increase with increasing ionic strength, particle size, and Hamaker constant. Since an equilibrium can develop between bound and bulk particles, the collision efficiency [alpha] can no longer be considered a constant for a given physical and chemical system. Rather, in many cases it can decrease over time until it eventually reaches zero as equilibrium is established. PMID:14740738

  15. Conditioned Place Avoidance of Zebrafish (Danio rerio) to Three Chemicals Used for Euthanasia and Anaesthesia

    PubMed Central

    Wong, Devina; von Keyserlingk, Marina A. G.; Richards, Jeffrey G.; Weary, Daniel M.

    2014-01-01

    Zebrafish are becoming one of the most used vertebrates in developmental and biomedical research. Fish are commonly killed at the end of an experiment with an overdose of tricaine methanesulfonate (TMS, also known as MS-222), but to date little research has assessed if exposure to this or other agents qualifies as euthanasia (i.e. a “good death”). Alternative agents include metomidate hydrochloride and clove oil. We use a conditioned place avoidance paradigm to compare aversion to TMS, clove oil, and metomidate hydrochloride. Zebrafish (n?=?51) were exposed to the different anaesthetics in the initially preferred side of a light/dark box. After exposure to TMS zebrafish spent less time in their previously preferred side; aversion was less pronounced following exposure to metomidate hydrochloride and clove oil. Nine of 17 fish exposed to TMS chose not to re-enter the previously preferred side, versus 2 of 18 and 3 of 16 refusals for metomidate hydrochloride and clove oil, respectively. We conclude that metomidate hydrochloride and clove oil are less aversive than TMS and that these agents be used as humane alternatives to TMS for killing zebrafish. PMID:24505365

  16. Conditioned place avoidance of zebrafish (Danio rerio) to three chemicals used for euthanasia and anaesthesia.

    PubMed

    Wong, Devina; von Keyserlingk, Marina A G; Richards, Jeffrey G; Weary, Daniel M

    2014-01-01

    Zebrafish are becoming one of the most used vertebrates in developmental and biomedical research. Fish are commonly killed at the end of an experiment with an overdose of tricaine methanesulfonate (TMS, also known as MS-222), but to date little research has assessed if exposure to this or other agents qualifies as euthanasia (i.e. a "good death"). Alternative agents include metomidate hydrochloride and clove oil. We use a conditioned place avoidance paradigm to compare aversion to TMS, clove oil, and metomidate hydrochloride. Zebrafish (n = 51) were exposed to the different anaesthetics in the initially preferred side of a light/dark box. After exposure to TMS zebrafish spent less time in their previously preferred side; aversion was less pronounced following exposure to metomidate hydrochloride and clove oil. Nine of 17 fish exposed to TMS chose not to re-enter the previously preferred side, versus 2 of 18 and 3 of 16 refusals for metomidate hydrochloride and clove oil, respectively. We conclude that metomidate hydrochloride and clove oil are less aversive than TMS and that these agents be used as humane alternatives to TMS for killing zebrafish. PMID:24505365

  17. The identification and measurement of components in gasoline, kerosene, and no. 2 fuel oil that partition into the aqueous phase after mixing

    Microsoft Academic Search

    W. Emile Coleman; Jean W. Munch; Robert P. Streicher; H. Paul Ringhand; Frederick C. Kopfler

    1984-01-01

    Some of the most common spills in waterways involve petroleum products, which are complex mixtures of varying compositions, depending on source and refining procedures. The tendency for components of potential toxicological significance to distribute to the aqueous phase under spill conditions needs to be determined. This paper is devoted to the chemical analysis of the water-soluble fractions (WSF) of gasoline,

  18. MICROWAVE-ASSISTED CYCLOCONDENSATION OF HYDRAZINE DERIVATIVES WITH ALKYL DIHALIDES OR DITOSYLATES IN AQUEOUS MEDIA: SYNTHESES OF PYRAZOLE, PYRAZOLIDINE AND PHTHALAZINE DERIVATIVES

    EPA Science Inventory

    Direct synthesis of 4,5-dihydro-pyrazole, pyrazolidine, and 1,2-dihydro-phthalazine derivatives via double alkylation of hydrazines by alkyl dihalides or ditosylates were accomplished in aqueous media under microwave irradiation conditions; the environmentally friendlier chemical...

  19. Ionic liquid-aqueous solution ultrasonic-assisted extraction of three kinds of alkaloids from Phellodendron amurense Rupr and optimize conditions use response surface.

    PubMed

    Wang, Wenchao; Li, Qingyong; Liu, Yuhui; Chen, Binbin

    2015-05-01

    In this paper, we chose diffident kinds of ionic liquids to optimal selection an optimal one to extract alkaloids from Phellodendron amurense Rupr. Four ionic liquids with diffident carbon chains or anions have been investigated and 1-butyl-3-methylimidazolium bromide with best productivity. Then, selections have been optimized in different conditions, including concentration of ionic liquid, time for ultrasonic treatment, ultrasonic power and solid-liquid ratio. Moreover, three conditions have been comprehensively assessment by response surface methodology, the optimal conditions were determined as follows ultrasonic power 100 W, extraction time 75 min and ratio of solvent to raw material 1:14. Under these conditions, the yield% (MIX) was 106.7% (extracted by heat reflux being defined 100%). Comparing with other methods, the advantages are saving conserving, time saving, high yield% and especially pollution-free. PMID:25443277

  20. Metalorganic Chemical Vapor Deposition Conditions for Efficient Silicon Doping in High Al-Composition AlGaN Films

    NASA Astrophysics Data System (ADS)

    Keller, Stacia; Cantu, Pablo; Moe, Craig; Wu, Yuan; Keller, Salka; Mishra, Umesh K.; Speck, James S.; DenBaars, Steven P.

    2005-10-01

    The influence of the metalorganic chemical vapor deposition conditions on the electrical and optical properties was investigated for silicon-doped AlxGa1-xN films with x>0.5 grown on sapphire and 6H--SiC substrates. At a constant silicon concentration in the layers, the electron carrier concentration was the highest in films deposited at reduced temperatures and high V/III ratios, despite the higher residual carbon and oxygen concentrations in the layers grown at lower temperatures. The electrical properties of the films were correlated with the intensity of the emission bands in the 410 to 440 nm and the 510 to 550 nm ranges observed in the 300 K photoluminescence spectra of the samples. The influence of impurities, native defects and threading dislocations on the film properties is discussed.

  1. Chemical and morphological characterization of Chardonnay and Gewürztraminer grapes and changes during chamber-drying under controlled conditions.

    PubMed

    Serratosa, Maria P; Marquez, Ana; Moyano, Lourdes; Zea, Luis; Merida, Julieta

    2014-09-15

    In this work, the morphological and chemical properties of Chardonnay and Gewürztraminer aromatic grapes (northern Spain) have been studied with the aim to assess their response to chamber-drying under controlled conditions and compare it with that of Pedro Ximenez grapes (southern Spain). Morphological characteristics, such as weight, size and roundness, and other of the skin such as thickness, enabled discrimination of the two types of grapes varieties. Changes in browning index, colour, antioxidant activity, aroma compounds determined by GC-MS and flavan-3-ols and flavonols concentrations determined by HPLC-DAD were studied during drying. Based on the results, Chardonnay and Gewürztraminer grapes contained increased amounts of flavan-3-ol derivatives, which are the greatest contributors to polymerization and condensation reactions. Also, their smaller size resulted in faster drying and leads to sugary musts that were lighter-coloured, less brown and more aromatic than Pedro Ximenez grapes. PMID:24767035

  2. Identification of morphological and chemical markers of dry- and wet-season conditions in female Anopheles gambiae mosquitoes

    PubMed Central

    2014-01-01

    Background Increased understanding of the dry-season survival mechanisms of Anopheles gambiae in semi-arid regions could benefit vector control efforts by identifying weak links in the transmission cycle of malaria. In this study, we examined the effect of photoperiod and relative humidity on morphologic and chemical traits known to control water loss in mosquitoes. Methods Anopheles gambiae body size (indexed by wing length), mesothoracic spiracle size, and cuticular hydrocarbon composition (both standardized by body size) were examined in mosquitoes raised from eggs exposed to short photoperiod and low relative humidity, simulating the dry season, or long photoperiod and high relative humidity, simulating the wet-season. Results Mosquitoes exposed to short photoperiod exhibited larger body size and larger mesothoracic spiracle length than mosquitoes exposed to long photoperiod. Mosquitoes exposed to short photoperiod and low relative humidity exhibited greater total cuticular hydrocarbon amount than mosquitoes exposed to long photoperiod and high relative humidity. In addition, total cuticular hydrocarbon amount increased with age and was higher in mated females. Mean n-alkane retention time (a measure of cuticular hydrocarbon chain length) was lower in mosquitoes exposed to short photoperiod and low relative humidity, and increased with age. Individual cuticular hydrocarbon peaks were examined, and several cuticular hydrocarbons were identified as potential biomarkers of dry- and wet-season conditions, age, and insemination status. Conclusions Results from this study indicate that morphological and chemical changes underlie aestivation of Anopheles gambiae and may serve as biomarkers of aestivation. PMID:24970701

  3. Kinetic studies of chemical shrinkage and residual stress formation in thermoset epoxy adhesives under confined curing conditions

    NASA Astrophysics Data System (ADS)

    Schumann, M.; Geiß, P. L.

    2015-05-01

    Faultless processing of thermoset polymers in demanding applications requires a profound mastering of the curing kinetics considering both the physico-chemical changes in the transition from the liquid to the solid state and the consolidation of the polymers network in the diffusion controlled curing regime past the gel point. Especially in adhesive joints shrinkage stress occurring at an early state of the curing process under confined conditions is likely to cause defects due to local debonding and thus reduce their strength and durability1. Rheometry is considered the method of choice to investigate the change of elastic and viscous properties in the progress of curing. Drawbacks however relate to experimental challenges in accessing the full range of kinetic parameters of thermoset resins with low initial viscosity from the very beginning of the curing reaction to the post-cure consolidation of the polymer due to the formation of secondary chemical bonds. Therefore the scope of this study was to interrelate rheological data with results from in-situ measurements of the shrinkage stress formation in adhesive joints and with the change of refractive index in the progress of curing. This combination of different methods has shown to be valuable in gaining advanced insight into the kinetics of the curing reaction. The experimental results are based on a multi component thermoset epoxy-amine adhesive.

  4. Aqueous phase processing of secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Tritscher, T.; Praplan, A. P.; Decarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.; Monod, A.

    2011-07-01

    The aging of secondary organic aerosol (SOA) by photooxidation in the aqueous phase was experimentally investigated. To simulate multiphase processes, the following experiments were sequentially performed in a smog chamber and in an aqueous phase photoreactor: (1) Gas-phase photooxidation of three different volatile organic compounds (VOC): isoprene, ?-pinene, and 1,3,5-trimethylbenzene (TMB) in the presence of NOx, leading to the formation of SOA which was subjected to on-line physical and chemical analysis; (2) particle-to-liquid transfer of water soluble species of SOA using filter sampling and aqueous extraction; (3) aqueous-phase photooxidation of the obtained water extracts; and (4) nebulization of the solutions for a repetition of the on-line characterization. SOA concentrations in the chamber measured with a scanning mobility particle sizer (SMPS) were higher than 200 ?g m-3, as the experiments were conducted under high initial concentrations of volatile organic compounds (VOC) and NOx. The aging of SOA through aqueous phase processing was investigated by measuring the physical and chemical properties of the particles online before and after processing using a high resolution time-of-flight aerosol mass spectrometer (AMS) and a hygroscopicity tandem differential mobility analyzer (H-TDMA). It was shown that, after aqueous phase processing, the particles were significantly more hygroscopic, and contained more fragmentation ions at m/z = 44 and less ions at m/z = 43, thus showing a significant impact on SOA aging for the three different precursors. Additionally, the particles were analyzed with a thermal desorption atmospheric pressure ionization aerosol mass spectrometer (TD-API-AMS). Comparing the smog chamber SOA composition and non processed nebulized aqueous extracts with this technique revealed that sampling, extraction and/or nebulization did not significantly impact the chemical composition of SOA formed from isoprene and ?-pinene, whereas it affected that formed from TMB. For the two first precursors, the aqueous phase chemical composition of SOA was further investigated using offline measurements, i.e. ion chromatography coupled to a mass spectrometer (IC-MS) and an atmospheric pressure chemical ionization mass spectrometer (APCI-MS) equipped with high pressure liquid chromatography (HPLC-MS). These analyses showed that aqueous phase processing enhanced the formation of some compounds already present in the SOA, thus confirming the aging effect of aqueous phase processes. For isoprene experiments, additional new compounds, likely oligomers, were formed through aqueous phase photooxidation, and their possible origins are discussed.

  5. Chemical analysis of size-tailored magnetic colloids using slurry nebulization in ICP-OES

    Microsoft Academic Search

    Marcelo H. Sousa; Geraldo J. da Silva; Jérôme Depeyrot; Francisco A. Tourinho; Luiz F. Zara

    2011-01-01

    In this work, inductively coupled plasma emission spectroscopy was utilized to directly determine the chemical composition of magnetic fluids constituted of size-sorted ferrite nanoparticles in aqueous solution. Nickel and cobalt nanoferrites were chemically synthesized following a bottom-up route and dispersed under various pH conditions. Size and structural characteristics of nanograins were investigated by X-ray diffraction using a synchrotron source. Chemical

  6. Parenteral peptide formulations: chemical and physical properties of native luteinizing hormone-releasing hormone (LHRH) and hydrophobic analogues in aqueous solution.

    PubMed

    Powell, M F; Sanders, L M; Rogerson, A; Si, V

    1991-10-01

    The degradation of native LHRH in aqueous buffers of pH approximately 1-10 obeyed the rate equation, kobs = kH + alpha H+ + ko + kHO-(alpha HO-)x, where x at 60-100 degrees C was approximately 0.64 and temperature independent. Extrapolation to 25 degrees C using the Arrhenius equation and secondary rate constants showed that native LHRH is reasonably stable at pH 5.4, giving a shelf life (t90) of approximately 5 years. Regarding physical properties, hydrophobic LHRH analogues nafarelin and detirelix were found to be surface active as demonstrated by a decrease in apparent surface tension with increased peptide concentration. The CMC for detirelix at pH 7.4 was determined to be 5.3 x 10(-4) M (0.88 mg/ml), and that for nafarelin, greater than 2 mg/ml. At higher concentrations (approximately 4-8 mg/ml), nafarelin and detirelix formed nematic liquid crystals of undulose extinction (birefringence, less than 0.001). The thermodynamic stability of these peptide liquid crystals was probed by determining their melting points (Tcm) in the presence of propylene glycol, a solvent which proved to be efficacious at suppressing gelation and at destabilizing liquid crystals as measured by a reduction in Tcm. PMID:1839059

  7. Distribution of fish, benthic invertebrate, and algal communities in relation to physical and chemical conditions, Yakima River basin, Washington, 1990

    USGS Publications Warehouse

    Cuffney, T.F.; Meador, M.R.; Porter, S.D.; Gurtz, M.E.

    1997-01-01

    Biological investigations were conducted in the Yakima River Basin, Washington, in conjunction with a pilot study for the U.S. Geological Survey's National Water-Quality Assessment Program. Ecological surveys were conducted at 25 sites in 1990 to (1) assess water-quality conditions based on fish, benthic invertebrate, and algal communities; (2) determine the hydrologic, habitat, and chemical factors that affect the distributions of these organisms; and (3) relate physical and chemical conditions to water quality. Results of these investigations showed that land uses and other associated human activities influenced the biological characteristics of streams and rivers and overall water-quality conditions. Fish communities of headwater streams in the Cascades and Eastern Cascades ecoregions of the Yakima River Basin were primarily composed of salmonids and sculpins, with cyprinids dominating in the rest of the basin. The most common of the 33 fish taxa collected were speckled dace, rainbow trout, and Paiute sculpin. The highest number of taxa (193) was found among the inverte- brates. Insects, particularly sensitive forms such as mayflies, stoneflies, and caddisflies (EPT--Ephemeroptera, Plecoptera, and Trichoptera fauna), formed the majority of the invertebrate communities of the Cascades and Eastern Cascades ecoregions. Diatoms dominated algal communities throughout the basin; 134 algal taxa were found on submerged rocks, but other stream microhabitats were not sampled as part of the study. Sensitive red algae and diatoms were predominant in the Cascades and Eastern Cascades ecoregions, whereas the abundance of eutrophic diatoms and green algae was large in the Columbia Basin ecoregion of the Yakima River Basin. Ordination of physical, chemical, and biological site characteristics indicated that elevation was the dominant factor accounting for the distribution of biota in the Yakima River Basin; agricultural intensity and stream size were of secondary importance. Ordination identified three site groups and three community types. Site groups consisted of (1) small streams of the Cascades and Eastern Cascades ecoregions, (2) small streams of the Columbia Basin ecoregions, and (3) large rivers of the Cascades and Columbia Basin ecoregions. The small streams of the Columbia Basin could be further subdivided into two groups--one where agricultural intensity was low and one where agricultural intensity was moderate to high. Dividing the basin into these three groups removed much of the influence of elevation and facilitated the analysis of land-use effects. Community types identified by ordination were (1) high elevation, cold-water communities associated with low agricultural intensity; (2) lower elevation, warm-water communities associated with low agricultural intensity, and (3) lower elevation, warm-water communities associated with moderate to high agricultural intensity. Multimetric community condition indices indicated that sites in the Cascades and Eastern Cascades site group were largely unimpaired. In contrast, all but two sites in the Columbia Basin site group were impaired, some severely. Agriculture (nutrients and pesticides) was the primary factor responsible for this impairment, and all impaired sites were characterized by multiple indicators of impairment. Three sites (Granger Drain, Moxee Drain, and Spring Creek) had high levels of impairment. Sites in the large-river site group were moderately to severely impaired downstream from the city of Yakima. High levels of impairment at large-river sites corresponded with high levels of pesticides in fish tissues and the occurrence of external anomalies. The response exhibited by invertebrates and algae to a gradient of agricultural intensity suggested a threshold response for sites in the Columbia Basin site group. Community condition declined precipitously at agricultural intensities above 50 (non-pesticide agricultural intensity index) and showed little respon

  8. Laboratory insights into the chemical and kinetic evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    Poch, O.; Kaci, S.; Stalport, F.; Szopa, C.; Coll, P.

    2014-11-01

    The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars' exploration. Understanding the chemical evolution of organic molecules under current martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? This paper presents the results of laboratory investigations dedicated to monitor the evolution of organic molecules when submitted to simulated Mars surface ultraviolet radiation (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) conditions. Experiments are done with the MOMIE simulation setup (for Mars Organic Molecules Irradiation and Evolution) allowing both a qualitative and quantitative characterization of the evolution the tested molecules undergo (Poch, O. et al. [2013]. Planet. Space Sci. 85, 188-197). The chemical structures of the solid products and the kinetic parameters of the photoreaction (photolysis rate, half-life and quantum efficiency of photodecomposition) are determined for glycine, urea, adenine and chrysene. Mellitic trianhydride is also studied in order to complete a previous study done with mellitic acid (Stalport, F., Coll, P., Szopa, C., Raulin, F. [2009]. Astrobiology 9, 543-549), by studying the evolution of mellitic trianhydride. The results show that solid layers of the studied molecules have half-lives of 10-103 h at the surface of Mars, when exposed directly to martian UV radiation. However, organic layers having aromatic moieties and reactive chemical groups, as adenine and mellitic acid, lead to the formation of photoresistant solid residues, probably of macromolecular nature, which could exhibit a longer photostability. Such solid organic layers are found in micrometeorites or could have been formed endogenously on Mars. Finally, the quantum efficiencies of photodecomposition at wavelengths from 200 to 250 nm, determined for each of the studied molecules, range from 10-2 to 10-6 molecule photon-1 and apply for isolated molecules exposed at the surface of Mars. These kinetic parameters provide essential inputs for numerical modeling of the evolution of Mars' current reservoir of organic molecules. Organic molecules adsorbed on martian minerals may have different kinetic parameters and lead to different endproducts. The present study paves the way for the interpretation of more complex simulation experiments where organics will be mixed with martian mineral analogs.

  9. Applicability of DLVO Approach to Predict Trends in Iron Oxide Colloid Mobility Under Various Physical And Chemical Soil Conditions

    NASA Astrophysics Data System (ADS)

    Florian Carstens, Jannis; Bachmann, Jörg; Neuweiler, Insa

    2014-05-01

    In soil and groundwater, highly mobile iron oxide colloids can act as "shuttles" for transport of adsorbed contaminants such as heavy metals and radionuclides. Artificial iron oxide colloids are injected into polluted porous media to accelerate bacterial degradation of pollutants in the context of bioremediation purposes. The mobility of iron oxide colloids is strongly affected by the hydraulic, physical and chemical conditions of the pore space, the solid particle surface properties, the fluid phase, and the colloids themselves. Most pioneering studies focused on iron oxide colloid transport and retention in simplified model systems. The aim of this study is to investigate iron oxide colloid mobility under more complex, soil-typical conditions that have as yet only been applied for model microspheres, i.e. functionalized latex colloids. Among these conditions is the pivotal impact of organic matter, either dissolved or adsorbed onto solid particles, modifying wettability properties. Of particular importance was to determine if effective chemical surface parameters derived from contact angle and zeta potential measurements can be used as a tool to predict general tendencies for iron oxide colloid mobility in porous media. In column breakthrough experiments, goethite colloids (particle size: 200-900 nm) were percolated through quartz sand (grain size: 100-300 µm) at pH 5. The impact of a multitude of conditions on colloid mobility was determined: dissolved organic matter (DOM) concentration, ionic strength, flow velocity, flow interruption, partial saturation, and drying with subsequent re-wetting. The solid matrix consisted of either clean sand, organic matter-coated sand, goethite-coated sand, or sand hydrophobized with dichlorodimethylsilane. Additionally, contact angles and zeta potentials of the materials applied in the column experiments were measured. By means of these surface parameters, traditional DLVO interaction energies based on zeta potential as well as extended DLVO energies including Lewis acid-base parameters based on contact angle measurements were estimated. The results elucidate that high mobility of goethite colloids was distinctly restricted to a narrow set of conditions: presence of DOM, sufficient flow velocity and constant flow, low ionic strength, full saturation as well as an uncoated and hydrophilic quartz sand matrix. Any deviation from these favorable transport conditions led from varying degrees of colloid retention up to complete immobilization. Results yielded by both traditional and extended DLVO interaction energy calculations demonstrated that increasing secondary minimum depth correlated well with higher colloid retention. Extended DLVO calculations revealed strong repulsive forces due to Lewis acid-base interactions at close distances that did not comply with experimental data. It is likely that Lewis acid-base interactions were limited due to surface roughness of the sand grains and colloids. It can be concluded that the impact of various soil and hydraulic conditions on goethite colloid mobility is in principle assessable with column flow experiments. Moreover, with restrictions for the interpretation of close-distance interactions, DLVO interaction energies are capable of predicting general trends of goethite colloid mobility.

  10. UV/TiO2 and UV/TiO2/chemical oxidant processes for the removal of humic acid, Cr and Cu in aqueous TiO2 suspensions.

    PubMed

    Jung, J-T; Choi, J-Y; Chung, J; Lee, Y-W; Kim, J-O

    2009-03-01

    The objective of this study was to investigate the treatment efficiency of UV/TiO2 and UV/TiO2/chemical oxidant processes for the removal of humic acid and hazardous heavy metals in aqueous TiO2 suspensions. The reaction rate (k) of humic acid and hazardous heavy metals by UV/TiO2 was higher than that of UV illumination alone or TiO2 alone. The removal efficiency for humic acid and Cr(VI) at acid or neutral pH values was higher than that at basic pH values. However, the removal efficiency for Cu(II) at acid pH values was smaller compared with that at neutral or basic pH values. The reaction rate (k) of humic acid and hazardous heavy metals in the TiO2 concentration range of 0.1-0.3 g l(-1) increased with increasing TiO2 dosage. However, amounts higher than a TiO2 dosage of 0.3 g l(-1) reduced the removal efficiency for humic acid and hazardous heavy metals because of the shielding effect on the UV light penetration in the aqueous solution caused by the presence of excessive amounts of TiO2. The addition of oxidants to the UV/TiO2 system showed an increase in degradation efficiency for the treatment of humic acid and hazardous heavy metals. The optimal concentration of oxidants was: H2O2 50 mg l(-1), O3 20 g m(-3) and K2S2O8 50 mg l(-1), respectively. The degradation efficiency of UV/TiO2/oxidant systems for the removal of humic acid and hazardous heavy metals was much greater when H2O2 was used as the oxidant. PMID:19438054

  11. An investigation on the chemical stability and a novel strategy for long-term stabilization of diphenylalanine nanostructures in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nezammahalleh, H.; Amoabediny, G.; Kashanian, F.; Foroughi Moghaddam, M. H.

    The stability of diphenylalanine (FF) microwires and microtubes in phosphate buffer solution was investigated and a novel strategy was developed for their chemical stabilization. This stability investigation was carried out by optical microscopy and by high performance liquid chromatography (HPLC). These microstructures dissolve in the solution depending upon their degree of FF saturation. The dissolution mechanisms of the structures in kinetically limited processes were found by accurately fitting the experimental dissolution data to a theoretical kinetic equation. The dissolution data were well fitted to the particular Avrami-Erofe'ev kinetic expression (R2 > 0.98). These findings suggest that the structures can be stabilized by a decrease in the hydration of the constituent molecules thorough a chemical conformational induced transition upon heat treatment. The stable microtubes were fabricated in a novel three step procedure consisting of the reduction of silver ions in unstable FF microtubes by a citrate reductant, the stabilization by chemical conformational induced transition upon heat treatment, and the consequent oxidation of the reduced silver by a persulfate oxidant. These materials were characterized by electron microscopy and powder X-ray diffraction techniques. The long-term stability of both structures was also confirmed by optical microscopy and HPLC.

  12. Modification of surface properties of Lentinus sajor-caju mycelia by physical and chemical methods: evaluation of their Cr6+ removal efficiencies from aqueous medium.

    PubMed

    Bayramo?lu, Gülay; Celik, Gökçe; Yalçin, Emine; Yilmaz, Meltem; Arica, M Yakup

    2005-03-17

    The hexavalent chromium biosorption onto untreated and heat-, acid- and alkali-treated Lentinus sajor-caju mycelia were studied from aqueous solutions. The particles sizes of the fungal mycelia ranged from 100 to 200 microm. The effect of pH, temperature, biosorbent dose, initial concentration of chromium ions, contact time parameters were investigated in a batch system. Biosorption equilibrium was established in about 4 h. The surface charge density of the fungal preparations varied with pH, and the maximum absorption of chromium ions on the fungal preparations were obtained at pH 2.0. The biosorption of chromium ions by the tested fungal preparations increased as the initial concentration of chromium ions increased in the medium. The maximum biosorption capacities of the untreated and heat, HCl- and NaOH-treated fungal biomass were 0.363, 0.613, 0.478 and 0.513 mmol Cr6+ per gram of dry biomass, respectively. The correlation regression coefficients and the Langmuir constant values show that the biosorption process can be well defined by Langmuir equation. The chromium adsorption data were analysed using the first- and the second-order kinetic models. The first-order equation is the most appropriate equation to predict the biosorption capacities of all the fungal preparations. In addition, the polarity and surface energy of the untreated and all the modified biomass film preparations were determined by contact angle measurement. All the tested fungal biomass preparations could be regenerated using 0.1 M NaOH solution. PMID:15752869

  13. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

    NASA Astrophysics Data System (ADS)

    Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-04-01

    The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor of 5 when mixed with nontronite at a concentration of 2.6×10-2 mole per gram. Moreover when the amount of nontronite in the sample of glycine is increased by a factor of two, the gain of photoprotection is multiplied by a factor of five. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect, but is at least partly due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate, in strong contrast with the other two molecules.

  14. Inverse hydrochemical models of aqueous extracts tests

    SciTech Connect

    Zheng, L.; Samper, J.; Montenegro, L.

    2008-10-10

    Aqueous extract test is a laboratory technique commonly used to measure the amount of soluble salts of a soil sample after adding a known mass of distilled water. Measured aqueous extract data have to be re-interpreted in order to infer porewater chemical composition of the sample because porewater chemistry changes significantly due to dilution and chemical reactions which take place during extraction. Here we present an inverse hydrochemical model to estimate porewater chemical composition from measured water content, aqueous extract, and mineralogical data. The model accounts for acid-base, redox, aqueous complexation, mineral dissolution/precipitation, gas dissolution/ex-solution, cation exchange and surface complexation reactions, of which are assumed to take place at local equilibrium. It has been solved with INVERSE-CORE{sup 2D} and been tested with bentonite samples taken from FEBEX (Full-scale Engineered Barrier EXperiment) in situ test. The inverse model reproduces most of the measured aqueous data except bicarbonate and provides an effective, flexible and comprehensive method to estimate porewater chemical composition of clays. Main uncertainties are related to kinetic calcite dissolution and variations in CO2(g) pressure.

  15. Coordination modes of multidentate ligands in fac-[Re(CO)(3)(polyaminocarboxylate)] analogues of (99m)Tc radiopharmaceuticals. dependence on aqueous solution reaction conditions.

    PubMed

    Lipowska, Malgorzata; He, Haiyang; Xu, Xiaolong; Taylor, Andrew T; Marzilli, Patricia A; Marzilli, Luigi G

    2010-04-01

    We study Re analogues of (99m)Tc renal agents to interpret previous results at the (99m)Tc tracer level. The relative propensities of amine donors versus carboxylate oxygen donors of four L = polyaminocarboxylate ligands to coordinate in fac-[Re(I)(CO)(3)L](n) complexes were assessed by examining the reaction of fac-[Re(I)(CO)(3)(H(2)O)(3)](+) under conditions differing in acidity and temperature. All four L [N,N-bis-(2-aminoethyl)glycine (DTGH), N,N-ethylenediaminediacetic acid, diethylenetriamine-N-malonic acid, and diethylenetriamine-N-acetic acid] can coordinate as tridentate ligands while creating a dangling chain terminated in a carboxyl group. Dangling carboxyl groups facilitate renal clearance in fac-[(99m)Tc(I)(CO)(3)L](n) agents. Under neutral conditions, the four ligands each gave two fac-[Re(I)(CO)(3)L](n) products with HPLC traces correlating well with known traces of the fac-[(99m)Tc(I)(CO)(3)L](n) mixtures. Such mixtures are common in renal agents because the needed dangling carboxyl group can compete for a coordination site. However, the HPLC separations needed to assess the biodistribution of a single tracer are impractical in a clinical setting. One goal in investigating this Re chemistry is to identify conditions for avoiding this problem of mixtures in preparations of fac-[(99m)Tc(I)(CO)(3)L](n) renal tracers. After separation and isolation of the fac-[Re(I)(CO)(3)L](n) products, NMR analysis of all products and single crystal X-ray crystallographic analysis of both DTGH products, as well as one product each from the other L, allowed us to establish coordination mode unambiguously. The product favored in acidic conditions has a dangling amine chain and more bound oxygen. The product favored in basic conditions has a dangling carboxyl chain and more bound nitrogen. At the elevated temperatures used for simulating tracer preparation, equilibration was facile (ca. 1 h or less), allowing selective formation of one product by utilizing acidic or basic conditions. The results of this fundamental study offer protocols and guidance useful for the design and preparation of fac-[(99m)Tc(I)(CO)(3)L](n) agents consisting of a single tracer. PMID:20201565

  16. Coordination Modes of Multidentate Ligands in fac-[Re(CO)3(polyaminocarboxylate)] Analogues of 99mTc Radiopharmaceuticals. Dependence on Aqueous Solution Reaction Conditions

    PubMed Central

    Lipowska, Malgorzata; He, Haiyang; Xu, Xiaolong; Taylor, Andrew T.; Marzilli, Patricia A.; Marzilli, Luigi G.

    2010-01-01

    We study Re analogues of 99mTc renal agents to interpret previous results at the 99mTc tracer level. The relative propensities of amine donors vs. carboxylate oxygen donors of four L = polyaminocarboxylate ligands to coordinate in fac-[ReI(CO)3L]n complexes were assessed by examining the reaction of fac-[ReI(CO)3(H2O)3]+ under conditions differing in acidity and temperature. All four L [N,N-bis-(2-aminoethyl)glycine (DTGH), N,N-ethylenediaminediacetic acid, diethylenetriamine-N-malonic acid, and diethylenetriamine-N-acetic acid] can coordinate as tridentate ligands while creating a dangling chain terminated in a carboxyl group. Dangling carboxyl groups facilitate renal clearance in fac-[99mTcI(CO)3L]n agents. Under neutral conditions, the four ligands each gave two fac-[ReI(CO)3L]n products with HPLC traces correlating well with known traces of the fac-[99mTcI(CO)3L]n mixtures. Such mixtures are common in renal agents because the needed dangling carboxyl group can compete for a coordination site. However, the HPLC separations needed to assess the biodistribution of a single tracer are impractical in a clinical setting. One goal in investigating this Re chemistry is to identify conditions for avoiding this problem of mixtures in preparations of fac-[99mTcI(CO)3L]n renal tracers. After separation and isolation of the fac-[ReI(CO)3L]n products, NMR analysis of all products and single crystal X-ray crystallographic analysis of both DTGH products as well as one product each from the other L allowed us to establish coordination mode unambiguously. The product favored in acidic conditions has a dangling amine chain and more bound oxygen. The product favored in basic conditions has a dangling carboxyl chain and more bound nitrogen. At the elevated temperatures used for simulating tracer preparation, equilibration was facile (ca. one hour or less), allowing selective formation of one product by utilizing acidic or basic conditions. The results of this fundamental study offer protocols and guidance useful for the design and preparation of fac-[99mTcI(CO)3L]n agents consisting of a single tracer. PMID:20201565

  17. Facilitated attachment of nanoparticles at primary minima by nanoscale roughness is susceptible to hydrodynamic drag under unfavorable chemical conditions.

    PubMed

    Shen, Chongyang; Jin, Yan; Li, Baoguo; Zheng, Wenjuan; Huang, Yuanfang

    2014-01-01

    This study investigated effects of flow velocity on attachment of nanoparticles at primary minima in the presence of surface roughness under unfavorable chemical conditions. Saturated sand-packed column experiments were conducted at 0.1 and 0.2M NaCl using 30 nm polystyrene latex nanoparticles as model colloids. Particle attachment at primary minima was unambiguously determined by removing particles attached at secondary minima through introducing deionized water and excavating the packed beds. The calculated primary-minimum attachment efficiency was found to decrease with increasing flow velocity, indicating that the fraction of a collector surface that is available for attachment at primary minima decreases with increasing flow velocity. The torque analysis, however, showed that the adhesive torque that the particle experiences at primary minima is much larger than the maximum hydrodynamic drags of a porous medium for the flow velocities used. We attributed the discrepancy to the reason that the sand surface is very rough and the roughness mainly causes the attachment in primary minima under the experimental conditions used in this study. By considering influence of surface roughness in the torque analysis, our calculations show that while particle attachment in primary minima is favored atop of nanoasperities under unfavorable conditions, the adhesive torque that the particle experiences can be greatly reduced and, thus, the attachment is susceptible to flow drag. Whereas the increase of adhesive torque by surface roughness has been widely recognized in the literature, our study indicates that the rough asperities can also decrease adhesive torques for particles attached atop of them. PMID:24013017

  18. Assigning chemical configurations to the XPS features observed at pristine (1 0 0) Si surface resulting after etching in HF aqueous solution

    NASA Astrophysics Data System (ADS)

    Cerofolini, G. F.; Romano, E.; Narducci, D.; Belanzoni, P.; Giorgi, G.

    2010-08-01

    While the analysis of the spectra resulting from energy- or angle-resolved X-ray photoelectron spectroscopy allows the in-depth atomic composition in the probed region to be determined even for complex samples, the determination of the bonding configuration is less trivial. In this paper it is shown that a description of the chemical shift in terms of partial charge and Madelung potential (as results from local modelling of the atom) can provide information even in complicate situations, like that characterizing the hydrogen-terminated (1 0 0) Si prepared by HF etching of the native oxide.

  19. Removal of transition metal ions from aqueous solutions by adsorption using a novel hybrid material silica gel chemically modified by triethylenetetraminomethylenephosphonic acid

    Microsoft Academic Search

    Yuan Tian; Ping Yin; Rongjun Qu; Chunhua Wang; Hegen Zheng; Zhongxi Yu

    2010-01-01

    A novel inorganic–organic hybrid material silica gel chemically modified by triethylenetetraminomethylenephosphonic acid (denoted as GH-T-P) has been synthesized and characterized. Its adsorption properties GH-T-P for Au(III), Hg(II), Cu(II), Pb(II), Co(II), Zn(II), Ni(II), Cr(III) and Cd(II) have been investigated, and the research results revealed that GH-T-P has the best adsorption capacity for Au(III). Furthermore, the adsorption selectivity results of GH-T-P for

  20. Mukaiyama Aldol Reactions in Aqueous Media

    PubMed Central

    Kitanosono, Taku; Kobayashi, Sh?

    2013-01-01

    Mukaiyama aldol reactions in aqueous media have been surveyed. While the original Mukaiyama aldol reactions entailed stoichiometric use of Lewis acids in organic solvents under strictly anhydrous conditions, Mukaiyama aldol reactions in aqueous media are not only suitable for green sustainable chemistry but are found to produce singular phenomena. These findings led to the discovery of a series of water-compatible Lewis acids such as lanthanide triflates in 1991. Our understanding on these beneficial effects in the presence of water will be deepened through the brilliant examples collected in this review. 1 Introduction 2 Rate Enhancement by Water in the Mukaiyama Aldol Reaction 3 Lewis Acid Catalysis in Aqueous or Organic Solvents 3.1 Water-Compatible Lewis Acids 4 Lewis-Base Catalysis in Aqueous or Organic Solvents 5 The Mukaiyama Aldol Reactions in 100% Water 6 Asymmetric Catalysts in Aqueous Media and Water 7 Conclusions and Perspective PMID:24971045

  1. Impact of chemical and meteorological boundary and initial conditions on air quality modeling: WRF-Chem sensitivity evaluation for a European domain

    NASA Astrophysics Data System (ADS)

    Ritter, Mathias; Müller, Mathias D.; Jorba, Oriol; Parlow, Eberhard; Liu, L.-J. Sally

    2013-01-01

    This study evaluates the impact of different chemical and meteorological boundary and initial conditions on the state-of-the-art Weather Research and Forecasting (WRF) model with its chemistry extension (WRF-Chem). The evaluation is done for July 2005 with 50 km horizontal resolution. The effect of monthly mean chemical boundary conditions derived from the chemical transport model LMDZ-INCA on WRF-Chem is evaluated against the effect of the preset idealized profiles. Likewise, the impact of different meteorological initial and boundary conditions (GFS and Reanalysis II) on the model is evaluated. Pearson correlation coefficient between these different runs range from 0.96 to 1.00. Exceptions exists for chemical boundary conditions on ozone and for meteorological boundary conditions on PM10, where coefficients of 0.90 were obtained. Best results were achieved with boundary and initial conditions from LMDZ-INCA and GFS. Overall, the European simulations show encouraging results for observed air pollutant, with ozone being the most and PM10 being the least satisfying.

  2. 1H NMR investigation of self-association of vanillin in aqueous solution

    NASA Astrophysics Data System (ADS)

    Bogdan, Mircea; Floare, Calin G.; Pîrnau, Adrian

    2009-08-01

    A self-association of vanillin have been studied by 1H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  3. Reaction mechanism for the aqueous-phase mineral carbonation of heat-activated serpentine at low temperatures and pressures in flue gas conditions.

    PubMed

    Pasquier, Louis-César; Mercier, Guy; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra

    2014-05-01

    Mineral carbonation is known as one of the safest ways to sequester CO2. Nevertheless, the slow kinetics and low carbonation rates constitute a major barrier for any possible industrial application. To date, no studies have focused on reacting serpentinite with a relatively low partial pressure of CO2 (pCO2) close to flue gas conditions. In this work, finely ground and heat-treated serpentinite [Mg3Si2O5(OH)4] extracted from mining residues was reacted with a 18.2 vol % CO2 gas stream at moderate global pressures to investigate the effect on CO2 solubility and Mg leaching. Serpentinite dissolution rates were also measured to define the rate-limiting step. Successive batches of gas were contacted with the same serpentinite to identify surface-limiting factors using scanning electron microscopy (SEM) analysis. Investigation of the serpentinite carbonation reaction mechanisms under conditions close to a direct flue gas treatment showed that increased dissolution rates could be achieved relative to prior work, with an average Mg dissolution rate of 3.55 × 10(-11) mol cm(-2) s(-1). This study provides another perspective of the feasibility of applying a mineral carbonation process to reduce industrial greenhouse gas (GHG) emissions from large emission sources. PMID:24669999

  4. Large-scale green chemical synthesis of adjacent quaternary chiral centers by continuous flow photodecarbonylation of aqueous suspensions of nanocrystalline ketones.

    PubMed

    Hernández-Linares, María Guadalupe; Guerrero-Luna, Gabriel; Pérez-Estrada, Salvador; Ellison, Martha; Ortin, Maria-Mar; Garcia-Garibay, Miguel A

    2015-02-01

    To demonstrate the ease of scale-up and synthetic potential of some organic solid state reactions, we report the synthesis, crystallization, and solid state photochemistry of acyclic, homochiral, hexasubstituted (+)-(2R,4S)-2-carbomethoxy-4-cyano-2,4-diphenyl-3-pentanone 1. We demonstrate that solid state photodecarbonylation of (+)-(2R,4S)-1 affords (+)-(2R,3R)-2-carbomethoxy-3-cyano-2,3-diphenyl-butane 2 with two adjacent stereogenic, all-carbon substituted quaternary centers, in quantitative chemical yield and 100% diastereoselectivity and enantiomeric excess. The efficient multigram photodecarbonylation of (+)-(2R,4S)-1 as a nanocrystalline suspension in water using a continuous flow photoreactor shows that the large-scale synthesis of synthetically challenging compounds using photochemical synthesis in the solid state can be executed in a remarkably simple manner. PMID:25578232

  5. Humid-air and aqueous corrosion models for corrosion-allowance barrier material

    SciTech Connect

    Lee, J.H.; Atkins, J.E.; Andrews, R.W. [INTERA, Inc./CRWMS M& O, Las Vegas, NV (United States)

    1995-12-31

    Humid-air and aqueous general and pitting corrosion models (including their uncertainties) for the carbon steel outer containment barrier were developed using the corrosion data from literature for a suite of cast irons and carbon steels which have similar corrosion behaviors to the outer barrier material. The corrosion data include the potential effects of various chemical species present in the testing environments. The atmospheric corrosion data also embed any effects of cyclic wetting and drying and salts that may form on the corroding specimen surface. The humid-air and aqueous general corrosion models are consistent in that the predicted humid-air general corrosion rates at relative humidities between 85 and 100% RH are close to the predicted aqueous general corrosion rates. Using the expected values of the model parameters, the model predicts that aqueous pitting corrosion is the most likely failure mode for the carbon steel outer barrier, and an earliest failure (or initial pit penetration) of the 100-mm thick barrier may occur as early as about 500 years if it is exposed continuously to an aqueous condition at between 60 and 70{degrees}C.

  6. Multiresidue screening of endocrine-disrupting chemicals and pharmaceuticals in aqueous samples by multi-stir bar sorptive extraction-single desorption-capillary gas chromatography/mass spectrometry.

    PubMed

    Van Hoeck, Els; Canale, Francesca; Cordero, Chiara; Compernolle, Sien; Bicchi, Carlo; Sandra, Pat

    2009-02-01

    A multiresidue method for screening endocrine-disrupting chemicals (EDCs) and pharmaceuticals in aqueous samples is presented. Four 10-mL aliquots of water were taken for stir bar sorptive extraction (SBSE) and they were treated in the following way. In sample one, in situ derivatization was performed with acetic acid anhydride to improve the extraction efficiencies and chromatographic analysis of phenolic compounds. For the same reasons, aliquot two was treated with ethyl chloroformate to improve amine and acid extraction and analysis, and aliquot three with tetraethylborate to enhance organotin compound extraction and analysis. Methanol was added to sample four to stop adsorption of apolar solutes on the wall. After SBSE, the four stir bars, together with a plug of glass wool impregnated with bis(trimethylylsilyl)trifluoroacetamide (BSTFA) to derivatize hydroxyl functionalities, were introduced into the same thermal desorption tube, heat-desorbed, and analyzed simultaneously by capillary GC/MS. The figures of merit of the method were evaluated with an EDC model mixture. In scan-mode MS, the limits of detection (LODs) were in the range 1-500 ng/L, while the LODs dropped by a factor of 50-100 when ion monitoring MS was applied to the targets. The performance of the method was illustrated by analysing some real-world water samples. PMID:18779956

  7. A comparative study of the electrodeposition and the aqueous chemical growth techniques for the utilization of ZnO nanorods on p-GaN for white light emitting diodes

    NASA Astrophysics Data System (ADS)

    Kishwar, S.; ul Hasan, K.; Alvi, N. H.; Klason, P.; Nur, O.; Willander, M.

    2011-01-01

    Vertically well aligned zinc oxide nanorods (ZnO NRs) were grown on p-GaN by electrodeposition (ED) and aqueous chemical growth (ACG) techniques and the structures were employed to fabricate white light emitting diodes (LEDs). Room temperature current voltage ( I-V), photoluminescence (PL), and electroluminescence (EL) measurements were performed to investigate and compare both LEDs. In general, the I-V characteristics and the PL spectra of both LEDs were rather similar. Nevertheless, the EL of the ED samples showed an extra emission peak shoulder at 730 nm. Moreover, at the same injection current, the EL spectrum of the ED light emitting diode showed a small UV shift of 12 nm and its white peak was found to be broader when compared to the ACG grown LED. The broadening of the EL spectrum of the LED grown by ED is due to the introduction of more radiative deep level defects. The presented LEDs have shown excellent color rendering indexes reaching a value as high as 95. These results indicate that the ZnO nanorods grown by both techniques possess very interesting electrical and optical properties but the ED is found to be faster and more suitable for the fabrication of white LEDs.

  8. Short-term variability of the phytoplankton community in coastal ecosystem in response to physical and chemical conditions' changes

    NASA Astrophysics Data System (ADS)

    Pannard, Alexandrine; Claquin, Pascal; Klein, Cécile; Le Roy, Bertrand; Véron, Benoît

    2008-11-01

    The short-term dynamics (time scale of a few days) of phytoplankton communities in coastal ecosystems, particularly those of toxic species, are often neglected. Such phenomena can be important, especially since these very species can endanger the sustainability of shellfish farming. In this study, we investigated the short-term changes in phytoplankton community structure (species succession) in two coastal zones in parallel with physical and chemical conditions. Mixing events with allochtonous waters could thus be distinguished from local processes associated with population growth when it was associated with a change in light or nutrient limitation. Mixing events and water advection influenced fluctuations in total phytoplankton biomass and concentration of dominant species, while local processes influenced delayed changes in community structure. The estuarine species Asterionellopsis glacialis increased in concentration when the water mass mixed with the nearest estuarine water masses. The biological response, measured as photosynthetic capacity, occurred after a time-lag of a few hours, while the changes in community structure occurred after a time-lag of a few days. Finally, the coastal water mass was constantly mixed with both the nearest estuarine and marine water masses, leading in turn to delayed changes in phytoplankton community structure. These changes in species composition and dominance were observed on a time scale of a few days, which means that some toxic species may be missed with a bi-weekly sampling strategy.

  9. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2013-01-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and ?-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for ?-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  10. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2012-09-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and ?-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for ?-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  11. A Monte-Carlo step-by-step simulation code of the non-homogeneous chemistry of the radiolysis of water and aqueous solutions—Part II: calculation of radiolytic yields under different conditions of LET, pH, and temperature

    Microsoft Academic Search

    Ianik Plante

    2011-01-01

    The importance of the radiolysis of water in the initial events following irradiation of biological systems has motivated\\u000a considerable theoretical and experimental work in the field of radiation chemistry of water and aqueous systems. These studies\\u000a include Monte-Carlo simulations of the radiation track structure and of the non-homogeneous chemical stage, which have been\\u000a successfully used to calculate the yields of

  12. Synthesis of Aqueous CdTe/CdS/ZnS Core/shell/shell Quantum Dots by a Chemical Aerosol Flow Method

    PubMed Central

    2010-01-01

    This work described a continuous method to synthesize CdTe/CdS/ZnS core/shell/shell quantum dots. In an integrated system by flawlessly combining the chemical aerosol flow system working at high temperature (200–300°C) to generate CdTe/CdS intermediate products and an additional heat-up setup at relatively low temperature to overcoat the ZnS shells, the CdTe/CdS/ZnS multishell structures were realized. The as-synthesized CdTe/CdS/ZnS core/shell/shell quantum dots are characterized by photoluminescence spectra, X-ray diffraction (XRD), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). Fluorescence and XRD results confirm that the obtained quantum dots have a core/shell/shell structure. It shows the highest quantum yield above 45% when compared to the rhodamine 6G. The core/shell/shell QDs were more stable via the oxidation experiment by H2O2. PMID:20652095

  13. Urban Air Pollution from Ethanol (E85) in the Presence of Aqueous Aerosols and Fog

    NASA Astrophysics Data System (ADS)

    Ginnebaugh, D. L.; Jacobson, M. Z.

    2010-12-01

    This is a study to examine the effect of ethanol (E85) versus gasoline on urban air pollution in the presence of aqueous aerosols and fog. In previous work, we analyzed the temperature-dependence of ethanol and gasoline exhaust chemistry and its impact on urban air pollution considering only gas-phase chemistry. We used the near-explicit Master Chemical Mechanism (MCM, version 3.1, LEEDS University) with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate explicit chemistry. The MCM has over 13,500 organic reactions and 4,600 species. SMVGEAR II is a sparse-matrix Gear solver that reduces the computation time significantly while maintaining any specified accuracy. We found that the average ozone concentrations through the range of temperatures tested could be higher with E85 than with gasoline by up to 8 parts per billion volume (ppbv) at room temperature but much higher at cold temperatures and low sunlight (winter conditions) for a region with a high nitrogen oxide (NOx) to non-methane organic gases (NMOG) ratio. We also found that the solution to chemistry in a 3-D urban airshed model was practical. We now extend our study to include aqueous chemistry in the presence of aerosols and fog. We combine the Chemical Aqueous Phase Radical Mechanism, CAPRAM 3.0 with the MCM 3.1 and gas-particle transfer in box model calculations. CAPRAM treats aqueous phase chemistry among 390 species and 829 reactions (including 51 gas-to-aqueous phase reactions). We investigate the impact aqueous reactions have on unburned ethanol and acetaldehyde mixing ratios in the atmosphere in particular because acetaldehyde is an ozone precursor and carcinogen, and aqueous oxidation has potential to speed the conversion of unburned ethanol to acetaldehyde. Acetaldehyde also forms acetic acid in aqueous solution. Acetic acid vapor is an eye, nose, and lung irritant, so both species contribute negatively to human health. We look at the impact of aerosol and fog liquid water content and temperature on the degradation of emitted aromatic and other species as well, from both gasoline and E85.

  14. Specific effect of magnesium ion on 2', 3'-cyclic amp synthesis from adenosine and trimeta phosphate in aqueous solution

    NASA Astrophysics Data System (ADS)

    Yamagata, Y.; Inoue, H.; Inomata, K.

    1995-06-01

    Phosphorylation of adenosine by trimetaphosphate was investigated using various catalysts in aqueous solution under mild conditions at pH ˜ 7.0 and at 41 °C. The product was primarily 2',3'-cyclic AMP together with smaller amounts of ATP. Magnesium ion was found to have a remarkable catalytic effect of approximately one hundred times greater than the other chemicals tested. The mechanism for the specific effect of magnesium ion is discussed.

  15. The Effect of Chemical Composition and Heat Treatment Conditions on Stacking Fault Energy for Fe-Cr-Ni Austenitic Stainless Steel

    NASA Astrophysics Data System (ADS)

    Yonezawa, Toshio; Suzuki, Ken; Ooki, Suguru; Hashimoto, Atsushi

    2013-12-01

    In order to establish more reliable formulae for calculating stacking fault energies (SFE) from the chemical compositions of austenitic stainless steels, SFE values were measured for 54 laboratory-melted heats and 2 commercial heats. The results were checked against those of a first-principle, atomistic calculation approach. More than ~20,000 data points for the width and angle of the Burgers vectors were determined from dark-field images of isolated extended dislocations in 56 heats of austenitic stainless steel using weak electron beams with g-3g diffraction conditions. Based on these numerous observations and on fundamental thermodynamic analyses, it is concluded that the SFE values for austenitic stainless steels are changed not only by chemical composition but also by heat treatment. In this paper, new formulae for calculating SFE values from the chemical compositions in three different heat treatment conditions have been proposed for austenitic stainless steels within given limited chemical composition ranges. In these formulae, the SFE values are calculated from the nickel, chromium, molybdenum, silicon, manganese, nitrogen, and carbon contents for the each heat treatment condition. The three heat treatment conditions studied were water cooling after solution heat treating (SHTWC), furnace cooling after solution heat treating, and aging after SHTWC.

  16. Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

    NASA Astrophysics Data System (ADS)

    Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic framework has been chosen to study the transfer kinetic processes at the microscale level. The rationale for our approach is based on both the activation energy of transfer of an ion and its velocity across the NAPL/APL interface. There are four major energies controlling the interfacial NAPL dissolution kinetics: (de)solvation energy, interfacial tension energy, electrostatic energy, and thermal fluctuation energy. Transfer of an ion across the NAPL/APL interface is accelerated by the viscous forces which can be described using the averaged Langevin master equation. The resulting energies and viscous forces were combined using the Boltzmann probability distribution. Asymptotic time limits of the resulting kinetics lead to instantaneous local equilibrium conditions that contradict the Nernst equilibrium equation. The NAPL/APL interface is not an ideal one: it does not conserve energy and heat. In our case the interface is treated as a thin film or slush zone that alters the thermodynamic variables. Such added zone, between the two phases, is itself a phase, and, therefore, the equilibrium does not occur between two phases but rather three. All these findings led us to develop a new non-linearly coupled flow and transport system of equations which is able to account for specific chemical dissolution processes and precludes the need for empirical mass-transfer parameters. Work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  17. Low temperature aqueous desulfurization of coal

    DOEpatents

    Slegeir, William A. (Hampton Bays, NY); Healy, Francis E. (Massapequa, NY); Sapienza, Richard S. (Shoreham, NY)

    1985-01-01

    This invention describes a chemical process for desulfurizing coal, especially adaptable to the treatment of coal-water slurries, at temperatures as low as ambient, comprising treating the coal with aqueous titanous chloride whereby hydrogen sulfide is liberated and the desulfurized coal is separated with the conversion of titanous chloride to titanium oxides.

  18. Low temperature aqueous desulfurization of coal

    DOEpatents

    Slegeir, W.A.; Healy, F.E.; Sapienza, R.S.

    1985-04-18

    This invention describes a chemical process for desulfurizing coal, especially adaptable to the treatment of coal-water slurries, at temperatures as low as ambient, comprising treating the coal with aqueous titanous chloride whereby hydrogen sulfide is liberated and the desulfurized coal is separated with the conversion of titanous chloride to titanium oxides.

  19. Cr(VI) removal from aqueous solution with bamboo charcoal chemically modified by iron and cobalt with the assistance of microwave.

    PubMed

    Wang, Wei; Wang, Xuejiang; Wang, Xin; Yang, Lianzhen; Wu, Zhen; Xia, Siqing; Zhao, Jianfu

    2013-09-01

    Bamboo charcoal (BC) was used as starting material to prepare Co-Fe binary oxideloaded adsorbent (Co-Fe-MBC) through its impregnation in Co(NO3)2, FeCl3 and HNO3 solutions simultaneously, followed by microwave heating. The low-cost composite was characterized and used as an adsorbent for Cr(VI) removal from water. The results showed that a cobalt and iron binary oxide (CoFe2O4) was uniformly formed on the BC through redox reactions. The composite exhibited higher surface area (331 m2/g) than that of BC or BC loaded with Fe alone (Fe-MBC). The adsorption of Cr(VI) strongly depended on solution pH, temperature and ionic strength. The adsorption isotherms followed the Langmuir isotherm model well, and the maximum adsorption capacities for Cr(VI) at 288 K and pH 5.0 were 35.7 and 51.7 mg/g for Fe-MBC and Co-Fe-MBC, respectively. The adsorption processes were well fitted by the pseudo second-order kinetic model. Thermodynamic parameters showed that the adsorption of Cr(VI) onto both adsorbents was feasible, spontaneous, and exothermic under the studied conditions. The spent Co-Fe-MBC could be readily regenerated for reuse. PMID:24520714

  20. PLD deposition of tungsten carbide contact for diamond photodiodes. Influence of process conditions on electronic and chemical aspects

    NASA Astrophysics Data System (ADS)

    Cappelli, E.; Bellucci, A.; Orlando, S.; Trucchi, D. M.; Mezzi, A.; Valentini, V.

    2013-08-01

    Tungsten carbide, WC, contacts behave as very reliable Schottky contacts for opto-electronic diamond devices. Diamond is characterized by superior properties in high-power, high frequency and high-temperature applications, provided that thermally stable electrode contacts will be realized. Ohmic contacts can be easily achieved by using carbide-forming metals, while is difficult to get stable Schottky contacts at elevated temperatures, due to the interface reaction and/or inter-diffusion between metals and diamond. Novel type of contacts, made of tungsten carbide, WC, seem to be the best solution, for their excellent thermal stability, high melting point, oxidation and radiation resistance and good electrical conductivity. Our research was aimed at using pulsed laser deposition for WC thin film deposition, optimizing experimental parameters, to obtain a final device characterized by excellent electronic properties, as a detector for radiation in deep UV or as X-ray dosimeter. We deposited our films by laser ablation from a target of pure WC, using different reaction conditions (i.e., substrate heating, vacuum or reactive atmosphere (CH4/Ar), RF plasma activated), to optimize both the stoichiometry of the film and its structure. Trying to obtain a material with the best electronic response, we used also two sources of laser radiation for target ablation, i.e., nano-second pulsed excimer laser ArF, and ultra-short fs Ti:Sapphire laser. The structure and chemical aspects have been evaluated by Raman and X-ray photoelectron spectroscopy (XPS), while the dosimeter photodiode response has been tested by the I-V measurements, under soft X-ray irradiation.

  1. Field lysimeters for the study of fate and transport of explosive chemicals in soils under variable environmental conditions

    Microsoft Academic Search

    Gloria M. Molina; Ingrid Padilla; Miguel Pando; Diego D. Pérez

    2006-01-01

    Landmines and other buried explosive devices pose in an immense threat in many places of the world, requiring large efforts on detection and neutralization of these objects. Many of the available detection techniques require the presence of chemicals near the soil-atmospheric surface. The presence of explosive related chemicals (ERCs) near this surface and their relation to the location of landmines,

  2. Bioethanol production from barley hull using SAA (soaking in aqueous ammonia) pretreatment

    Microsoft Academic Search

    Tae Hyun Kim; Frank Taylor; Kevin B. Hicks

    2008-01-01

    Barley hull, a lignocellulosic biomass, was pretreated using aqueous ammonia, to be converted into ethanol. Barley hull was soaked in 15 and 30 wt.% aqueous ammonia at 30, 60, and 75°C for between 12h and 11 weeks. This pretreatment method has been known as “soaking in aqueous ammonia” (SAA). Among the tested conditions, the best pretreatment conditions observed were 75°C,

  3. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

    PubMed Central

    Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

    2015-01-01

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

  4. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule.

    PubMed

    Zheng, Peng; Arantes, Guilherme M; Field, Martin J; Li, Hongbin

    2015-01-01

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

  5. Chemical composition and physical quality characteristics of Ghanaian cocoa beans as affected by pulp pre-conditioning and fermentation

    Microsoft Academic Search

    Emmanuel Ohene Afoakwa; Jennifer Quao; Jemmy Takrama; Agnes Simpson Budu; Firibu Kwesi Saalia

    Investigations were conducted to evaluate the effects of pod storage (as a means of pulp preconditioning) and fermentation\\u000a on the chemical composition and physical characteristics of Ghanaian cocoa beans. A 4?×?2 full factorial design with factors\\u000a as pod storage (0, 7, 14, 21 days) and cocoa treatment (fermented and unfermented) were conducted. Samples were analyzed for\\u000a their chemical composition (moisture, crude

  6. SPACCIM simulations of chemical aerosol-cloud interactions with the multiphase chemical mechanism MCM-CAPRAM3.0i

    NASA Astrophysics Data System (ADS)

    Tilgner, A.; Schrödner, R.; Bräuer, P.; Wolke, R.; Herrmann, H.

    2010-07-01

    Heterogeneous and multiphase processes in fog droplets, cloud droplets and deliquescent particles can potentially alter the physico-chemical composition of the tropospheric aerosol on global scale. In order to model such complex tropospheric multiphase chemical interactions of clouds, fogs and deliquescent aerosol particles, chemical mechanisms with a detailed description of chemical processes in both the gas and aqueous phase are required. Currently, both near-explicit gas and aqueous phase mechanisms are available. However, a near-explicit chemical multiphase mechanism was still missing. Therefore, the near-explicit chemical gas phase mechanism MCM v3 (Master Chemical Mechanism, Saunder et al., 2003) with about 13502 reactions and the explicit aqueous phase mechanism CAPRAM3.0i (Chemical Aqueous Phase Radical Mechanism, Herrmann et al., 2005) with about 777 reactions were coupled and integrated into the model framework SPACCIM (SPectral Aerosol Cloud Chemistry Interaction Model; Wolke et al., 2005). The parcel model SPACCIM combines a complex microphysical and multiphase chemistry model. First SPACCIM simulations have been carried out for different environmental conditions using a non-permanent cloud scenario. The model studies were aimed to investigate multiphase chemistry in tropospheric deliquescent aerosol particles, fogs and clouds in more detail. The model investigations were focused on the multiphase chemistry of tropospheric radical oxidants such as OH and NO3, organic compounds and closely linked chemical subsystems. The model results have been analysed including time-resolved reaction flux analyses. The obtained model results of the near-explicit multiphase mechanism MCM-CAPRAM3.0i have been compared with results of former model studies using the non-explicit gas phase mechanism RACM-MIM2ext and CAPRAM3.0i (Tilgner and Herrmann, 2010). Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0, Atmos Environ, 39, 4351-4363, 2005. Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos Chem Phys, 3, 161-180, 2003. Tilgner, A., and Herrmann, H.: Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM, submitted to Atmospheric Environment, 2010. Wolke, R., Sehili, A. M., Simmel, M., Knoth, O., Tilgner, A., and Herrmann, H.: SPACCIM: A parcel model with detailed microphysics and complex multiphase chemistry, Atmos Environ, 39, 4375-4388, 2005.

  7. Influence of Chemical Composition on Rupture Properties at 1200 Degrees F. of Forged Chromium-Cobalt-Nickel-Iron Base Alloys in Solution-Treated and Aged Condition

    NASA Technical Reports Server (NTRS)

    Reynolds, E E; Freeman, J W; White, A E

    1951-01-01

    The influence of systematic variations of chemical composition on rupture properties at 1200 degrees F. was determined for 62 modifications of a basic alloy containing 20 percent chromium, 20 percent nickel, 20 percent cobalt, 3 percent molybdenum, 2 percent tungsten, 1 percent columbium, 0.15 percent carbon, 1.7 percent manganese, 0.5 percent silicon, 0.12 percent nitrogen and the balance iron. These modifications included individual variations of each of 10 elements present and simultaneous variations of molybdenum, tungsten, and columbium. Laboratory induction furnace heats were hot-forged to round bar stock, solution-treated at 2200 degrees F., and aged at 1400 degrees F. The melting and fabrication conditions were carefully controlled in order to minimize all variable effects on properties except chemical composition. Information is presented which indicates that melting and hot-working conditions play an important role in high-temperature properties of alloys of the type investigated.

  8. Unlocking the Sporicidal Potential of Ethanol: Induced Sporicidal Activity of Ethanol against Clostridium difficile and Bacillus Spores under Altered Physical and Chemical Conditions

    PubMed Central

    Nerandzic, Michelle M.; Sunkesula, Venkata C. K.; C., Thriveen Sankar; Setlow, Peter; Donskey, Curtis J.

    2015-01-01

    Background Due to their efficacy and convenience, alcohol-based hand sanitizers have been widely adopted as the primary method of hand hygiene in healthcare settings. However, alcohols lack activity against bacterial spores produced by pathogens such as Clostridium difficile and Bacillus anthracis. We hypothesized that sporicidal activity could be induced in alcohols through alteration of physical or chemical conditions that have been shown to degrade or allow penetration of spore coats. Principal Findings Acidification, alkalinization, and heating of ethanol induced rapid sporicidal activity against C. difficile, and to a lesser extent Bacillus thuringiensis and Bacillus subtilis. The sporicidal activity of acidified ethanol was enhanced by increasing ionic strength and mild elevations in temperature. On skin, sporicidal ethanol formulations were as effective as soap and water hand washing in reducing levels of C. difficile spores. Conclusions These findings demonstrate that novel ethanol-based sporicidal hand hygiene formulations can be developed through alteration of physical and chemical conditions. PMID:26177038

  9. Chemical Models for Aqueous Biodynamical Processes

    E-print Network

    Mata-Segreda, Julio F.

    1975-05-01

    of Transfer of Potassium Chloride from Light to Heavy Water from Solubilities of Sparingly Soluble Salts," Acta Chem. Scand. 3 25, 361 (1971). (25) P. Salomaa, "Solvent Deuterium Isotope Effects on Acid-Base Reactions. Part V. Assignment of Individual... Ionic Contributions to Transfer Free Energies of Electrolytes from H20 to D20," Acta Chem. Scand. 3 25, 365 (19 71). (26) P. Salomaa and M. Mattsén, "Solubility of Picric Acid in Light and Heavy Water and Isotopic Fractionation of Hydrogen Between...

  10. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...aqueous solution ([HCl], [NaOH]=1 mol/L). (4 ) In theory, all chemical species other than that being tested... (2) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical...

  11. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...aqueous solution ([HCl], [NaOH]=1 mol/L). (4 ) In theory, all chemical species other than that being tested... (2) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical...

  12. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...aqueous solution ([HCl], [NaOH]=1 mol/L). (4 ) In theory, all chemical species other than that being tested... (2) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical...

  13. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...aqueous solution ([HCl], [NaOH]=1 mol/L). (4 ) In theory, all chemical species other than that being tested... (2) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical...

  14. 40 CFR 796.1050 - Absorption in aqueous solution: Ultraviolet/visible spectra.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...aqueous solution ([HCl], [NaOH]=1 mol/L). (4 ) In theory, all chemical species other than that being tested... (2) Katelaar, J.A.A., Photoelectric Spectrometry Group Bulletin, 8, (Cambridge, 1955). (3) Chemical...

  15. Pretreatment of rice straw with combined process using dilute sulfuric acid and aqueous ammonia

    PubMed Central

    2013-01-01

    Background Use of lignocellulosic biomass has received attention lately because it can be converted into various versatile chemical compounds by biological processes. In this study, a two-step pretreatment with dilute sulfuric acid and aqueous ammonia was performed efficiently on rice straw to obtain fermentable sugar. The soaking in aqueous ammonia process was also optimized by a statistical method. Results Response surface methodology was employed. The determination coefficient (R2) value was found to be 0.9607 and the coefficient of variance was 6.77. The optimal pretreatment conditions were a temperature of 42.75°C, an aqueous ammonia concentration of 20.93%, and a reaction time of 48 h. The optimal enzyme concentration for saccharification was 30 filter paper units. The crystallinity index was approximately 60.23% and the Fourier transform infrared results showed the distinct peaks of glucan. Ethanol production using Saccharomyces cerevisiae K35 was performed to verify whether the glucose saccharified from rice straw was fermentable. Conclusions The combined pretreatment using dilute sulfuric acid and aqueous ammonia on rice straw efficiently yielded fermentable sugar and achieved almost the same crystallinity index as that of ?-cellulose. PMID:23898802

  16. Radiolysis of Bicarbonate and Carbonate Aqueous Solutions: Product Analysis and Simulation of Radiolytic Processes

    SciTech Connect

    Cai Zhongli; Li Xifeng; Katsumura, Yosuke; Urabe, Osamu [University of Tokyo (Japan)

    2001-11-15

    An understanding of the radiation-induced effects in groundwater is essential to evaluate the safe geological disposal of spent fuel. In groundwater, the bicarbonate ion is the predominant and common anion; this work investigated radiation-induced chemical reactions of (bi)carbonate aqueous solutions with steady-state irradiation and pulse radiolysis methods. Aqueous solutions of sodium (bi)carbonate as high as 50 mmol.dm{sup -3} were used. The formation of formate, oxalate, and H{sub 2}O{sub 2} were measured under different conditions. A complete set of reaction steps and reliable kinetic data for the radiolysis of (bi)carbonate aqueous solutions at ionic strength close to the groundwater were proposed. Kinetic calculations were completed based on the proposed reaction steps and the kinetic data obtained in the present work. The results from the calculation are in good agreement with the experimental results. With these proposed reaction steps and kinetic data, computer simulation can be performed to predict the yield of radiolytic products of (bi)carbonate aqueous solutions as a function of irradiation time and used to evaluate the safety of geological disposal options of spent fuel.

  17. Leaching of lead from zinc leach residue in acidic calcium chloride aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Le; Mu, Wen-ning; Shen, Hong-tao; Liu, Shao-ming; Zhai, Yu-chun

    2015-05-01

    A process with potentially reduced environmental impacts and occupational hazards of lead-bearing zinc plant residue was studied to achieve a higher recovery of lead via a cost-effective and environmentally friendly process. This paper describes an optimization study on the leaching of lead from zinc leach residue using acidic calcium chloride aqueous solution. Six main process conditions, i.e., the solution pH value, stirring rate, concentration of CaCl2 aqueous solution, liquid-to-solid (L/S) ratio, leaching temperature, and leaching time, were investigated. The microstructure and components of the residue and tailing were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). On the basis of experimental results, the optimum reaction conditions were determined to be a solution pH value of 1, a stirring rate of 500 r·min-1, a CaCl2 aqueous solution concentration of 400 g·L-1, a liquid-to-solid mass ratio of 7:1, a leaching temperature of 80°C, and a leaching time of 45 min. The leaching rate of lead under these conditions reached 93.79%, with an iron dissolution rate of 19.28%. Silica did not take part in the chemical reaction during the leaching process and was accumulated in the residue.

  18. Kinetics studies of some physico-chemical substances during roasting and preparation of beverage made by Cassia occidentalis seeds

    Microsoft Academic Search

    Gabriel Nama Medoua; Carl M. F. Mbofung

    2007-01-01

    Cassia occidentalis seeds are commonly used in West of Africa to prepare a beverage which serves as a substitute for coffee. A study was carried out to investigate the effect of roasting conditions on some organic compounds in the seeds and to determine the extraction rate of some physico-chemical constituents into an aqueous infusion. With the exception of phytate, the

  19. Chemical sensor

    NASA Technical Reports Server (NTRS)

    Rauh, R. David (Inventor)

    1990-01-01

    A sensor for detecting a chemical substance includes an insertion element having a structure which enables insertion of the chemical substance with a resulting change in the bulk electrical characteristics of the insertion element under conditions sufficient to permit effective insertion; the change in the bulk electrical characteristics of the insertion element is detected as an indication of the presence of the chemical substance.

  20. OVIPOSITION OF THE SOUTHERN GREEN STINK BUG, NEZARA VIRIDULA (L.) ON ARTIFICIAL SUBSTRATES CONDITIONED BY CHEMICAL EXTRACTS FROM SOYBEAN PLANTS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A laboratory bioassay was developed for testing oviposition preference of the southern green stink bug, Nezara viridula (L.) (Heteroptera: Pentatomidae) toward chemicals extracted from soybean pods and leaves. In this bioassay, an artificial substrate (cheesecloth) was stretched over a wooden ring ...

  1. Chemical geodynamics

    Microsoft Academic Search

    A. Zindler; S. R. Hart

    1986-01-01

    Consideration is given to the following three principal boundary conditions relating to the nature and development of chemical structure in the earth's mantle: (1) inferred scale lengths for mantle chemical heterogeneities, (2) interrelationships of the various isotopic tracers, and (3) the bulk composition of the earth. These boundary conditions are integrated with geophysical constraints in order to evaluate models for

  2. Aqueous Alteration on Mars. Chapter 23

    NASA Technical Reports Server (NTRS)

    Ming, Douglas W.; Morris, Richard V.; Clark, Benton C.

    2007-01-01

    Aqueous alteration is the change in composition of a rock, produced in response to interactions with H2O-bearing ices, liquids, and vapors by chemical weathering. A variety of mineralogical and geochemical indicators for aqueous alteration on Mars have been identified by a combination of surface and orbital robotic missions, telescopic observations, characterization of Martian meteorites, and laboratory and terrestrial analog studies. Mineralogical indicators for aqueous alteration include goethite (lander), jarosite (lander), kieserite (orbiter), gypsum (orbiter) and other Fe-, Mg-, and Ca-sulfates (landers), halides (meteorites, lander), phyllosilicates (orbiter, meteorites), hematite and nanophase iron oxides (telescopic, orbiter, lander), and Fe-, Mg-, and Ca-carbonates (meteorites). Geochemical indicators (landers only) for aqueous alteration include Mg-, Ca-, and Fe-sulfates, halides, and secondary aluminosilicates such as smectite. Based upon these indicators, several styles of aqueous alteration have been suggested on Mars. Acid-sulfate weathering (e.g., formation of jarosite, gypsum, hematite, and goethite), may occur during (1) the oxidative weathering of ultramafic igneous rocks containing sulfides, (2) sulfuric acid weathering of basaltic materials, and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials. Near-neutral or alkaline alteration occurs when solutions with pH near or above 7 move through basaltic materials and form phases such as phyllosilicates and carbonates. Very low water:rock ratios appear to have been prominent at most of the sites visited by landed missions because there is very little alteration (leaching) of the original basaltic composition (i.e., the alteration is isochemical or in a closed hydrologic system). Most of the aqueous alteration appears to have occurred early in the history of the planet (3 to 4.5 billion years ago); however, minor aqueous alteration may be occurring at the surface even today (e.g., in thin films of water or by acid fog).

  3. Fine particle emissions in three different combustion conditions of a wood chip-fired appliance - Particulate physico-chemical properties and induced cell death

    NASA Astrophysics Data System (ADS)

    Leskinen, J.; Tissari, J.; Uski, O.; Virén, A.; Torvela, T.; Kaivosoja, T.; Lamberg, H.; Nuutinen, I.; Kettunen, T.; Joutsensaari, J.; Jalava, P. I.; Sippula, O.; Hirvonen, M.-R.; Jokiniemi, J.

    2014-04-01

    A biomass combustion reactor with a moving grate was utilised as a model system to produce three different combustion conditions corresponding to efficient, intermediate, and smouldering combustion. The efficient conditions (based on a CO level of approximately 7 mg MJ-1) corresponded to a modern pellet boiler. The intermediate conditions (CO level of approximately 300 mg MJ-1) corresponded to non-optimal settings in a continuously fired biomass combustion appliance. The smouldering conditions (CO level of approximately 2200 mg MJ-1) approached a batch combustion situation. The gaseous and particle emissions were characterised under each condition. Moreover, the ability of fine particles to cause cell death was determined using the particle emissions samples. The physico-chemical properties of the emitted particles and their toxicity were considerably different between the studied combustion conditions. In the efficient combustion, the emitted particles were small in size and large in number. The PM1 emission was low, and it was composed of ash species. In the intermediate and smouldering combustion, the PM1 emission was higher, and the particles were larger in size and smaller in number. In both of these conditions, there were high-emission peaks that produced a significant fraction of the emissions. The PAH emissions were the lowest in the efficient combustion. The smouldering combustion conditions produced the largest PAH emissions. In efficient combustion conditions, the emitted fine particles had the highest potential to cause cell death. This finding was most likely observed because these fine particles were mainly composed of inorganic ash species, and their relative contents of Zn were high. Thus, even the PM1 from optimal biomass combustion might cause health effects, but in these conditions, the particle emissions per energy unit produced were considerably lower.

  4. Thermoanalytical investigation of iron phosphate obtained by spontaneous precipitation from aqueous solutions

    Microsoft Academic Search

    Silvera Scaccia; Maria Carewska; Angelo Di Bartolomeo; Pier Paolo Prosini

    2002-01-01

    Iron(III) phosphate has been precipitated under supersaturation conditions from equimolecular aqueous solutions of 0.025M Fe(NO3)3·9H2O and K2HPO4, at pH=2.00 and at ambient temperature. The precipitate has been characterised by TG\\/DTG\\/DTA and DSC techniques, chemical analysis, IR-spectroscopy and X-ray powder diffraction. A yellowish-white amorphous solid of formula Fe2(HPO4)3·xH2O has been obtained. Alternatively, a pinkish-white amorphous precipitate of formula FePO4·2H2O is obtained

  5. Thermoanalytical investigation of nanocrystalline iron (II) phosphate obtained by spontaneous precipitation from aqueous solutions

    Microsoft Academic Search

    Silvera Scaccia; Maria Carewska; Angelo Di Bartolomeo; Pier Paolo Prosini

    2003-01-01

    Fe3(PO4)2·8H2O has been precipitated under supersaturation conditions from deaerated Fe(NH4)2(SO4)2·6H2O and K2HPO4 aqueous, ethanol–water and iso-propanol–water solutions at pH=6.5 and ambient temperature. The precipitates have been characterised by TG\\/DTG\\/DTA and DSC techniques, chemical analysis, BET, and X-ray powder diffraction. The presence of ethanol and iso-propanol in the spontaneous precipitation process of ferrous phosphate leads to highly crystalline powder. Thermal treatment

  6. Reflectance of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Querry, M. R.

    1972-01-01

    The optical properties and optical constants of water and aqueous solutions were studied to develop an accurate tabulation of graphical representations of the optical constants through a broad spectrum. Manuscripts of articles are presented concerning extinction coefficients, relative specular reflectance, and temperature effect on the water spectrum. Graphs of absolute reflectance, phase shifts, index of refraction, and extinction coefficients for water, heavy water and aqueous solutions are included.

  7. Fractionation of Lignocellulosics by Steam-Aqueous Pretreatments

    Microsoft Academic Search

    R. P. Overend; E. Chornet; J. A. Gascoigne

    1987-01-01

    Physical processing or pretreatment of lignocellulosics concerns the ultrastructural modification of materials such as wood, straw and bagasse. The substrates produced can be subsequently converted by chemicals. The various pretreatment options will be discussed in the light of the ultrastructural, polymeric and chemical modifications that are obtained. The processes can be classified as follows: (i) steam; (ii) aqueous; and (iii)

  8. Surface chemical characteristics of coal fly ash particles after interaction with seawater under natural deep sea conditions

    SciTech Connect

    Brami, Y.; Shemesh, A.; Cohen, H. [Weizmann Inst. of Science, Rehovot (Israel)] [Weizmann Inst. of Science, Rehovot (Israel); Herut, B. [National Inst. of Oceanography, Haifa (Israel)] [National Inst. of Oceanography, Haifa (Israel)

    1999-01-15

    The surface chemical characteristics of coal fly ash (CFA) before and after interaction with Mediterranean deep seawater was studied by X-ray photoelectron spectroscopy (XPS). Significantly lower values of Si, Ca, and S and higher values of Mg and Cl were found in the retrieved CFA as compared to fresh CFA. It is suggested that hydrolysis of the oxide matrixes results in an alkaline environment which rapidly leads to several chemical reactions. The two most important are (a) dissolution of the amorphous silicate and the calcium phases and (b) precipitation of Mg(OH){sub 2}-brucite. A depth profile of the retrieved CFA was measured by both line-shape analysis of the XPS spectra and by consecutive cycle of sputtering. The thickness of the brucite layer is estimated to be 1.3 nm.

  9. Rheological Properties of Aqueous Peanut Flour Dispersions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The rheological behaviors of aqueous peanut flour dispersions were characterized across a range of conditions, including controlled heating and cooling rates under both large and small-strain deformations. Fat content of the dry flours influenced rheological changes, as dispersions of higher fat fl...

  10. Thermal energy storage with saturated aqueous solutions

    Microsoft Academic Search

    K. W. Kauffman; H. G. Lorsch

    1976-01-01

    A method of thermal energy storage at temperatures of 0 C to 120 C is being developed for application to solar space heating, water heating, and air conditioning. The method uses saturated aqueous solutions of salts which dissolve endothermically and have large coefficients of solubility with temperature. Latent heat of crystallization is continuously released on cooling and absorbed on heating,

  11. Effect of annealing conditions on the microstructure of RuO2 thin films deposited by metalorganic chemical vapor deposition

    Microsoft Academic Search

    Woong-Chul Shin; Soon-Gil Yoon; Seaung-Suk Lee

    1997-01-01

    Ruthenium dioxide thin films were deposited on SiO2\\/Si substrate at low temperatures by hot-wall metalorganic chemical vapor deposition using the ruthenocene and oxygen gas mixtures.The RuO2 films annealed at 700°C in 1 atm. oxygen ambient showed a dense and improved microstructure. However, above 750°C evaporation of RuO2 was observed at the interface between RuO2 and SiO2\\/Si substrates as well as

  12. Evaluation of regional climate - air quality simulations over Europe for the period 1996-2006 with emphasis on tropospheric ozone: The impact of chemical boundary conditions

    NASA Astrophysics Data System (ADS)

    Akritidis, D.; Zanis, P.; Katragkou, E.; Tegoulias, I.; Poupkou, A.; Markakis, K.; Karacostas, Th.; Pytharoulis, I.

    2012-04-01

    A modeling system based on the air quality model CAMx driven off-line by the regional climate model RegCM3 is used for assessing the impact of lateral boundary conditions on tropospheric ozone over Europe for the period 1996-2006. The RegCM3 and CAMx simulations were performed on a 50 km x 50 km grid over Europe with RegCM3 driven by NCEP reanalysis fields. Average monthly concentration values obtained from the global chemistry climate model ECHAM5-MOZ were used as chemical boundary conditions for the CAMx simulations. The present period (1996-2006) was simulated two times. The first run (clean) was forced from constant lateral chemical boundary conditions and constant emissions based on the EMEP emissions of the year 1996. The second simulation (run1) was based on ECHAM5-MOZ chemical boundary conditions and emissions fixed for the year 1996. In order to evaluate the ability of the RegCM3/CAMx modeling system, simulated ozone concentrations are compared against near surface ozone measurements from the EMEP network. Since many of the stations of the EMEP network were not operating continuously during the time period of our study (1996-2006), we have used in the evaluation analysis only those stations that fulfill the criteria of 75% data availability for near surface ozone, choosing 87 stations from 23 European countries. Various statistical metrics are used for the model evaluation, including correlation coefficient (R), normalized standard deviation (NSD) and modified normalized mean bias (MNMB). The different lateral boundary conditions forcing resulted in changes of near surface ozone concentrations and variability. Using lateral boundary conditions obtained from the global chemistry climate model ECHAM5-MOZ (run1), the RegCM3/CAMx modeling system is capturing in a much better way the ozone monthly variability than using constant lateral boundary conditions (clean), especially for stations of northern and northwestern Europe. Concerning the correlation between simulated and observed monthly ozone values, the run1 simulation exhibit R values greater than the clean simulation for 95% of the stations. Furthermore, both clean and run1 simulations show a tendency of model overestimation concerning near surface ozone concentrations, as the MNMB median is 5.15% for clean and 4.67% for run1 respectively.

  13. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions.

    PubMed

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0±1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1?) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ?10(4)s(-1) at pH 7.4 and 37°C, the activation energy, 50.2kJ/mol and its pH dependence at 1.1°C was fitted to: k (s(-1))=520+6.5×10(7)[H(+)]+3.0×10(9)[OH(-)]. PMID:24632100

  14. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions

    NASA Astrophysics Data System (ADS)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2 ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0 ± 1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1?) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ?104 s-1 at pH 7.4 and 37 °C, the activation energy, 50.2 kJ/mol and its pH dependence at 1.1 °C was fitted to: k (s-1) = 520 + 6.5 × 107[H+] + 3.0 × 109[OH-].

  15. Distribution of small dispersive coal dust particles and absorbed radioactive chemical elements in conditions of forced acoustic resonance in iodine air filter at nuclear power plant

    E-print Network

    Ledenyov, Oleg P

    2013-01-01

    The physical features of distribution of the small dispersive coal dust particles and the adsorbed radioactive chemical elements and their isotopes in the absorber with the granular filtering medium with the cylindrical coal granules were researched in the case of the intensive air dust aerosol stream flow through the iodine air filter (IAF). It was shown that, at the certain aerodynamic conditions in the IAF, the generation of the acoustic oscillations is possible. It was found that the acoustic oscillations generation results in an appearance of the standing acoustic waves of the air pressure (density) in the IAF. In the case of the intensive blow of the air dust aerosol, it was demonstrated that the standing acoustic waves have some strong influences on both: 1) the dynamics of small dispersive coal dust particles movement and their accumulation in the IAF; 2) the oversaturation of the cylindrical coal granules by the adsorbed radioactive chemical elements and their isotopes in the regions, where the antin...

  16. Aqueous foam surfactants for geothermal drilling fluids: 1. Screening

    SciTech Connect

    Rand, P.B.

    1980-01-01

    Aqueous foam is a promising drilling fluid for geothermal wells because it will minimize damage to the producing formation and would eliminate the erosion problems of air drilling. Successful use of aqueous foam will require a high foaming surfactant which will: (1) be chemically stable in the harsh thermal and chemical environment, and (2) form stable foams at high temperatures and pressures. The procedures developed to generate and test aqueous foams and the effects of a 260/sup 0/C temperature cycle on aqueous surfactant solutions are presented. More than fifty selected surfactants were evaluated with representatives from the amphoteric, anionic, cationic, and nonionic classes included. Most surfactants were severely degraded by this temperature cycle; however, some showed excellent retention of their properties. The most promising surfactant types were the alkyl and alkyl aryl sulfonates and the ethoxylated nonionics.

  17. Biothanol production from barley hull using SAA (Soaking in aqueous ammonia) pretreatment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Barley hull, a type of lignocellulosic biomass, was pretreated using aqueous ammonia to improve its enzymatic saccharification. Barley hull was soaked in 15-30 wt.% aqueous ammonia (SAA method) at 30-75'C for 1 day-11 weeks using a batch reactor. Under these conditions, SAA (soaking in aqueous ammon...

  18. Removal characteristics of As(III) and As(V) from acidic aqueous solution by steel making slag.

    PubMed

    Oh, Chamteut; Rhee, Sungsu; Oh, Myounghak; Park, Junboum

    2012-04-30

    This study focused on the environmental risk of steel making slag itself, arsenic removal mechanism and re-leaching possibility of arsenic to aqueous state after the adsorption. The purpose of the study is to promote the use of steel making slag as a low-cost adsorbent for arsenic in aqueous system. Calcium was easily dissolved out from the slag and become the dominant substance in the leachate. Some of the calcium could form amorphous calcium carbonate in alkaline condition, and arsenic in the aqueous solution would be removed by being co-precipitated with or adsorbed onto the amorphous calcium carbonate. Most of the amorphous calcium carbonate containing arsenic would be bound to amorphous iron oxide of the slag. When the slag was used as an adsorbent for arsenic removal, a little amount of toxic chemicals were leached from the slag itself under pH 0.8 to 13.6. Also, 70-80% of arsenic laden on the slag was bound to amorphous iron oxide which would not easily desorb unless given a reducing and complexing condition. Showing 95-100% removal efficiency near initial pH 2, the slag, therefore, could be used as an appropriate adsorbent for eliminating arsenic in acidic aqueous solution. PMID:22349716

  19. First aqueous chemistry with seaborgium (element 106)

    Microsoft Academic Search

    Matthias Schädel

    1998-01-01

    Chemical separations of element 106 (seaborgium, Sg) were performed in aqueous solutions. The isotopes 265Sg and 266Sg, produced in the 248Cm+22Ne reaction, were continuously transported to the automated liquid chromatography system ARCA. In 0.1 M HNO3\\/5×10?4 M HF, Sg was found to be eluted from cation-exchange columns together with the hexavalent Mo- and W-ions, while hexavalent U-ions were strongly retained

  20. Characterization of the growth of polyelectrolyte multilayers formed at interfaces between aqueous phases and thermotropic liquid crystals.

    PubMed

    Gupta, Jugal K; Tjipto, Elvira; Zelikin, Alexander N; Caruso, Frank; Abbott, Nicholas L

    2008-05-20

    Polyelectrolyte multilayers (PEMs) formed at interfaces between aqueous solutions and thermotropic (water-immiscible) liquid crystals (LCs) offer the basis of a new method to tailor the nanometer-scale structure and chemical functionality of these interfaces. Toward this end, we report a study that compares the growth of PEMs formed at mobile and deformable interfaces defined by LCs relative to growth observed at model (rigid) solid surfaces. Experiments aimed at determining if polyelectrolytes such as poly(sodium-4-styrenesulfonate) (PSS) can partition from the aqueous phase into the bulk of the LC yielded no evidence of such partitioning. Whereas measurements of the growth of PEMs formed from poly(allylamine hydrochloride) (PAH) and PSS at the aqueous-LC interface revealed growth characteristics similar to those measured at both hydrophobic and hydrophilic interfaces of solids, the growth of PEMs from PAH and poly(acrylic acid) (PAA) at the aqueous-LC interface was found to differ substantially from the solids investigated: (i) the linear growth of PEMs of PAH/PAA that was measured at the aqueous-LC interface under conditions that did not lead to the growth of PEMs at the interface of octadecyltrichlorosilane (OTS)-treated glass (a hydrophobic solid surface), and (ii) in comparison to the growth of PEMs of PAH/PAA at the surface of glass (a hydrophilic charged surface), a higher rate of growth was observed at the aqueous-LC interface. The finding that the growth rate of PEMs of PAH/PAA at aqueous-LC interfaces is greater than on solid surfaces is supported by additional measurements of growth as a function of pH. Finally, the pH-triggered reorganization of PAH/PAA PEMs supported at the aqueous-LC interface led to changes in the order and optical properties of the LC. These data are discussed in light of the nature of aqueous-LC interfaces, including the mobility and deformability of the interface and recent measurements of the zeta-potentials of aqueous-LC interfaces. PMID:18419143

  1. 3D mapping of chemical distribution from melting at lower mantle conditions in the laser-heated diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Dorfman, S. M.; Nabiei, F.; Cantoni, M.; Badro, J.; Gaal, R.; Gillet, P.

    2014-12-01

    The laser-heated diamond anvil cell is a unique tool for subjecting materials to pressures over few hundreds of GPa and temperatures of thousands of Kelvins which enables us to experimentally simulate the inaccessible interiors of planets. However, small sample size, laser profile and thermally conductive diamonds cause temperature gradients of 1000s K over a few microns which also affects chemical and structural distribution of phases in the sample. We have examined samples of San Carlos olivine (Mg,Fe)2SiO3 powder melted in the diamond anvil cell by double-sided and single-sided laser heating for 3-6 minutes to ~3000 K at 35-37 GPa. Moreover, MgO is used as an insulating media in one of the sample. Recovered samples were analyzed by a combination of focused ion beam (FIB) and scanning electron microscope (SEM) equipped with energy dispersive x-ray (EDX) detector. Images and chemical maps were acquired for ~300 slices with ~70 nm depth from each sample, comprising about half of the heated zone. Detailed chemical and structural analysis by transmission electron microscopy (TEM) of lamellas prepared from the remaining section of the samples will also be presented. In all samples the heated zone included (Mg,Fe)SiO3 perovskite-structured bridgmanite (PV) phase and two (Mg, Fe)O phases, one of which, magnesiowüstite (MW), is richer in iron than the other one, ferropericlase (FP). In double-side heated samples we observe a Fe-rich quenched melt core surrounded by MW phase. Our results show that with increasing heating time, Fe migrates to the molten center of the sample. In the single-side heated sample, the Fe-rich MW phase is concentrated in the center of heated zone. In all samples a FP crust was observed around the heated zone. This crust, however, is broken in the upper part (colder part) of the single-side heated sample due the high asymmetrical temperature gradient within the sample. The results confirm the importance of double-side heating and insulating media for generating homogenous central temperature and chemical distribution.

  2. Phase formation and chemical phase equilibria in aqueous-based systems pertinent to waste-management: calcium oxide-alluminum oxide-borate-water, calcium oxide-lead oxide-phosphate-water and calcium oxide-arsenate-water

    NASA Astrophysics Data System (ADS)

    Bothe, James Vincent, Jr.

    This thesis explores three aqueous-based systems that have importance in the area of waste-management: (1) CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, (2) CaO-PbO-Psb2Osb5-Hsb2O and (3) CaO-Assb2Osb5-Hsb2O. More specifically, the objective of this research is to identify various precipitated compounds that can effectively immobilize certain elements that either directly or indirectly have an adverse effect on the environment. In the first quaternary system, CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, boron is the element desired to be ``fixed'' because ``free'' boron is the cause of delayed hardening in cement paste intended for the encapsulation of nuclear waste. Soluble boron also causes the cement paste to prematurely set, a phenomenon called ``flash-set.'' Isothermal calorimetry was used to track the progress of tricalcium aluminate hydration in the presence of boric acid and Ca(OH)sb2 and revealed the presence of a pronounced induction period, the length of which varied with both temperature and boric acid concentration. It was determined that a diffusion barrier, most likely an amorphous calcium borate, deposited onto the active anhydrous tricalcium aluminate grains inhibiting further hydration. Also, under certain conditions, the precipitation of crystalline 4CaO{*}Alsb2Osb3{*}1/2Bsb2Osb3{*}12Hsb2O may be responsible for the observed flash-set due to its flat, plate-like morphology. Another quaternary hydrate, 6CaO{*}Alsb2Osb3{*}2Bsb2Osb3{*}39Hsb2O (boro-ettringite) was also synthesized during this research and crystallized as hexagonal prisms. In contrast to the fast crystallization of 4CaO{*}Alsb2Osb3{*}1/2Bsb2Osb3{*}12Hsb2O, boro-ettringite was observed to form slowly and in stages with the precipitation of the transient phase CaO-Bsb2Osb3{*}6Hsb2O preceding it. Further investigation of these two hydrates lead to the construction of a quaternary phase diagram and to the determination of their solubility products (pKsp = -logKsp), which were determined to be 44.23 for boro-ettringite and 28.51 for 4CaO{*}Alsb2Osb3{*}1/2Bsb2Osb3{*}12Hsb2O. The formation of a solid-solution series between the two apatites, Casb{10}(POsb4)sb6(OH)sb2 and Pbsb{10}(POsb4)sb6(OH)sb2, under ambient conditions and using only oxide starting materials was studied. It was observed that under those conditions, a very limited range of miscibility occurred resulting in the formation of the quaternary apatite, Pbsb{x}Casb{10-x}(POsb4)sb6(OH)sb2 where 5? x<6. The ternary system, CaO-Assb2Osb5-Hsb2O, was also studied under ambient conditions in order to identify a potential host compound suitable for the stabilization of soluble arsenic. Analyses of the solid precipitates and their saturated solutions have revealed the following compounds along with their solubility products (pKsp = -logKsp): Casb4(OH)sb2(AsOsb4)sb2{*}4Hsb2O (29.20), Casb5(AsOsb4)sb3OH (38.04), Casb3(AsOsb4)sb2{*}3{2/3}Hsb2O (21.00), Casb3(AsOsb4)sb2{*}4{1/4}Hsb2O (21.00), Casb5Hsb2(AsOsb4)sb4{*}9Hsb2O-ferrarisite (31.49), Casb5Hsb2(AsOsb4)sb4{*}9Hsb2O-guerinite (30.69), and CaHAsOsb4{*}Hsb2O (4.79). The conditions under which the hydrates Casb4(OH)sb2(AsOsb4)sb2{*}4Hsb2O and Casb5(AsOsb4)sb3OH (arsenate-apatite) precipitated were determined to be best in terms of immobilizing soluble arsenic. Both are highly insoluble and are associated with the lowest concentrations of dissolved arsenic under equilibrium conditions. However, the conditions under which they preferentially form are slightly different. Casb4(OH)sb2(AsOsb4)sb2{*}4Hsb2O was observed to form consistently in the presence of magnesium impurity, whereas the arsenate-apatite formed phase-pure only in the absence of magnesium impurity. This can be advantageous in the sense that the arsenate ion is assured to be stabilized via the precipitation of either one or the other, making the presence of magnesium impurity inconsequential under those conditions which precipitate these two stable hydrates.

  3. Extractive bioconversion in aqueous two-phase systems

    Microsoft Academic Search

    Rajni Kaul; Bo Mattiasson

    1986-01-01

    The transformation of hydrocortisone to prednisolone was studied in aqueous two-phase systems, as a model for the extractive bioconversion of fine chemicals. The bacterium, Arthrobacter simplex, was able to grow in the two-phase system and the cells could be revitalized after a period of use. Use of aqueous two-phase systems made it possible to operate the reaction at higher substrate

  4. Multi-day ozone formation for alkenes and carbonyls investigated with a master chemical mechanism under European conditions

    NASA Astrophysics Data System (ADS)

    Derwent, R. G.; Jenkin, M. E.; Saunders, S. M.; Pilling, M. J.; Passant, N. R.

    A photochemical trajectory model together with a master chemical mechanism and a highly speciated emission inventory have been used to characterise the multi-day formation of photochemical ozone in north west Europe for 123 organic compounds. Multi-day reactivity is apparent for both short-lived as well as long-lived organic compounds and arises for a number of mechanistic reasons. Unreacted organic compounds may be carried over from one day to the next. Degradation products formed on the first day may take part in the formation of ozone over longer timescales compared with those of ozone formation from parent compounds. For the highly reactive alkenes and carbonyls, two additional mechanisms account for much of the ozone formation on the second day. These involved the formation of peroxyacylnitrates and aldehydes during the first day which were carried over into the second day to stimulate additional ozone formation. The implications of these findings are discussed for the highly simplified and parameterised chemical mechanisms employed in some policy applications.

  5. Adaptive plasticity of Laguncularia racemosa in response to different environmental conditions: integrating chemical and biological data by chemometrics.

    PubMed

    da Souza, Iara; Bonomo, Marina Marques; Morozesk, Mariana; Rocha, Lívia Dorsch; Duarte, Ian Drumond; Furlan, Larissa Maria; Arrivabene, Hiulana Pereira; Monferrán, Magdalena Victoria; Matsumoto, Silvia Tamie; Milanez, Camilla Rozindo Dias; Wunderlin, Daniel Alberto; Fernandes, Marisa Narciso

    2014-04-01

    Mangroves are dynamic environments under constant influence of anthropic contaminants. The correlation between environmental contamination levels and possible changes in the morphology of plants, evaluated by multivariate statistics helps to highlight matching between these variables. This study aimed to evaluate the uptake and translocation of metals and metalloids in roots and leaves as well as the changes induced in both anatomy and histochemistry of roots of Laguncularia racemosa inhabiting two estuaries of Espírito Santo (Brazil) with different pollution degrees. The analysis of 14 elements in interstitial water, sediments and plants followed by multivariate statistics, allowed the differentiation of studied sites, showing good match between levels of elements in the environment with the corresponding in plants. L. racemosa showed variations in their root anatomy in different collection areas, with highest values of cortex/vascular cylinder ratio, periderm thickness and air gap area in Vitória Bay, the most polluted sampling area. These three parameters were also important to differentiate the mangrove areas by linear discriminant analysis. The development stage of aerenchyma in roots reflected the oxygen availability in the water, being found a negative correlation between these variables. The combined use of chemical and biological analyses responded quite well to different pollution scenarios, matching morphological responses to physical and chemical parameters, measured at different partitions within the estuary. Thus, L. racemosa can be confirmed as a reliable sentinel plant for biomonitoring of estuaries impacted by anthropic pollution. PMID:24445776

  6. Phytoplankton and physical-chemical conditions in selected rivers and the coastal zone of Lake Michigan, 1972

    SciTech Connect

    Schelske, C.L.; Feldt, L.E.; Simmons, M.S.

    1980-01-01

    A very large data set was obtained on the nearshore environment of Lake Michigan during 1972. The data set is probably unique in that samples were collected and analyzed for a number of physical-chemical parameters and for phytoplankton standing crop and species composition. Phytoplankton identified during the study totaled 431 taxa of which 306 were diatoms, which serves to illustrate the magnitude of available data. Results are presented for eleven different transects sampled in April and for three of these transects which were sampled in September. In addition, transects for the St. Joseph, Kalamazoo, and Grand Rivers were sampled four or five times and each of these rivers were sampled from seven to eleven times in July. Data collected with depth presented in this report include water temperature. Secchi disc transparency, pH, specific conductance, dissolved reactive silica, nitrate nitrogen, and total phosphorus as physical-chemical variables. On transects samples with depth were obtained at stations 0, .2, .8, 1.6, 3.2, 6.4, 13, 26, and 52 km from shore, although the stations from 13 to 52 km were not sampled on every transect. Data related to phytoplankton include species composition and abundance, species diversity, chlorophyll a, and rates of carbon fixation. All these data were obtained only at 2 meters.

  7. [Distribution of 137Cs, 90Sr and their chemical analogues in the components of an above-ground part of a pine in a quasi-equilibrium condition].

    PubMed

    Mamikhin, S V; Manakhov, D V; Shcheglov, A I

    2014-01-01

    The additional study of the distribution of radioactive isotopes of caesium and strontium and their chemical analogues in the above-ground components of pine in the remote from the accident period was carried out. The results of the research confirmed the existence of analogy in the distribution of these elements on the components of this type of wood vegetation in the quasi-equilibrium (relatively radionuclides) condition. Also shown is the selective possibility of using the data on the ash content of the components of forest stands of pine and oak as an information analogue. PMID:25764848

  8. ADVANCED CHEMICAL OXIDATION OF 2,4,6 TRICHLOROPHENOL IN AQUEOUS PHASE BY FENTON'S REAGENT-PART I: EFFECTS OF THE AMOUNTS OF OXIDANT AND CATALYST ON THE TREATMENT REACTION

    Microsoft Academic Search

    SOMNATH BASU; IRVINE W. WEI

    1998-01-01

    Fenton's Reagent is a strong oxidant for 2,4,6 Trichlorophenol (TCP) in aqueous phase. This reaction can be effectively utilized to treat an industrial wastewater containing TCP, and reduce the toxicity of the discharge. This paper reports the effects of the amounts of the oxidant (hydrogen peroxide) and the catalyst (ferrous ions), relative to TCP, on the rates and extents of

  9. Petrophysical core characterization at supercritical geothermal conditions

    NASA Astrophysics Data System (ADS)

    Kummerow, Juliane; Raab, Siegfried

    2015-04-01

    There is a growing scientific interest in the exploitation of supercritical geothermal reservoirs to increase the efficiency of geothermal power plants. The utilisation of geothermal energy requires in any case the detailed knowledge of the reservoir. In reservoir engineering, the characterisation of the geothermal system by electrical resistivity tomography (ERT) is a common geophysical exploration and monitoring strategy. For a realistic interpretation of the field measurements it is necessary to know both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. While there have been made great effort in determine the physical and chemical properties of water above its critical point (Tcritical = 374.21° C and pcritical = 221.2 bar), the influence of fluid-rock interactions on petrophysical properties in supercritical aqueous systems is nearly unknown. At supercritical conditions the viscosity of the fluid is low, which enhances the mass transfer and diffusion-controlled chemical reactions. This may have considerable effects on the porosity and hydraulic properties of a rock. To investigate high-enthalpy fluid-rock systems, in the framework of the EU-funded project IMAGE we have built a new percolation set-up, which allows for the measurement of electrical resistivity and permeability of rock samples at controlled supercritical conditions of aqueous fluids (pore pressure = 400 bar and a temperature = 400° C). First results will be presented.

  10. Responsive aqueous foams.

    PubMed

    Fameau, Anne-Laure; Carl, Adrian; Saint-Jalmes, Arnaud; von Klitzing, Regine

    2015-01-12

    Remarkable properties have emerged recently for aqueous foams, including ultrastability and responsiveness. Responsive aqueous foams refer to foams for which the stability can be switched between stable and unstable states with a change in environment or with external stimuli. Responsive foams have been obtained from various foam stabilizers, such as surfactants, proteins, polymers, and particles, and with various stimuli. Different strategies have been developed to design this type of soft material. We briefly review the two main approaches used to obtain responsive foams. The first approach is based on the responsiveness of the interfacial layer surrounding the gas bubbles, which leads to responsive foams. The second approach is based on modifications that occur in the aqueous phase inside the foam liquid channels to tune the foam stability. We will highlight the most sophisticated approaches, which use light, temperature, and magnetic fields and lead to switchable foam stability. PMID:25384466

  11. Rechargeable hybrid aqueous batteries

    NASA Astrophysics Data System (ADS)

    Yan, Jing; Wang, Jing; Liu, Hao; Bakenov, Zhumabay; Gosselink, Denise; Chen, P.

    2012-10-01

    A new aqueous rechargeable battery combining an intercalation cathode with a metal (first order electrode) anode has been developed. The concept is demonstrated using LiMn2O4 and zinc metal electrodes in an aqueous electrolyte containing two electrochemically active ions (Li+ and Zn2+). The battery operates at about 2 V and preliminarily tests show excellent cycling performance, with about 90% initial capacity retention over 1000 charge-discharge cycles. Use of cation-doped LiMn2O4 cathode further improves the cyclability of the system, which reaches 95% capacity retention after 4000 cycles. The energy density for a prototype battery, estimated at 50-80 Wh kg-1, is comparable or superior to commercial 2 V rechargeable batteries. The combined performance attributes of this new rechargeable aqueous battery indicate that it constitutes a viable alternative to commercial lead-acid system and for large scale energy storage application.

  12. ESTIMATION OF HYDROLYSIS RATE CONSTANTS OF CARBOXYLIC ACID ESTER AND PHOSPHATE ESTER COMPOUNDS IN AQUEOUS SYSTEMS FROM MOLECULAR STRUCTURE BY SPARC

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid ester and phosphate ester compounds in aqueous non- aqueous and systems strictly from molecular structure. The energy diffe...

  13. Preliminary considerations of high temperature aqueous chemistry for representative hot springs in Guangdong, China

    NASA Astrophysics Data System (ADS)

    Lu, G.; Liu, R.; Gu, R.; Wang, Y.

    2013-12-01

    This presentation aims at helping understand general physical and chemical conditions that control geothermal flow to the ground surface. Conditions directly under the ground surface play critical roles in determining the pattern of geothermal flow fields. Controlling factors include structural features, source temperature, hydraulic properties, chemical conditions etc. However, they are hardly measured in a comprehensive way in laboratory or field experimental conditions. There are needs for characterizing conditions evolving during upward thermal flow and to relate physics and chemistry to heat distribution. Geothermal flow depends on exactly how heat diffusion works in the deep ground (the heat conductivity and convection), and the physics and chemistry behind this is complex and not well understood. We employed aqueous geochemistry methods to study heat and geochemistry behavior in deep underground. We develop scheme to relate elevated temperatures and heat to chemistry. The setup for elevated heat is expected to expand the capability of numerical models, so that the temperature effect can be more completely described. The heat has a significant effect on the speciation of water, tending to be more acidic and at more reduced state at an elevated temperature. For example, given an average pH 8.3 for spring outflow cooled down to 25oC, the corresponding hot water at 200oC could have pH as low as 5.8. The findings show that the numerical model effectively simulates chemical behavior in deep ground.

  14. Drying kinetics and physico-chemical characteristics of Osmo- dehydrated Mango, Guava and Aonla under different drying conditions.

    PubMed

    Kumar, P Suresh; Sagar, V R

    2014-08-01

    Mango (Mangiferra indica L), guava (Psiduim guajava L.) slices and aonla (Emblica officinalis L) segments were osmo-dried under four different dying conditions viz., cabinet drier (CD), vacuum oven drier (VOD), low temperature drier (LTD) and solar drier (SD) to evaluate the best drying condition for the fruits. It was found that vacuum oven drying was superior to other mode of drying as it holds maximum nutrients like acidity, ascorbic acid, sugar and water removal and moisture ratio of products. It was found through regression analysis that drying ratio and rehydration ratio was also superior in vacuum drying followed by cabinet drying. In addition, descriptive analysis on sensory score was also found best with vacuum drying while the Non-enzymatic browning (NEB), which is undesirable character on dried product, was more with solar drier. PMID:25114345

  15. Germination response of black and yellow seed coated canola ( Brassica napus ) lines to chemical treatments under cold temperature conditions

    Microsoft Academic Search

    Wentao Zhang; Lawrence V. Gusta

    2010-01-01

    Seed quality is a key critical component to produce well established and vigorous seedlings under cool soil (<10°C) conditions\\u000a experienced in Western Canada. A simple, relatively quick germination assay is required to separate small differences in seed\\u000a germination which can have a significant impact on seedling growth. It has long been established that phytohormones regulate\\u000a seed germination: abscisic acid inhibits

  16. Ion mobility spectrometry versus classical physico-chemical analysis for assessing the shelf life of extra virgin olive oil according to container type and storage conditions.

    PubMed

    Garrido-Delgado, Rocío; Dobao-Prieto, M Mar; Arce, Lourdes; Aguilar, Joaquín; Cumplido, José L; Valcárcel, Miguel

    2015-03-01

    An experimental study was conducted to assess the stability of a single-variety (Arbequina) extra virgin olive oil (EVOO) as a function of container type and storage conditions over a period of 11 months. EVOO quality was assessed by using ion mobility spectrometry (IMS), which provides increased simplicity, expeditiousness, and relative economy. The results were compared with the ones obtained by using the official method based on classical physico-chemical analysis. Bag-in-box, metal, dark glass, clear glass, and polyethylene terephthalate containers holding EVOO were opened on a periodic basis for sampling to simulate domestic use; in parallel, other containers were kept closed until analysis to simulate the storage conditions on market shelves. The results of the physico-chemical and instrumental analyses led to similar conclusions. Thus, samples packaged in bag-in-box containers preserved oil quality for 11 months, better than other container types. The HS-GC-IMS results confirm that 2-heptenal and 1-penten-3-one are two accurate markers of EVOO quality. PMID:25645180

  17. Effect of chromatographic conditions on retention behavior and system efficiency for HPTLC of selected psychotropic drugs on chemically bonded stationary phases.

    PubMed

    Petruczynik, Anna; Wróblewski, Karol; Waksmundzka-Hajnos, Monika

    2015-01-01

    Selected psychotropic drug standards have been chromatographed on RP18, CN and diol layers with a variety of aqueous and nonaqueous mobile phases. The effect of buffers at acidic or basic pH, acetic acid, ammonia and diethylamine (DEA) in aqueous mobile phases on retention, efficiency and peak symmetry was examined. Improved peak symmetry and separation selectivity for investigated compounds were observed when ammonia or DEA were used as mobile phase additives. The effect of diethylamine concentration in aqueous eluents on retention, peak symmetry and theoretical plate number obtained on CN plates was also investigated. Because of the strong retention of these basic drugs on stationary phases bonded on silica matrix, nonaqueous eluents containing medium polar diluents, strongly polar modifiers and silanol blockers (ammonia or diethylamine) were applied. Aqueous and nonaqueous eluent systems with the best selectivity and efficiency were used for separate psychotropic drug standards' mixture on CN layer by 2D TLC. PMID:25850199

  18. An effective freezing/thawing method for human pluripotent stem cells cultured in chemically-defined and feeder-free conditions

    PubMed Central

    Nishishita, Naoki; Muramatsu, Marie; Kawamata, Shin

    2015-01-01

    Culturing human Pluripotent Stem Cells (hPSC)s in chemically defined medium and feeder-free condition can facilitate metabolome and proteome analysis of culturing cells and medium, and reduce regulatory concerns for clinical application of cells. And in addition, if hPSC are passaged and cryopreserved in single cells it also facilitates quality control of cells at single cell level. Here we report a robust single cell freezing and thawing method of hPSCs cultured in chemically-defined medium TeSRTM-E8TM and on cost-effective recombinant human Vitronectin-N (rhVTN-N)-coated dish. Cells are dissociated into single cells with recombinant TrypLETM Select and 0.5 mM EDTA/PBS (3:1 solution) in the presence of Rock inhibitor and cryopreserved with chemically defined CryoStemTM. Approximately 60% of cells were viable after dissociation. AggrewellTM 400 was used to form cell clumps of 500 cells after thaw in the presence of Rock inhibitor and cells were cultured for two days with TeSR-E8. Cells clumps were then seeded on rhVTN-N-coated dish and cultured with TeSR-E8 for two days prior to the first passage after thawing. Number of viable cells at the first passage increased around 10 times of that just before freezing. This robust single cell freezing method for hPSCs cultured in chemically defined medium will facilitate quality control of cultured cells at single cell level before cryopreservation and consequently assure the quality of cells in frozen vials for further manipulation after thawing. PMID:25973330

  19. Distribution of small dispersive coal dust particles and absorbed radioactive chemical elements in conditions of forced acoustic resonance in iodine air filter at nuclear power plant

    E-print Network

    Oleg P. Ledenyov; Ivan M. Neklyudov

    2013-06-14

    The physical features of distribution of the small dispersive coal dust particles and the adsorbed radioactive chemical elements and their isotopes in the absorber with the granular filtering medium with the cylindrical coal granules were researched in the case of the intensive air dust aerosol stream flow through the iodine air filter (IAF). It was shown that, at the certain aerodynamic conditions in the IAF, the generation of the acoustic oscillations is possible. It was found that the acoustic oscillations generation results in an appearance of the standing acoustic waves of the air pressure (density) in the IAF. In the case of the intensive blow of the air dust aerosol, it was demonstrated that the standing acoustic waves have some strong influences on both: 1) the dynamics of small dispersive coal dust particles movement and their accumulation in the IAF; 2) the oversaturation of the cylindrical coal granules by the adsorbed radioactive chemical elements and their isotopes in the regions, where the antinodes of the acoustic waves are positioned. Finally, we completed the comparative analysis of the theoretical calculations with the experimental results, obtained for the cases of: 1) the experimental aerodynamic modeling of physical processes of the absorbed radioactive chemical elements and their isotopes distribution in the IAF; and 2) the gamma-activation spectroscopy analysis of the absorbed radioactive chemical elements and their isotopes distribution in the IAF. We made the innovative propositions on the necessary technical modifications with the purpose to improve the IAF technical characteristics and increase its operational time at the nuclear power plant (NPP), going from the completed precise characterization of the IAF parameters at the long term operation.

  20. Chemical composition and selected mechanical properties of Al-Zn alloy modified in plasma conditions by RF CVD

    NASA Astrophysics Data System (ADS)

    Kyzio?, Karol; Kluska, Stanis?awa; Janu?, Marta; ?roda, Marcin; Jastrz?bski, Witold; Kaczmarek, ?ukasz

    2014-08-01

    The paper reports results of the study of surface composition and selected functional properties of 7075 (Al-Zn) alloys modified in Ar, N2, SiH4 and CH4 atmosphere at reduced pressure. RF CVD (Radio Frequency Chemical Vapour Deposition) technique was used in the study. The type or weight percentage of carbon in each modification varied in the resultant SiN:H and SiCN:H coatings. Alloy samples were treated with Ar+ plasma etching and N+ ion implantation at reduced pressure. The tests proved the values of selected mechanical properties (hardness ca. 10.5 GPa, Young modulus ca. 95 GPa) and adhesion (delamination force ca. 11.5 mN) to be higher in the case of SiCN:H anti-wear coating (deposited in SiH4:CH4:N2 = 1:1:2 gas mixture) than the values of the respective parameters obtained in the remaining modifications. Further, carbon doped coatings (SiCN:H) exhibited significantly improved hardness (by about 50 to 70%) and nearly threefold increase in delamination force in comparison with SiCN:H coatings.

  1. Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

    USGS Publications Warehouse

    Kent, D.B.; Davis, J.A.; Joye, J.L.; Curtis, G.P.

    2008-01-01

    Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.

  2. Laboratory study of chemical speciation of mercury in lake sediment and water under aerobic and anaerobic conditions

    SciTech Connect

    Regnell, O.; Tunlid, A. (Univ. of Lund (Sweden))

    1991-03-01

    Chemical speciation and partitioning of radiolabeled HgCl{sub 2} were studied in model aquatic systems consisting of undisturbed eutrophic lake sediment and water in plastic cylinders. The cylinders were either gradually made anaerobic by a gentle flow of N{sub 2}-CO{sub 2} or kept aerobic by air flow. The proportion of methylated {sup 203}Hg was significantly higher, in both water and sediment, in the anaerobic systems than in the aerobic systems. The composition and total concentration of fatty acids originating from bacterial phospholipids, as well as the concentration of vitamin B{sub 12}, including related cobalamins, were similar in sediments from the anaerobic and aerobic systems. Bacterial cell numbers were, on average, 3.6 times higher in the anaerobic water columns than in the aerobic ones. Volatilization of {sup 203}Hg occurred in all systems except in an autoclaved control and was of similar magnitudes in the anaerobic and aerobic systems. Incorporation of {sup 203}Hg into the sediment was significantly faster in the aerobic systems than in the anaerobic systems. These results suggest that episodes of anoxia in bottom waters and sediment cause an increase in net mercury methylation and, hence, an increase in bioavailable mercury.

  3. Continuous aqueous tritium monitor

    DOEpatents

    McManus, Gary J. (Idaho Falls, ID); Weesner, Forrest J. (Idaho Falls, ID)

    1989-05-30

    An apparatus for a selective on-line determination of aqueous tritium concentration is disclosed. A moist air stream of the liquid solution being analyzed is passed through a permeation dryer where the tritium and moisture and selectively removed to a purge air stream. The purge air stream is then analyzed for tritium concentration, humidity, and temperature, which allows computation of liquid tritium concentration.

  4. Method for processing aqueous wastes

    DOEpatents

    Pickett, John B. (3922 Wood Valley Dr., Aiken, SC 29803); Martin, Hollis L. (Rt. 1, Box 188KB, McCormick, SC 29835); Langton, Christine A. (455 Sumter St. SE., Aiken, SC 29801); Harley, Willie W. (110 Fairchild St., Batesburg, SC 29006)

    1993-01-01

    A method for treating waste water such as that from an industrial processing facility comprising the separation of the waste water into a dilute waste stream and a concentrated waste stream. The concentrated waste stream is treated chemically to enhance precipitation and then allowed to separate into a sludge and a supernate. The supernate is skimmed or filtered from the sludge and blended with the dilute waste stream to form a second dilute waste stream. The sludge remaining is mixed with cementitious material, rinsed to dissolve soluble components, then pressed to remove excess water and dissolved solids before being allowed to cure. The dilute waste stream is also chemically treated to decompose carbonate complexes and metal ions and then mixed with cationic polymer to cause the precipitated solids to flocculate. Filtration of the flocculant removes sufficient solids to allow the waste water to be discharged to the surface of a stream. The filtered material is added to the sludge of the concentrated waste stream. The method is also applicable to the treatment and removal of soluble uranium from aqueous streams, such that the treated stream may be used as a potable water supply.

  5. Method for processing aqueous wastes

    DOEpatents

    Pickett, J.B.; Martin, H.L.; Langton, C.A.; Harley, W.W.

    1993-12-28

    A method is presented for treating waste water such as that from an industrial processing facility comprising the separation of the waste water into a dilute waste stream and a concentrated waste stream. The concentrated waste stream is treated chemically to enhance precipitation and then allowed to separate into a sludge and a supernate. The supernate is skimmed or filtered from the sludge and blended with the dilute waste stream to form a second dilute waste stream. The sludge remaining is mixed with cementitious material, rinsed to dissolve soluble components, then pressed to remove excess water and dissolved solids before being allowed to cure. The dilute waste stream is also chemically treated to decompose carbonate complexes and metal ions and then mixed with cationic polymer to cause the precipitated solids to flocculate. Filtration of the flocculant removes sufficient solids to allow the waste water to be discharged to the surface of a stream. The filtered material is added to the sludge of the concentrated waste stream. The method is also applicable to the treatment and removal of soluble uranium from aqueous streams, such that the treated stream may be used as a potable water supply. 4 figures.

  6. Mars Aqueous Chemistry Experiment (MACE)

    NASA Technical Reports Server (NTRS)

    Benton, Clark C. (Editor)

    1995-01-01

    The concept of an aqueous-based chemical analyzer for Martian surface materials has been demonstrated to be feasible. During the processes of analysis, design, breadboarding, and most importantly, testing, it has become quite apparent that there are many challenges in implementing such a system. Nonetheless, excellent progress has been made and a number of problems which arose have been solved. The ability to conduct this work under a development environment which is separate and which precedes the project-level development has allowed us to find solutions to these implementation realities at low cost. If the instrument had been selected for a mission without this laboratory pre-project work, the costs of implementation would be much higher. In the four areas covered in Sections D, E, F, and G of this Final Report, outstanding progress has been made. There still remains the task of flight-qualifying certain of the components. This is traditionally done under the aegis of a Flight Project, but just as the concept development can be done at much lower cost when kept small and focused, so could the qualification program of critical parts benefit. We recommend, therefore, that NASA consider means of such qualifications and brass-boarding, in advance of final flight development. This is a generic recommendation, but hardware such as the Mars aqueous chemistry experiment (MACE) and other similarly-new concepts are particularly applicable. MACE now has wide versatility, in being able to reliably dispense both liquids and solids as chemical reagents to an entire suite of samples. The hardware and the experiment is much simpler than was developed for the Viking Biology instrument, yet can accomplish all the inorganic chemical measurements that the Viking desing was capable of. In addition, it is much more flexible and versatile to new experiment protocols (and reagents) than the Viking design ever could have been. MACE opens up the opportunity for many different scientific disciplines to design sub- experiments and to benefit from the investigations that can be conducted. In this sense, it will have the value of a facility, although our recommendation would be that it be under the stewardship of a single lead investigator to insure that conflicting requirements not compromise the straight-forward design that have been achieved. MACE is an excellent candidate for upcoming Mars missions, including the Mars Surveyor Program (MSP) lander missions in 2001 and 2003. In addition, it could be used for any mission to the surface of any other planet or planetary body (including small bodies). An important next step is to encourage various investigators to propose specific uses for this experiment that specifically address their major scientific objectives for upcoming missions.

  7. Role of intra-hippocampal orexin 1 and orexin 2 receptors in conditioned place preference induced by chemical stimulation of the lateral hypothalamus.

    PubMed

    Rashidy-Pour, Ali; Moradi, Marzieh; Fatahi, Zahra; Haghparast, Amir; Haghparast, Abbas

    2015-02-15

    Evidence from animal models suggests a role for orexinergic system in reward processing and drug addiction. The lateral hypothalamus (LH) orexin neurons send projections to the dorsal hippocampus (CA1 region) which plays a pivotal role in reward processes. Moreover, it has been shown that orexin containing terminals and orexin receptors are distributed in the hippocampal formation. In this study, we assessed the role of orexin 1 (OX1r) and orexin2 (OX2r) receptors in the CA1 on the development of LH stimulation-induced conditioned place preference (CPP). Animals weighing 230-280 g were unilaterally implanted by two separate cannulae into the LH and CA1. The CPP paradigm was done; SB334867 and TCSOX229, as selective OX1r and OX2r antagonists (1, 3, 10 and 30 nM/0.5 ?l DMSO) administrated into the CA1 prior to intra-LH carbachol microinjection (250 nM; the most effective dose) during the 3-days conditioning phase, respectively. Conditioning scores and locomotor activities were recorded by Ethovision software on the test day. The results showed that the administration of OX1r and OX2r antagonists into the CA1 attenuated the development of CPP induced by chemical stimulation of the LH. However, this decrease in OX1r antagonist treated groups was more significant than that in OX2r antagonist treated animals. Our findings suggest that OX1 and OX2 receptors in the CA1 region of the hippocampus were involved in the development of CPP induced by chemical stimulation of the LH and the efficiency of OX1 receptors in this phenomenon was more considerable than OX2 receptors in rats. PMID:25446766

  8. An Investigation on Soil Chemical Composition and Shallow Groundwater Condition in a Saline Area in Nakhon Panom Province, Thailand

    NASA Astrophysics Data System (ADS)

    Seeboonruang, U.

    2010-12-01

    The Mekong River Basin region is a potential salt-accumulated neighborhood. Several subbasin areas have been reported to have the saline soil problem and these include Lower Songkram River, Nam Oon Brook, Nam Thew Brook, and Namkam Brook. The study area is located on the lower of the Namkam River Basin mainly in 3 districts of the Nakhon Panom Province and these districts are Amphoe That Panom, Amphoe Nakae, and Amphoe Renu Nakhon. Soil salinity is found risen sparsely in some villages of these three districts. Generally, shallow groundwater is known to facilitate the distribution of dissolved salts away from the salinity sources and to pick up the salts to the top soils. Thus, groundwater plays a major role in salinity distribution everywhere. The objective of this research is to investigate the soil chemical composition and shallow groundwater evolution in the study area. Soil samples are analyzed using X-Ray Fluorescence Spectrometer (XRF). The depth to groundwater, groundwater pH, total dissolved solids (TDS), electrical resistivity (EC), and salinity are the parameters and the measurement takes place from October 2007 to present. There are 19 sampling locations distributed in the study area. The depth of the observation wells varies from 4 m to 40 m. Groundwater table is found to be up to 7 m below the groundwater surface and the depth is increasing from December to April. Groundwater pH is constantly less than 7 and greater than 4. Groundwater pH varies significantly between 10 mg/l to 45,000 mg/l and EC also differs between 10 µS/cm to 90,000 µS/cm. Most of groundwater sampled in the study area is slight blackish with salinity measured below 1.00 ppt and these are Ban Don Dang, Ban Wang Yang, Ban Na Khu, Ban Piman Ta, Pan Sala, and Ban Lao Tung. On the other hand, Ban Bo Dong Sorn and Ban Pra Song Noi have very saline shallow groundwater with salinity greater 1ppt. The results from the XRF show that SiO2 and Al2O3 are the main composition and the soil is made up of SiO2 more than 50% and Al2O3 more than 15%. The minor chemical elements are Fe2O3, K2O, MgO, CaO, SO3, TiO2, Cl, CuO, and MnO. The percentages of these elements on the average are as following 8, 5, 5, 4, 3, 2, 0.7, 0.2, and 0.2, respectively. The soil sample from one of the salt pits is composed of Na2O almost 60% and Cl more than 30%.

  9. Chemical, petrologic and experimental constraints on the pre-eruptive conditions of Lascar volcano, Central Andean magma systems

    NASA Astrophysics Data System (ADS)

    Torresi, G.; Botcharnikov, R. E.; Holtz, F.; Banaszak, M.; Worner, G.

    2009-04-01

    Lascar Volcano is a calc-alkaline stratovolcano located in the Central Volcanic Zone (CVZ), Northern Chile. The volcanic activity of Lascar started about 5 Ma ago and moved first eastwards and then westwards. Lascar represents the most active volcano of this area. Volcanic sequence has been divided into four main stages (43 to 26.5 ka for stage I, 26.5 ka for stage II, 22.3 to 9.3 ka for stage III and 7.1 to present for stage IV). The major rock types of Lascar are mainly porphyritic andesites to dacites with plagioclase as the dominant phenocryst. The activity of Lascar has been characterised by cyclic behaviour involving the growth and subsidence of lava domes, degassing of the magma, and vulcanian to plinian eruptive events culminated in the bigger eruption on 1993. Geochemical analyses combined with experimental simulations are used to discuss the role of mixing and fractionation during magma ascent and the pre-eruptive conditions in the magma chamber. Hornblende-plagioclase and clinopyroxene-orthopyroxene thermometry, magnetite-ilmenite thermo-oxy-barometry and amphibole barometry, were applied to characterize the magmatic conditions of the most recent eruptions from stage IV (for details see Banaszak et al., this session). Hornblende-plagioclase thermometry as well as clinopyroxene-orthopyroxene pairs yielded a large and continuous temperature interval of crystallization from ~ 850 to 1010°C. Temperature and oxygen fugacity determined from magnetite-ilmenite pairs vary from 840 to 950 °C at oxidizing conditions from 1.0 to 2.0 log units above NNO. The compositions of amphiboles provide estimates for pressures from 200 to 500 MPa for Lascar andesites. Geochemical data such as strontium (87Sr/86Sr = 0.7057-0.7066) and oxygen isotopes (?18O = 6.5-7.1) from Lascar volcanic sequence demonstrate significant crustal contamination. Additional constraints on the pre-eruptive conditions could be derived from melt inclusions in mineral phenocrysts of Lascar lavas, bombs and pyroclastics. Several samples have been investigated, showing that phenocrysts of plagioclase, ortho- and clinopyroxenes and also rare olivines contain entrapped and well-preserved melt inclusions. The dimensions of inclusions vary from less than 10 to more than 100 µm. For the measurements only the inclusion larger than 50 µm were selected. Plagioclase phenocrysts were analysed first, and melt inclusions reveal dacitic to rhyolitic compositions. The analysis of volatiles indicates the presence of chlorine, fluorine and sulphur but in relatively small concentrations. Further work is in progress to analyse concentrations of H2O and CO2 in the inclusions (in particular, in olivine). An andesitic white pumice has been chosen as starting composition for the crystallization experiments. This sample is representative of the last stage (i.e. stage IV) eruptions, with magma composition containing ~ 58 wt% of SiO2 and ~ 5 wt% of MgO. The major phases present in this sample are plagioclase, two pyroxenes and amphibole. Accessory phases are also oxides, sulphides and rare olivine. Plagioclase has a calcic composition (An30-70), while clinopyroxenes are dominated by augite composition. First experimental results will be presented.

  10. Evaluation of chemical, biological, and physical conditions in the Winter Haven chain of lakes, Florida, March-June 1976

    USGS Publications Warehouse

    Reichenbaugh, R.C.; Hughes, G.H.

    1977-01-01

    Reconnaissance of water-quality conditions of 14 interconnected navigable lakes, in and around Winter Haven, Fla., revealed that in March and May, 1976 most were eutrophic, on the basis of high nutrient (nitrogen and phosphorus) concentrations. Lakes Lulu and Shipp were the most enriched as a result of surface runoff from residential, agricultural, and highly urbanized areas, and many years of municipal and industrial waste effluent input. Phytoplankton counts were greater than a million cells per milliliter in some lakes sampled; algal blooms have ocurred, and water clarity was low. The level of Lake Howard fell to the lowest stage recorded in 31 years during May 1976. The record low was likely due to rainfall deficiency. Leakage of water through the lake beds to the ground-water system is also possible, but determination of the escaping water volume would require additional study. (Woodard-USGS)

  11. Spectroscopic evidence for selenium(iv) dimerization in aqueous solution.

    PubMed

    Kretzschmar, J; Jordan, N; Brendler, E; Tsushima, S; Franzen, C; Foerstendorf, H; Stockmann, M; Heim, K; Brendler, V

    2015-05-27

    The aqueous speciation of selenium(iv) was elucidated by a combined approach applying quantum chemical calculations, infrared (IR), Raman, and (77)Se NMR spectroscopy. The dimerization of hydrogen selenite (HSeO3(-)) was confirmed at concentrations above 10 mmol L(-1) by both IR and NMR spectroscopy. Quantum chemical calculations provided the assignment of vibrational bands observed to specific molecular modes of the (HSeO3)2(2-) ion. The results presented will provide a better understanding of the chemistry of aqueous Se(iv) which is of particular interest for processes occurring at mineral/water interfaces. PMID:25986391

  12. Fiber-Optic Chemiluminescent Biosensors for Monitoring Aqueous Alcohols and Other Water Quality Parameters

    NASA Technical Reports Server (NTRS)

    Verostko, Charles E. (Inventor); Atwater, James E. (Inventor); Akse, James R. (Inventor); DeHart, Jeffrey L. (Inventor); Wheeler, Richard R. (Inventor)

    1998-01-01

    A "reagentless" chemiluminescent biosensor and method for the determination of hydrogen peroxide, ethanol and D-glucose in water is disclosed. An aqueous stream is basified by passing it through a solid phase base bed. Luminol is then dissolved in the basified effluent at a controlled rate. Oxidation of the luminol is catalyzed by the target chemical to produce emitted light. The intensity of the emitted light is detected as a measure of the target chemical concentration in the aqueous stream. The emitted light can be transmitted by a fiber optic bundle to a remote location from the aqueous stream for a remote reading of the target chemical concentration.

  13. Characterization of the pivotal carbon metabolism of Streptococcus suis serotype 2 under ex vivo and chemically defined in vitro conditions by isotopologue profiling.

    PubMed

    Willenborg, Jörg; Huber, Claudia; Koczula, Anna; Lange, Birgit; Eisenreich, Wolfgang; Valentin-Weigand, Peter; Goethe, Ralph

    2015-02-27

    Streptococcus suis is a neglected zoonotic pathogen that has to adapt to the nutritional requirements in the different host niches encountered during infection and establishment of invasive diseases. To dissect the central metabolic activity of S. suis under different conditions of nutrient availability, we performed labeling experiments starting from [(13)C]glucose specimens and analyzed the resulting isotopologue patterns in amino acids of S. suis grown under in vitro and ex vivo conditions. In combination with classical growth experiments, we found that S. suis is auxotrophic for Arg, Gln/Glu, His, Leu, and Trp in chemically defined medium. De novo biosynthesis was shown for Ala, Asp, Ser, and Thr at high rates and for Gly, Lys, Phe, Tyr, and Val at moderate or low rates, respectively. Glucose degradation occurred mainly by glycolysis and to a minor extent by the pentose phosphate pathway. Furthermore, the exclusive formation of oxaloacetate by phosphoenolpyruvate (PEP) carboxylation became evident from the patterns in de novo synthesized amino acids. Labeling experiments with S. suis grown ex vivo in blood or cerebrospinal fluid reflected the metabolic adaptation to these host niches with different nutrient availability; however, similar key metabolic activities were identified under these conditions. This points at the robustness of the core metabolic pathways in S. suis during the infection process. The crucial role of PEP carboxylation for growth of S. suis in the host was supported by experiments with a PEP carboxylase-deficient mutant strain in blood and cerebrospinal fluid. PMID:25575595

  14. Effects of aqueous organosulfur chemistry on particulate methanesulfonate to non-sea salt sulfate ratios in the marine atmosphere

    NASA Astrophysics Data System (ADS)

    Zhu, Lei; Nenes, Athanasios; Wine, Paul H.; Nicovich, J. Michael

    2006-03-01

    The oxidation of dimethyl sulfide (DMS, CH3SCH3) in the atmosphere could influence climate by affecting cloud condensation nuclei concentrations and cloud properties. This work focuses on elucidating the importance of DMS-cloud interactions, especially the poorly understood aqueous phase chemical transformations of DMS oxidation products. For this purpose, we incorporate an oxidation mechanism of atmospheric DMS and its products within the modeling framework of a trajectory ensemble model (TEM). Both marine cumulus and stratocumulus clouds are considered. It is found that the aqueous phase reactions of sulfur compounds contribute >97% of methanesulfonate (MS, CH3(O)S(O)O-) and >80% of non-sea salt sulfate (NSS) production in particles and that about 30% of total MS and NSS production is from the aqueous phase oxidation of the organosulfur compounds. The aqueous phase methanesulfinate (MSI, CH3S(O)O-) + Cl2- reaction is found to be more important than MSI + OH as an MS source. The MS + OH reaction could consume almost 20% of MS and produce about 8% of total NSS within 3 days under typical marine atmospheric conditions.

  15. PHYSIOLOGICAL ONTOGENY : A. CHICKEN EMBRYOS. II. CATABOLISM. CHEMICAL CHANGES IN FERTILE EGGS DURING INCUBATION. SELECTION OF STANDARD CONDITIONS.

    PubMed

    Murray, H A

    1925-09-20

    As this paper goes to press a complete review of the chemistry of the fertile egg will be appearing (19). The author, Mr. J. Needham, was kind enough to allow me to inspect his manuscript and thus avail myself of the comprehensive bibliography and discussion. It is surprising that no biochemists have estimated the changing water content of the egg during incubation. Many of the analyses reported in Needham's review were expressed in per cent of total weight or per cent of dry solid, and consequently are of questionable value, since these latter functions are themselves changing; the former due to water evaporation and the latter through the addition of shell constituents and the burning of oxidizable organic compounds. Moreover, there has been no statistical treatment of the results, and the reliability of the average, figures obtained has consequently been difficult to estimate. Tangl's work, quoted throughout this paper, except for its lack of statistical treatment is more enlightening. However, his concept of the so called "Energy of Embryogenesis" which he propounds, seems to me misleading and unwarranted. What Tangl measured was the amount and the caloric value of the solid material burned and thus the quantity of energy lost during the embryonic period. The latter is equivalent to the usual measurements of catabolism. In the case of the embryo it is not basal metabolism which is being estimated, since the conditions are not basal. The embryo is absorbing and assimilating nutriment all the while at a relatively rapid rate. The calorific value of the oxidized solid, which is in truth the amount of energy lost during a certain chosen interval, in Tangl's judgment stands for the energy of embryogenesis; i.e., the energy of development (growth + differentiation). We believe that this conception is erroneous. The two processes, anabolism and catabolism, occur together and undoubtedly have some relationship, but surely one is not a measure of the other. In a starving animal, and so probably in a starving embryo, there is a considerable amount of so called basal metabolism. Thus if the "Embryogenetic Energy" were measured under these conditions a figure would be obtained for which there was no growth to correspond, or in other words there would be a value for something which did not exist. It will be seen in our later communications that the changes with age of metabolic rate and growth rate do not coincide. The amount of catabolism under certain circumstances does not accelerate growth or anabolism, but seems rather to be a limiting factor. It is as if when the absorbed energy were constant an increase of catabolism would make inroads upon the amount of energy which otherwise would remain for storage (growth). If, as Pembrey's (20) experiments would tend to show, there is an increase of metabolism in the oldest embryos when the outside temperature is lowered, one would find at the end of incubation in such cases that there was a greater amount of so called "Energy of Development" but smaller embryo. It seems that the potential energy amassed as growth comes from that remaining after the needs of the body have been satisfied. The results of the experiments described in this paper have formed the basis for judgment in the selection of suitable standard conditions for the incubation of hen's eggs. Standardization was necessary so that in future experiments the more important environmental factors might be kept uniform within a certain appropriate range and therefore not be held accountable for deviations observed in the embryos. Henceforth in this series of papers the term "standard incubation conditions" will signify that (1) the temperature was constantly at 38.8 +/- 0.4 degrees C., (2) the humidity at 67.5 +/- 2.5 per cent, (3) there was a continuous flow of warm air into the incubator to provide the necessary circulation, and (4) the eggs were rolled once a day within the constant temperature room. The incubator, a double-walled copper cabinet, stands in a constant temperature room

  16. Kinetics and thermodynamics of atmospherically relevant aqueous phase reactions of ?-pinene oxide.

    PubMed

    Bleier, Dylan B; Elrod, Matthew J

    2013-05-23

    Recent work has demonstrated that isoprene-derived epoxide intermediates are responsible for a wide variety of chemical species found in ambient secondary organic aerosol (SOA). Since the second most abundant biogenic hydrocarbon, ?-pinene, is also known to form an epoxide intermediate, nuclear magnetic resonance techniques were used to study products, kinetics, and equilibria of the aqueous phase reactions of that epoxide, ?-pinene oxide. The present results indicate that ?-pinene oxide will react very quickly with aqueous atmospheric particles, even under low acidity conditions. Depending on the acid concentration of the aqueous solutions, a number of new products are observed from the reaction of ?-pinene oxide, some of which are expected to partition back to the gas phase. In contrast to some previous results, no long-lived organosulfate or organonitrate species are observed, and no species which retain the ?-pinene bicyclic carbon backbone are observed. Rather, the overall product distribution can be explained by various rearrangements of the initial carbocation intermediate formed in the ring opening of ?-pinene oxide, all of which can be rationalized by the thermodynamically driven relief of the bicyclic ring strain in the ?-pinene carbon backbone. PMID:23614856

  17. Occurrence of surface polysulfides during the interaction between ferric (hydr)oxides and aqueous sulfide.

    PubMed

    Wan, Moli; Shchukarev, Andrey; Lohmayer, Regina; Planer-Friedrich, Britta; Peiffer, Stefan

    2014-05-01

    Polysulfides are often referred to as key reactants in the sulfur cycle, especially during the interaction of ferric (hydr)oxides and sulfide, forming ferrous-sulphide minerals. Despite their potential relevance, the extent of polysulfide formation and its relevance for product formation pathways remains enigmatic. We applied cryogenic X-ray Photoelectron Spectroscopy and wet chemical analysis to study sulfur oxidation products during the reaction of goethite and lepidocrocite with aqueous sulfide at different initial Fe/S molar ratios under anoxic conditions at neutral pH. The higher reactivity of lepidocrocite leads to faster and higher electron turnover compared to goethite. We were able to demonstrate for the first time the occurrence of surface-associated polysulfides being the main oxidation products in the presence of both minerals, with a predominance of disulfide (S2(2-)(surf)), and elemental sulfur. Concentrations of aqueous polysulfide species were negligible (<1%). With prior sulfide fixation by zinc acetate, the surface-associated polysulfides could be precipitated as zerovalent sulfur (S°), which was extracted by methanol thereafter. Of the generated S°, 20-34% were associated with S2(2-)(surf). Varying the Fe/S ratio revealed that surface polysulfide formation only becomes dominant when the remaining aqueous sulfide concentration is low (<0.03 mmol L(-1)). We hypothesize these novel surface sulfur species, particularly surface disulfide, to act as pyrite precursors. We further propose that these species play an overlooked role in the sulfur cycle. PMID:24735157

  18. Uranium (VI) recovery from aqueous medium using novel floating macroporous alginate-agarose-magnetite cryobeads.

    PubMed

    Tripathi, Anuj; Melo, Jose Savio; D'Souza, Stanislaus Francis

    2013-02-15

    This study presents a novel development of a floating polymeric-magnetite cryobead for the recovery of hexavalent uranium from the aqueous sub-surfaces. The alginate-agarose-magnetite cryobeads were synthesized by the process of cryotropic-gelation at subzero-temperature. The physico-chemical properties of cryobeads showed high surface area and high interconnected porosity (? 90%). Low density of these cryobeads explains their floating property in the aqueous medium. The rheological analysis of cryobeads showed its stability and increased stiffness after uranium adsorption. The presence of magnetite nanoparticles in the porous cryobeads facilitates the recovery of these beads by applying an external magnetic field. Maximum uranium adsorption (97 ± 2%) was observed in the pH range of 4.5-5.5. The thermodynamic parameters suggest passive endothermic adsorption behaviour. HCl was found to be an efficient eluent for the uranium desorption. Five repeated cycles for the desorption of uranium from biosorbent showed 69 ± 3% of uranium recovery. These results suggest stability of these novel floating magnetite-cryobeads under environmental conditions with potential for the recovery of uranium from contaminated aqueous subsurfaces. PMID:23280054

  19. Manipulation of cellulose nanocrystal surface sulfate groups toward biomimetic nanostructures in aqueous media.

    PubMed

    Zoppe, Justin O; Johansson, Leena-Sisko; Seppälä, Jukka

    2015-08-01

    We report a facile aqueous procedure to create multivalent displays of sulfonated ligands on CNCs for future applications as viral inhibitors. CNCs were decorated with model compounds containing sulfonate groups via reactions of epoxides and isothiocyanates with amines under alkaline conditions. At first, surface sulfate groups of CNCs were hydrolytically cleaved by alkaline hydrolysis to increase the number of available surface hydroxyls. Success of desulfation was confirmed via dynamic light scattering (DLS), zeta potential measurements and thermogravimetric analysis (TGA). CNC surface hydroxyl groups were then activated with epichlorohydrin before subsequent reactions. As proof of concept toward aqueous pathways for functionalizing nanoparticles with sulfonated ligands, 3-chloro-2-hydroxy-1-propanesulfonic acid sodium salt hydrate (CPSA) and 4-sulfophenyl isothiocyanate sodium salt monohydrate (4-SPITC) were chosen as model compounds to react with homobifunctional 2,2'-(ethylenedioxy)bis(ethylamine) (EBEA) molecular spacer. The approaches presented are not only applicable to polysaccharide nanocrystals, but also other classes of polymeric and inorganic substrates presenting surface hydroxyl groups, as in the case of poly(2-hydroxyethyl methacrylate) (PHEMA), silica or glass. CNCs carrying sulfonated ligands were characterized by ATR-FTIR and UV-vis spectroscopy. Surface chemical compositions of desired elements were determined via X-ray photoelectron spectroscopy (XPS). We anticipate that with these facile aqueous procedures as the proof of concept, a diverse library of target-specific functionalities can be conjugated to CNCs for applications in nanomedicine, especially related to viral inhibition. PMID:25933518

  20. TiO2 nanofibre assisted photocatalytic degradation of reactive blue 19 dye from aqueous solution.

    PubMed

    Rezaee, A; Ghaneian, M T; Taghavinia, N; Aminian, M K; Hashemian, S J

    2009-03-01

    The photocatalytic degradation of Reactive Blue 19 (RB19) dye has been studied using TiO2 nanofibre as the photocatalyst in aqueous solution under UV irradiation. Titanium dioxide nanofibre was prepared using a templating method with tetraisopropylorthotitanate as a precursor. The experiments were carried out in the presence of the TiO2 nanofibre, and the effects of pH and electron acceptors on the degradation process were investigated. In order to observe the quality of the aqueous solution, chemical oxygen demand (COD) measurements were also carried out before and after the treatments. The photocatalytic decomposition of RB19 was most efficient in acidic solution. With the addition of hydrogen peroxide and potassium persulphate, as electron acceptors, into illuminated TiO2 nanofibre suspensions, a synergistic effect was observed leading to an enhancement of the decolorization. From experimental results, under the condition of 1 g TiO2 nanofibre l(-1), pH 3, and UVC light irradiation, decolorization would be complete in two hours. A significant decrease in the COD values was observed, which clearly indicates that the photocatalytic method offers good potential for the removal of RB19 from aqueous solution. The kinetic of photocatalytic removal of RB19 followed the Langmuir-Hinshelwood model. These results suggest that TiO2 nanofibres with UV photocatalysis can be envisaged as a method for the treatment of coloured wastewaters, in particular in textile industries. PMID:19438055

  1. Estimating pesticide sampling rates by the polar organic chemical integrative sampler (POCIS) in the presence of natural organic matter and varying hydrodynamic conditions

    USGS Publications Warehouse

    Charlestra, Lucner; Amirbahman, Aria; Courtemanch, David L.; Alvarez, David A.; Patterson, Howard

    2012-01-01

    The polar organic chemical integrative sampler (POCIS) was calibrated to monitor pesticides in water under controlled laboratory conditions. The effect of natural organic matter (NOM) on the sampling rates (Rs) was evaluated in microcosms containing -1 of total organic carbon (TOC). The effect of hydrodynamics was studied by comparing Rs values measured in stirred (SBE) and quiescent (QBE) batch experiments and a flow-through system (FTS). The level of NOM in the water used in these experiments had no effect on the magnitude of the pesticide sampling rates (p > 0.05). However, flow velocity and turbulence significantly increased the sampling rates of the pesticides in the FTS and SBE compared to the QBE (p < 0.001). The calibration data generated can be used to derive pesticide concentrations in water from POCIS deployed in stagnant and turbulent environmental systems without correction for NOM.

  2. Influence of preparation conditions in the textural and chemical properties of activated carbons from a novel biomass precursor: the coffee endocarp.

    PubMed

    Nabais, João Valente; Carrott, Peter; Ribeiro Carrott, M M L; Luz, Vânia; Ortiz, Angel L

    2008-10-01

    In this work a novel biomass precursor for the production of activated carbons (AC) was studied. The lignocellulosic material used as precursor is the coffee bean endocarp, which constitutes an industrial residue from the Portuguese coffee industry. Activation by carbon dioxide and potassium hydroxide produces activated carbons with small external areas and pore volumes up to 0.22 and 0.43cm3g(-1), respectively, for CO2 and KOH activation. All the AC's produced are very basic in nature with point of zero charge higher than 8. SEM/EDX studies indicate the presence of K, O, Ca and Si. By FTIR it was possible to identify the formation on the AC's surface of several functional groups, namely phenol, alcohol, quinone, lactone, pyrone and ether as well as SiH groups. The tailoring of the porous and chemical structure of the activated carbons produced is possible by selecting the appropriate production conditions. PMID:18262413

  3. Performance of on-site pilot static granular bed reactor (SGBR) for treating dairy processing wastewater and chemical oxygen demand balance modeling under different operational conditions.

    PubMed

    Oh, Jin Hwan; Park, Jaeyoung; Ellis, Timothy G

    2015-02-01

    The performance and operational stability of a pilot-scale static granular bed reactor (SGBR) for the treatment of dairy processing wastewater were investigated under a wide range of organic and hydraulic loading rates and temperature conditions. The SGBR achieved average chemical oxygen demand (COD), biological oxygen demand (BOD), and total suspended solids (TSS)-removal efficiencies higher than 90% even at high loading rates up to 7.3 kg COD/m(3)/day, with an hydraulic retention time (HRT) of 9 h, and at low temperatures of 11 °C. The average methane yield of 0.26 L CH4/g COD(removed) was possibly affected by a high fraction of particulate COD and operation at low temperatures. The COD mass balance indicated that soluble COD was responsible for most of the methane production. The reactor showed the capacity of the methanogens to maintain their activity and withstand organic and hydraulic shock loads. PMID:25164570

  4. Aqueous Corrosion Behavior of Iron aluminide Intermetallics

    NASA Astrophysics Data System (ADS)

    Sharma, Garima; Singh, P. R.; Sharma, R. K.; Gaonkar, K. B.; Ramanujan, R. V.

    2007-12-01

    Iron aluminide intermetallics based on DO3 ordered structure are being developed for use as structural materials and cladding material for conventional engineering alloys. Aqueous corrosion behavior of iron aluminides has been studied extensively by electrochemical techniques. Studies were carried out on pure Fe (99.9%), Fe-28Al (at.%), Fe-28Al-3Cr (at.%), and AISI SS 304 so as to compare and contrast their behavior in same experimental condition. Polarization behavior under different pH conditions was examined to evaluate their performance in acidic, basic, and neutral solutions. Pitting behavior was also studied in solution containing Cl-1 ions. The stability of the passive film formed was studied by current time transients and potential decay profiles. The presence of 3 at.% Cr in iron aluminides was found to improve the aqueous corrosion resistance and makes it comparable to AISI SS 304.

  5. Role of hydraulic and chemical signals in leaves, stems and roots in the stomatal behaviour of olive trees under water stress and recovery conditions.

    PubMed

    Torres-Ruiz, Jose M; Diaz-Espejo, Antonio; Perez-Martin, Alfonso; Hernandez-Santana, Virginia

    2015-04-01

    The control of plant transpiration by stomata under water stress and recovery conditions is of paramount importance for plant performance and survival. Although both chemical and hydraulic signals emitted within a plant are considered to play a major role in controlling stomatal dynamics, they have rarely been assessed together. The aims of this study were to evaluate (i) the dynamics of chemical and hydraulic signals at leaf, stem and root level, and (ii) their effect on the regulation of stomatal conductance (gs) during water stress and recovery. Measurements of gs, water potential, abscisic acid (ABA) content and loss of hydraulic functioning at leaf, stem and root level were conducted during a water stress and recovery period imposed on 1-year-old olive plants (Olea europaea L.). Results showed a strong hydraulic segmentation in olive plants, with higher hydraulic functioning losses in roots and leaves than in stems. The dynamics of hydraulic conductance of roots and leaves observed as water stress developed could explain both a protection of the hydraulic functionality of larger organs of the plant (i.e., branches, etc.) and a role in the down-regulation of gs. On the other hand, ABA also increased, showing a similar pattern to gs dynamics, and thus its effect on gs in response to water stress cannot be ruled out. However, neither hydraulic nor non-hydraulic factors were able to explain the delay in the full recovery of gs after soil water availability was restored. PMID:25030936

  6. Sorption of tetracycline antibiotics on hyper-crosslinked polystyrene from aqueous and aqueous-organic media

    NASA Astrophysics Data System (ADS)

    Udalova, A. Yu.; Dmitrienko, S. G.; Apyari, V. V.

    2015-06-01

    The sorption of tetracycline, oxytetracycline, chlortetracycline, and doxycycline on hyper-cross-linked polystyrene from aqueous and aqueous-organic solutions is studied under static and dynamic conditions in order to extend the range of the sorbents suitable for sorption isolation and the preconcentration of tetracycline antibiotics. Features of tetracycline sorption depending on the acidity of a solution and the nature and concentration of the compounds are explained. It is shown that hyper-crosslinked polystyrene can be used for the group sorption preconcentration of these compounds.

  7. Multispecies reactive tracer test in an aquifer with spatially variable chemical conditions, Cape Cod, Massachusetts: Dispersive transport of bromide and nickel

    USGS Publications Warehouse

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

    2002-01-01

    Dispersive transport of groundwater solutes was investigated as part of a multispecies reactive tracer test conducted under spatially variable chemical conditions in an unconfined, sewage-contaminated sand and gravel aquifer on Cape Cod, Massachusetts. Transport of the nonreactive tracer bromide (Br) reflected physical and hydrologic processes. Transport of the reactive tracer nickel (Ni) complexed with an organic ligand (NiEDTA) varied in response to pH and other chemical conditions within the aquifer. A loss of about 14% of the Ni mass was calculated from the distribution of tracers through time. This loss is consistent with reversible adsorption of NiEDTA onto the iron and aluminum oxyhydroxide coatings on the aquifer sediments. The Ni consistently lagged behind Br with a calculated retardation coefficient of 1.2. Longitudinal dispersivities reached constant values of 2.2 and 1.1 m for Br and Ni, respectively, by at least 69 m of travel. The smaller dispersivity for Ni possibly was due to nonlinear or spatially variant adsorption of NiEDTA. In the upper, uncontaminated zone of the aquifer, longitudinal dispersion of Ni was greater than that of Br early in the test as a result of reversible adsorption of NiEDTA. In general, transverse dispersivities were much smaller (horizontal: 1.4-1.5 ?? 10-2 m; vertical: 0.5-3.8 ?? 10-3 m) than the longitudinal dispersivities. The Br results are similar to those from a test conducted eight years earlier, suggesting that transport parameters are spatially stationary within the aquifer at the scale of 300 m covered by the spatially overlapping tests. A significant difference between the two tests was the travel distance (69 and 26 m) needed to reach a constant longitudinal dispersivity.

  8. Reduced or diminished stabilization of the telomere G-quadruplex and inhibition of telomerase by small chemical ligands under molecular crowding condition.

    PubMed

    Chen, Zhao; Zheng, Ke-Wei; Hao, Yu-hua; Tan, Zheng

    2009-08-01

    Telomere DNA in human cells shortens during each round of DNA replication. In cancer cells, telomere shortening is compensated by telomerase or the alternative lengthening of telomere (ALT) mechanism to maintain cell division potential. The G-rich strand of telomere DNA can fold into a G-quadruplex structure and disrupt these two processes. Therefore, stabilization of the G-quadruplex by chemical ligands is emerging as a promising anticancer strategy. So far, in vitro studies on such ligands are exclusively carried out in dilute solutions. However, the intracellular environment is highly crowded with biomolecules. How G-quadruplex ligands behave under molecular crowding condition is critical for their in vivo anticancer effect. In this work, we studied several ligands for their ability to stabilize the telomere G-quadruplex and inhibit telomerase under both dilute and crowding conditions. Surprisingly, the ligands became significantly less effective or even lost the ability to stabilize the G-quadruplex and inhibit telomerase under crowding conditions. Our data attributed this consequence to the decreased binding affinity of ligands to the G-quadruplex as a result of reduced water activity and increased viscosity of the medium associated with molecular crowding. This effect is irrelevant to and overweighs the influences from other factors such as the G-quadruplex structure, cation, and ligand species. Our work illustrates a possibility that molecular crowding inside cells may reduce or limit the potency of ligands although they may be effective in dilute solution, thus strongly arguing for the necessity of evaluating ligands under more physiologically relevant conditions and designing drugs with this concern in mind. PMID:19588966

  9. Continuous aqueous tritium monitor

    DOEpatents

    McManus, G.J.; Weesner, F.J.

    1987-10-19

    An apparatus for a selective on-line determination of aqueous tritium concentration is disclosed. A moist air stream of the liquid solution being analyzed is passed through a permeation dryer where the tritium and moisture are selectively removed to a purge air stream. The purge air stream is then analyzed for tritium concentration, humidity, and temperature, which allows computation of liquid tritium concentration. 2 figs.

  10. Phase formation and chemical phase equilibria in aqueous-based systems pertinent to waste-management: calcium oxide-alluminum oxide-borate-water, calcium oxide-lead oxide-phosphate-water and calcium oxide-arsenate-water

    Microsoft Academic Search

    James Vincent Bothe Jr.

    1998-01-01

    This thesis explores three aqueous-based systems that have importance in the area of waste-management: (1) CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, (2) CaO-PbO-Psb2Osb5-Hsb2O and (3) CaO-Assb2Osb5-Hsb2O. More specifically, the objective of this research is to identify various precipitated compounds that can effectively immobilize certain elements that either directly or indirectly have an adverse effect on the environment. In the first quaternary system, CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, boron is

  11. AQUEOUS Pb REDUCTION IN Pb-CONTAMINATED SOILS BY FLORIDA PHOSPHATE ROCKS

    E-print Network

    Ma, Lena

    AQUEOUS Pb REDUCTION IN Pb-CONTAMINATED SOILS BY FLORIDA PHOSPHATE ROCKS LENA Q. MA and GADE N. RAO Florida phosphate rocks (PR) to immobilize aqueous Pb from Pb-contaminated soils. Occidental Chemical PR effectively immobilized Pb from 13 Pb- contaminated soils, but its effectiveness was affected by soil p

  12. Determination of particle size distribution of salt crystals in aqueous slurries. [From reprocessing of fuel elements

    Microsoft Academic Search

    1977-01-01

    A method for determining particle size distribution of water-soluble crystals in aqueous slurries is described. The salt slurries, containing sodium salts of predominantly nitrate, but also nitrite, sulfate, phosphate, aluminates, carbonate, and hydroxide, occur in radioactive, concentrated chemical waste from the reprocessing of nuclear fuel elements. The method involves separating the crystals from the aqueous phase, drying them, and then

  13. Catalytic ozone aqueous decomposition promoted by natural zeolite and volcanic sand

    Microsoft Academic Search

    Héctor Valdés; Víctor J. Farfán; Jorge A. Manoli; Claudio A. Zaror

    2009-01-01

    Chemical oxidation using ozone in the presence of appropriate catalysts offers an attractive option for removing poorly biodegradable pollutants. However, the effect of such catalysts on ozone aqueous decomposition is not well documented. This study compares experimental results on ozone aqueous decomposition promoted by zeolite and volcanic sand. These are two low costs natural materials identified as suitable catalysts for

  14. Analizing Aqueous Imbibition into Shale and the Effects of Optimizing Critical Fracturing Fluid Additives

    E-print Network

    Qureshi, Maha

    2013-09-29

    ANALYZING AQUEOUS SOLUTION IMBIBITON INTO SHALE AND THE EFFECTS OF OPTIMIZING CRITICAL CHEMICAL ADDITIVES An Undergraduate Research Scholars Thesis by MATTHEW WIESE, SAMMAZO PLAMIN and MAHA QURESHI Submitted to Honors and Undergraduate... 21 APPENDIX A 22 1 ABSTRACT Analyzing Aqueous Solution Imbibition into Shale and the Effects...

  15. Analyzing Aqueous Solution Imbibition into Shale and the Effects of Optimizing Critical Fracturing Fluid Additives

    E-print Network

    Plamin, Sammazo Jean-bertrand

    2013-09-29

    ANALYZING AQUEOUS SOLUTION IMBIBITON INTO SHALE AND THE EFFECTS OF OPTIMIZING CRITICAL CHEMICAL ADDITIVES An Undergraduate Research Scholars Thesis by MATTHEW WIESE, SAMMAZO PLAMIN and MAHA QURESHI Submitted to Honors and Undergraduate... 21 APPENDIX A 22 1 ABSTRACT Analyzing Aqueous Solution Imbibition into Shale and the Effects...

  16. Antioxidant Activity of Aqueous Tea Infusions Prepared from Oregano, Thyme and Wild Thyme

    Microsoft Academic Search

    Tea Kuli; Verica Dragovi; Mladen Milo

    Summary Using a multiple-method approach, antioxidant activity of aqueous tea infusions pre- pared from oregano (Origanum vulgare L. ssp. hirtum), thyme (Thymus vulgaris L.) and wild thyme (Thymus serpyllum L.) were tested in relation to their chemical composition. Total phenolic, flavonoid, catechin and anthocyanin content was determined by spectrophoto- metric methods. Oregano aqueous tea infusion had the highest amount of

  17. Ultra-slow water diffusion in aqueous sucrose glasses.

    PubMed

    Zobrist, Bernhard; Soonsin, Vacharaporn; Luo, Bei P; Krieger, Ulrich K; Marcolli, Claudia; Peter, Thomas; Koop, Thomas

    2011-02-28

    We present measurements of water uptake and release by single micrometre-sized aqueous sucrose particles. The experiments were performed in an electrodynamic balance where the particles can be stored contact-free in a temperature and humidity controlled chamber for several days. Aqueous sucrose particles react to a change in ambient humidity by absorbing/desorbing water from the gas phase. This water absorption (desorption) results in an increasing (decreasing) droplet size and a decreasing (increasing) solute concentration. Optical techniques were employed to follow minute changes of the droplet's size, with a sensitivity of 0.2 nm, as a result of changes in temperature or humidity. We exposed several particles either to humidity cycles (between ?2% and 90%) at 291 K or to constant relative humidity and temperature conditions over long periods of time (up to several days) at temperatures ranging from 203 to 291 K. In doing so, a retarded water uptake and release at low relative humidities and/or low temperatures was observed. Under the conditions studied here, the kinetics of this water absorption/desorption process is controlled entirely by liquid-phase diffusion of water molecules. Hence, it is possible to derive the translational diffusion coefficient of water molecules, D(H(2)O,) from these data by simulating the growth or shrinkage of a particle with a liquid-phase diffusion model. Values for D(H(2)O)-values as low as 10(-24) m(2) s(-1) are determined using data at temperatures down to 203 K deep in the glassy state. From the experiment and modelling we can infer strong concentration gradients within a single particle including a glassy skin in the outer shells of the particle. Such glassy skins practically isolate the liquid core of a particle from the surrounding gas phase, resulting in extremely long equilibration times for such particles, caused by the strongly non-linear relationship between concentration and D(H(2)O). We present a new parameterization of D(H(2)O) that facilitates describing the stability of aqueous food and pharmaceutical formulations in the glassy state, the processing of amorphous aerosol particles in spray-drying technology, and the suppression of heterogeneous chemical reactions in glassy atmospheric aerosol particles. PMID:21229162

  18. Effect of process conditions and chemical composition on the microstructure and properties of chemically vapor deposited SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x)

    NASA Technical Reports Server (NTRS)

    Pickering, Michael A.; Taylor, Raymond L.; Goela, Jitendra S.; Desai, Hemant D.

    1992-01-01

    Subatmospheric pressure CVD processes have been developed to produce theoretically dense, highly pure, void-free and large area bulk materials, SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x). These materials are used for optical elements, such as mirrors, lenses and windows, over a wide spectral range from the VUV to the IR. We discuss the effect of CVD process conditions on the microstructure and properties of these materials, with emphasis on optical performance. In addition, we discuss the effect of chemical composition on the properties of the composite material ZnS(x)Se(1-x). We first present a general overview of the bulk CVD process and the relationship between process conditions, such as temperature, pressure, reactant gas concentration and growth rate, and the microstructure, morphology and properties of CVD-grown materials. Then we discuss specific results for CVD-grown SiC, Si, ZnSe, ZnS and ZnS(x)Se(1-x).

  19. Low-temperature chemical bath deposition of crystalline ZnO

    Microsoft Academic Search

    Klaus Jacobs; Denis Balitsky; Pascale Armand; Philippe Papet

    2010-01-01

    ZnO crystals can be grown from alkaline aqueous solution not only by the standard hydrothermal technique at temperatures between 350°C and 400°C, but also by chemical bath deposition (CBD) at temperatures below 100°C. In the presence of ZnO and ScAlMgO4 (SCAM) substrates almost all ZnO deposits on the substrate, with different habits, however. Under optimized conditions even homoepitaxial layers can

  20. Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states

    NASA Astrophysics Data System (ADS)

    Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag; Ceder, Gerbrand

    2012-06-01

    We present an efficient scheme for combining ab initio calculated solid states with experimental aqueous states through a framework of consistent reference energies. Our work enables accurate prediction of phase stability and dissolution in equilibrium with water, which has many important application areas. We formally outline the thermodynamic principles of the scheme and show examples of successful applications of the proposed framework on (1) the evaluation of the water-splitting photocatalyst material Ta3N5 for aqueous stability, (2) the stability of small nanoparticle Pt in acid water, and (3) the prediction of particle morphology and facet stabilization of olivine LiFePO4 as a function of aqueous conditions.

  1. Compatible compositions based on aqueous polyurethane dispersions and sodium alginate.

    PubMed

    Daemi, Hamed; Barikani, Mehdi; Barmar, Mohammad

    2013-01-30

    A series of aqueous polyurethane dispersions were synthesized by the reaction of polytetramethylene glycol and isophorone diisocyanate, extended with dimethylol propionic acid. Their chemical structures were characterized using FTIR, (1)H NMR, and (13)C NMR, and thermal properties were determined by DMTA. Then, a number of aqueous polyurethane dispersions-sodium alginate (PUD/SA) compositions were prepared by addition of sodium alginate solution with different concentrations into the aqueous polyurethane dispersion. Characterization of chemical structure and thermal properties of these blends were performed by FTIR, EDX and DMTA, respectively. The morphology of the alginate in polyurethane matrix was studied by SEM. The hydrophilicity of the prepared samples decreases by increasing the content of sodium alginate in blends. These observations were attributed to the increase of hydrophilicity of the blends as a consequence of addition of hydrophilic carboxylate, hydroxyl and ether functional groups of the alginate to them. PMID:23218325

  2. In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars

    USGS Publications Warehouse

    Squyres, S.W.; Grotzinger, J.P.; Arvidson, R.E.; Bell, J.F., III; Calvin, W.; Christensen, P.R.; Clark, B.C.; Crisp, J.A.; Farrand, W.H.; Herkenhoff, K.E.; Johnson, J.R.; Klingelhofer, G.; Knoll, A.H.; McLennan, S.M.; McSween, H.Y., Jr.; Morris, R.V.; Rice, J.W., Jr.; Rieder, R.; Soderblom, L.A.

    2004-01-01

    Sedimentary rocks at Eagle crater in Meridiani Planum are composed of fine-grained siliciclastic materials derived from weathering of basaltic rocks, sulfate minerals (including magnesium sulfate and jarosite) that constitute several tens of percent of the rock by weight, and hematite. Cross-stratification observed in rock outcrops indicates eolian and aqueous transport. Diagenetic features include hematite-rich concretions and crystal-mold vugs. We interpret the rocks to be a mixture of chemical and siliciclastic sediments with a complex diagenetic history. The environmental conditions that they record include episodic inundation by shallow surface water, evaporation, and desiccation. The geologic record at Meridiani Planum suggests that conditions were suitable for biological activity for a period of time in martian history.

  3. Surface Charge and Hydrophobicity of Endospores of Bacillus anthracis and Related Species in Aqueous Solution

    EPA Science Inventory

    The surface properties of microorganisms play an important role in attachment and detachment in the environment. The change in surface charge can effect coagulation, disinfection, adhesion to surfaces, uptake of chemicals, and environmental transport. In aqueous solution, cell s...

  4. Chemical stability of silicate coloring

    Microsoft Academic Search

    V. M. Ivanova; M. N. Novikova; T. D. Utkina; G. I. Tratnikova; T. I. Shitova; A. M. Zaitsev

    1982-01-01

    The problems of the chemical resistance of colored coatings on high-grade glassware are particularly important from the health and hygiene point of view since such glassware is subject during use to the action of water and aqueous solutions. The aim of our work here was to determine the chemical stability of coloring made from a flux developed at the Gusev

  5. Device for aqueous detection of nitro-aromatic compounds

    DOEpatents

    Reagen, William K. (Stillwater, MN); Schulz, Amber L. (Bremerton, WA); Ingram, Jani C. (Idaho Falls, ID); Lancaster, Gregory D. (Idaho Falls, ID); Grey, Alan E. (Idaho Falls, ID)

    1994-01-01

    This invention relates to a compact and portable detection apparatus for ro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound.

  6. Device for aqueous detection of nitro-aromatic compounds

    DOEpatents

    Reagen, W.K.; Schulz, A.L.; Ingram, J.C.; Lancaster, G.D.; Grey, A.E.

    1994-04-26

    This invention relates to a compact and portable detection apparatus for nitro-aromatic based chemical compounds, such as nitrotoluenes, dinitrotoluenes, and trinitrotoluene (TNT). The apparatus is based upon the use of fiber optics using filtered light. The preferred process of the invention relies upon a reflective chemical sensor and optical and electronic components to monitor a decrease in fluorescence when the nitro-aromatic molecules in aqueous solution combine and react with a fluorescent polycyclic aromatic compound. 4 figures.

  7. Aqueous ferrofluids based on manganese and cobalt ferrites

    Microsoft Academic Search

    Francisco Augusto Tourinho; Raymonde Franck; René Massart

    1990-01-01

    Synthesis of two new aqueous ferrofluids is performed chemically according to Massart's procedure. Manganese and cobalt ferrite magnetic particles are precipitated and treated in order to obtain colloidal sols by creating a charge density on their surface. Such “ionic” ferrofluids can be prepared in an acidic (after a treatment by ferric nitrate) or in an alkaline medium at a concentration

  8. New aqueous waste treatment facility at Rocky Flats

    Microsoft Academic Search

    1978-01-01

    The New Waste Treatment facility at Rocky Flats, Building 374, is designed to remove radioactive and chemical contaminants from aqueous process effluents collected from operations throughout the plant. By utilizing evaporation as well as precipitation, flocculation, and clarification, plant wastes are converted into reusable distilled water, disposable and retrievable solids, and exhaust gases. Total average capacity of the facility is

  9. DEWATERING OF DILUTE AQUEOUS HAZARDOUS WASTES USING REVERSIBLE GEL ABSORPTION

    EPA Science Inventory

    The feasiability of using crosslinked gels in a reversible process for extracting pure water from aqueous waste solutions has been investigated. It has potential for concentrating waste streams that contain hazardous chemicals. Near critical gels have been developed which swell a...

  10. Viscosities of aqueous blended amines

    SciTech Connect

    Hsu, C.H.; Li, M.H. [Chung Yuan Christian Univ., Chung Li (Taiwan, Province of China). Dept. of Chemical Engineering] [Chung Yuan Christian Univ., Chung Li (Taiwan, Province of China). Dept. of Chemical Engineering

    1997-07-01

    Solutions of alkanolamines are an industrially important class of compounds used in the natural gas, oil refineries, petroleum chemical plants, and synthetic ammonia industries for the removal of acidic components like CO{sub 2} and H{sub 2}S from gas streams. The viscosities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA), DEA + 2-amino-2-methyl-1-propanol (AMP), and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) were measured from 30 C to 80 C. A Redlich-Kister equation for the viscosity deviation was applied to represent the viscosity. On the basis of the available viscosity data for five ternary systems, MEA + MDEA + H{sub 2}O, MEA + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. For the viscosity calculation of the systems tested, the overall average absolute percent deviation is about 1.0% for a total of 499 data points.

  11. Densities of aqueous blended amines

    SciTech Connect

    Hsu, C.H.; Li, M.H. [Chung Yuan Christian Univ., Chung Li (Taiwan, Province of China). Dept. of Chemical Engineering] [Chung Yuan Christian Univ., Chung Li (Taiwan, Province of China). Dept. of Chemical Engineering

    1997-05-01

    Solutions of alkanolamines are an industrially important class of compounds used in the natural gas and synthetic ammonia industries and petroleum chemical plants for the removal of CO{sub 2} and H{sub 2}S from gas streams. The densities of aqueous mixtures of diethanolamine (DEA) + N-methyldiethanolamine (MDEA) + water, DEA + 2-amino-2-methyl-1-propanol (AMP) + water, and monoethanolamine (MEA) + 2-piperidineethanol (2-PE) + water were measured from 30 C to 80 C. A Redlich-Kister equation of the excess volume was applied to represent the density. Based on the available density data for five ternary systems: MEA + MDEA + H{sub 2}O, MEA + AMP + H{sub 2}O, DEA + MDEA + H{sub 2}O, DEA + AMP + H{sub 2}O, and MEA + 2-PE + H{sub 2}O, a generalized set of binary parameters were determined. The density calculations show quite satisfactory results. The overall average absolute percent deviation is about 0.04% for a total of 686 data points.

  12. Immobilization of Rose Waste Biomass for Uptake of Pb(II) from Aqueous Solutions

    PubMed Central

    Ansari, Tariq Mahmood; Hanif, Muhammad Asif; Mahmood, Abida; Ijaz, Uzma; Khan, Muhammad Aslam; Nadeem, Raziya; Ali, Muhammad

    2011-01-01

    Rosa centifolia and Rosa gruss an teplitz distillation waste biomass was immobilized using sodium alginate for Pb(II) uptake from aqueous solutions under varied experimental conditions. The maximum Pb(II) adsorption occurred at pH 5. Immobilized rose waste biomasses were modified physically and chemically to enhance Pb(II) removal. The Langmuir sorption isotherm and pseudo-second-order kinetic models fitted well to the adsorption data of Pb(II) by immobilized Rosa centifolia and Rosa gruss an teplitz. The adsorbed metal is recovered by treating immobilized biomass with different chemical reagents (H2SO4, HCl and H3PO4) and maximum Pb(II) recovered when treated with sulphuric acid (95.67%). The presence of cometals Na, Ca(II), Al(III), Cr(III), Cr(VI), and Cu(II), reduced Pb(II) adsorption on Rosa centifolia and Rosa gruss an teplitz waste biomass. It can be concluded from the results of the present study that rose waste can be effectively used for the uptake of Pb(II) from aqueous streams. PMID:21350666

  13. The effect of processing conditions on the structural morphology and physical properties of ZnO and CdS thin films produced via sol–gel synthesis and chemical bath deposition techniques

    Microsoft Academic Search

    Shahzad Salam; Mohammad Islam; Mahboob Alam; Aftab Akram; Mujtaba Ikram; Asif Mahmood; Majid Khan; Mohammad Mujahid

    2011-01-01

    Cadmium sulfide (CdS) and zinc oxide (ZnO) are used in thin film solar cells as buffer layer and transparent conducting oxide, respectively. The effect of annealing conditions on the morphology and physical properties of CdS and ZnO films prepared using chemical bath deposition and sol–gel synthesis techniques, respectively, was investigated. CdS films obtained from the chemical bath deposition (CBD) process

  14. Equilibria in aqueous iodine solutions

    E-print Network

    Burger, Joanne Denise

    1970-01-01

    EQUILIBRIA IN AQUEOUS IODINE SOLUTIONS A Thesis JOANNE DENISE BURGER Submitted to the Graduate College of Texas AkN University in partial fulfillment of the requirement for the degree of NASTER OP SCIENCE December i 9 "/0 Najor Sub...)ect: Chemistry EQUILIBRIA IN AQUEOUS IODINE SOLUTIONS A Thesis by JOANNE DENISE BURGER Approved as to style and content by: i I I / Chairman o ommittee ( Yiember Head of Department Nember December 1970 ABSTRACT Equilibria in Aqueous Iodine Solutions...

  15. Equilibria in aqueous iodine solutions 

    E-print Network

    Burger, Joanne Denise

    1970-01-01

    EQUILIBRIA IN AQUEOUS IODINE SOLUTIONS A Thesis JOANNE DENISE BURGER Submitted to the Graduate College of Texas AkN University in partial fulfillment of the requirement for the degree of NASTER OP SCIENCE December i 9 "/0 Najor Sub...)ect: Chemistry EQUILIBRIA IN AQUEOUS IODINE SOLUTIONS A Thesis by JOANNE DENISE BURGER Approved as to style and content by: i I I / Chairman o ommittee ( Yiember Head of Department Nember December 1970 ABSTRACT Equilibria in Aqueous Iodine Solutions...

  16. Identification of adducts between an odoriferous volatile thiol and oxidized grape phenolic compounds: kinetic study of adduct formation under chemical and enzymatic oxidation conditions.

    PubMed

    Nikolantonaki, Maria; Jourdes, Michael; Shinoda, Kentaro; Teissedre, Pierre-Louis; Quideau, Stéphane; Darriet, Philippe

    2012-03-14

    HPLC-MS and (1)H, (13)C, and 2D NMR analyses were used to identify new addition products between 3-sulfanylhexan-1-ol (3SH) and o-quinones derived from (+)-catechin, (-)-epicatechin, and caftaric acid. The kinetics of formation of these adducts were monitored in a wine model solution and in a must-like medium by HPLC-UV-MS with the aim of understanding the chemical mechanism involved in reactions between volatile thiols and o-quinones. One o-quinone-caftaric acid/3SH adduct, three o-quinone-(+)-catechin/3SH adducts, and three o-quinone-(-)-epicatechin/3SH adducts were characterized. Caftaric acid was oxidized faster than (-)-epicatechin and (+)-catechin when these phenolic compounds were incubated in a one-component mixture with polyphenoloxidase (PPO) in the presence of 3SH. Consequently, o-quinone-caftaric acid formed adducts with 3SH more rapidly than o-quinone-(+)-catechin and o-quinone-(-)-epicatechin in the absence of other nucleophilic species. Furthermore, o-quinone-(-)-epicatechin reacted faster than o-quinone-(+)-catechin with 3SH. Sulfur dioxide decreased the yield of adduct formation to a significant extent. Under chemical oxidation conditions, the rates and yields of adduct formation were lower than those observed in the presence of PPO, and o-quinone-caftaric acid was slightly less reactive with 3SH, compared to oxidized flavan-3-ols. The identification of o-quinone-caftaric acid/3SH and o-quinone-(+)-catechin/3SH adducts in a must matrix suggests that the proposed reaction mechanism is responsible for 3SH loss in dry wines during their vinification and aging process. PMID:22324817

  17. Bacterial Acclimation Inside an Aqueous Battery

    PubMed Central

    Dong, Dexian; Chen, Baoling; Chen, P.

    2015-01-01

    Specific environmental stresses may lead to induced genomic instability in bacteria, generating beneficial mutants and potentially accelerating the breeding of industrial microorganisms. The environmental stresses inside the aqueous battery may be derived from such conditions as ion shuttle, pH gradient, free radical reaction and electric field. In most industrial and medical applications, electric fields and direct currents are used to kill bacteria and yeast. However, the present study focused on increasing bacterial survival inside an operating battery. Using a bacterial acclimation strategy, both Escherichia coli and Bacillus subtilis were acclimated for 10 battery operation cycles and survived in the battery for over 3 days. The acclimated bacteria changed in cell shape, growth rate and colony color. Further analysis indicated that electrolyte concentration could be one of the major factors determining bacterial survival inside an aqueous battery. The acclimation process significantly improved the viability of both bacteria E. coli and B. subtilis. The viability of acclimated strains was not affected under battery cycle conditions of 0.18-0.80 mA cm-2 and 1.4-2.1 V. Bacterial addition within 1.0×1010 cells mL-1 did not significantly affect battery performance. Because the environmental stress inside the aqueous battery is specific, the use of this battery acclimation strategy may be of great potential for the breeding of industrial microorganisms. PMID:26070088

  18. Development of the Conceptual Models for Chemical Conditions and Hydrology Used in the 1996 Performance Assessment for the Waste Isolation Pilot Plant

    SciTech Connect

    LARSON, KURT W.

    2000-05-24

    The Waste Isolation Pilot Plant (WIPP) is a US Department of Energy (DOE) facility for the permanent disposal of defense-related transuranic (TRU) waste. US Environmental Protection Agency (EPA) regulations specify that the DOE must demonstrate on a sound basis that the WIPP disposal system will effectively contain long-lived alpha-emitting radionuclides within its boundaries for 10,000 years following closure. In 1996, the DOE submitted the ''40 CFR Part 191 Compliance Certification Application for the Waste Isolation Pilot Plant'' (CCA) to the EPA. The CCA proposed that the WIPP site complies with EPA's regulatory requirements. Contained within the CCA are descriptions of the scientific research conducted to characterize the properties of the WIPP site and the probabilistic performance assessment (PA) conducted to predict the containment properties of the WIPP disposal system. In May 1998, the EPA certified that the TRU waste disposal at the WIPP complies with its regulations. Waste disposal operations at WIPP commenced on March 28, 1999. The 1996 WIPP PA model of the disposal system included conceptual and mathematical representations of key hydrologic and geochemical processes. These key processes were identified over a 22-year period involving data collection, data interpretation, computer models, and sensitivity studies to evaluate the importance of uncertainty and of processes that were difficult to evaluate by other means. Key developments in the area of geochemistry were the evaluation of gas generation mechanisms in the repository; development of a model of chemical conditions in the repository and actinide concentrations in brine; selecting MgO backfill and demonstrating its effects experimentally; and determining the chemical retardation capability of the Culebra. Key developments in the area of hydrology were evacuating the potential for groundwater to dissolve the Salado Formation (the repository host formation), development of a regional model for hydrologic conditions, development of a stochastic, probabilistic representation of hydraulic properties in the Culebra Member of the Rustler Formation; characterization of physical transport in the Culebra, and the evaluation of brine and gas flow in the Salado. Additional confidence in the conceptual models used in the 1996 WIPP PA was gained through independent peer review in many stages of their development.

  19. Modeling of thermo-chemical properties of the sub-solidus MgO-FeO binary, under Earth's lower mantle conditions

    NASA Astrophysics Data System (ADS)

    Sciascia, Luciana; Merli, Marcello; Pavese, Alessandro; Diella, Valeria

    2015-04-01

    The stability field of the Mg-wüstite solid solution, (Mg,Fe)O, under high PT conditions, has been investigated by performing quantum mechanical calculations combined with statistical thermodynamics. The interest in this field comes from the consideration that the Mg-wüstite is the second most abundant phase in the Earth's lower mantle. A thoughtful understanding of the thermodynamic stability of this phase under deep mantle conditions is thus crucial for developing accurate models of the Earth's interior and the importance of drawing a complete picture of the stability fields of the Mg-wustite solid solution, especially at high pressure/temperature regimes, is straightforward. The experimental research in this field can be conveniently integrated by computational methods that allow not only to explore the extreme conditions that cannot be realized in a laboratory but also to express the mixing energies of the system as a function of the different factors affecting it. In the light of the above considerations, the present work has been undertaken where the thermo-chemical properties of the (Mg,Fe)O solid solution, over a wide PT range, have been modelled. Calculations have been performed by means of quantum mechanical and semi-empirical techniques by applying different external hydrostatic pressures in the range 0-140 GPa. The effect of the different spin configurations have been taken into account by exploring both the diamagnetic (low spin, S=0, NM) and antiferromagnetic (high spin, S=2, AFM) cases. The obtained energies have been then employed for the parameterization of the excess energy by the interaction parameters determined via Cluster Expansion (CE) method. The critical values of Pressure and Temperature beyond which the AFM-model, which is energetically more convenient in the low pressure regime, ends up promoting decomposition into MgO-FeO end members, have been determined for each investigated composition over the MgO-FeO binary. The proposed approach allowed us to achieve a comprehensive picture of the principles underlying the stability of (Mg,Fe)O-solid solution, as a function of those aspects that primarily affect its reactivity, i.e. pressure, temperature, composition and iron spin-configuration, and to determine, therefore, those conditions which favors the stability of the solid solution.

  20. Salt Effect Model for Aqueous Solubility of TBP in a 5 to 100% TBP\\/n-Dodecane-Nitric Acid-Water Biphasic System at 298.2 K

    Microsoft Academic Search

    Shekhar Kumar; Sudhir Babu Koganti

    2000-01-01

    The solubilities of nonelectrolytes in aqueous electrolyte solutions have traditionally been modeled by using the Setschenow equation for salt effect. The aqueous solubility of tri-n-butyl phosphate (TBP) during operating conditions of the Purex process is an important parameter for safety considerations. Use of the Setschenow equation for aqueous solubility of TBP under limited conditions has been reported in the literature.