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Sample records for aqueous chemical conditions

  1. Chemical reactions at aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Vecitis, Chad David

    2009-12-01

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2002-01-01

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

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

    PubMed

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

    2015-05-19

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

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

    EPA Science Inventory

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

  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-Base reactions · Oxidation-Reduction reactions · Reversible reactions Classes of Chemical Reactions Water (H2O;Classes of Chemical Reactions The solubility of ionic compounds: dissociation O H H + NaCl Cl- Cl- Cl- Na

  8. Chemical Equilibrium Composition of Aqueous Systems

    Energy Science and Technology Software Center (ESTSC)

    1996-12-30

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

  9. 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...

  10. Chemical Models for Aqueous Biodynamical Processes

    E-print Network

    Mata-Segreda, Julio F.

    1975-05-01

    . K. Wynne-Jones and H. Eyring, "The Absolute Rate of Reactions in Condensed Phases ," J. Chem. Phi¡s. > j3, 492 (1935). (7) K. J. Laidler, "Chemical Kinetics," 2nd ed. , McGraw-Hill Book Company, 1965, a) p. 75; b) pp. 110-112. (8) S. H. Maron... and C. F. Prutton, "Principles of Physical Chemis try." 4th ed. , The McMillan Company, 1970, pp. 767-769. (9) M. M. Kreevoy, in S. L. Friess, E. S. Lewis, and A. Weissberger, eds. , "Technique of Organic Chemistry," 8, part III, 1361 (1963). (10) D...

  11. Physical-chemical conditions of ore deposition

    USGS Publications Warehouse

    Barton, P.B., Jr.

    1981-01-01

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

  12. Thermodynamics of Water and Aqueous Solutions under Mantle Conditions

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  13. Establishing and maintaining specific pathogen free (SPF) conditions in aqueous solutions using ozone

    NASA Astrophysics Data System (ADS)

    Vestergård, B.

    1994-11-01

    The paper discusses the use of ozone in space applications for the elimination of pathogens, and the enhancement of the oxidation potential of ozone using hydrogen peroxide and ultraviolet radiation. These combinations will be possible to set up in space conditions. The sterilizing effect versus free radical generation is an important equilibrium to establish when specific pathogen free conditions are wanted in aqueous solutions containing organic matter. In situ sterilization of plant roots in hydroponic systems, as well as the oxidation of root exudates, will be discussed. The paper will contain examples of the chemical interaction of ozone with some of the other compounds found in hydroponic systems.

  14. Establishing and maintaining specific pathogen free (SPF) conditions in aqueous solutions using ozone.

    PubMed

    Vestergard, B

    1994-11-01

    The paper discusses the use of ozone in space applications for the elimination of pathogens, and the enhancement of the oxidation potential of ozone using hydrogen peroxide and ultraviolet radiation. These combinations will be possible to set up in space conditions. The sterilizing effect versus free radical generation is an important equilibrium to establish when specific pathogen free conditions are wanted in aqueous solutions containing organic matter. In situ sterilization of plant roots in hydroponic systems, as well as the oxidation of root exudates, will be discussed. The paper will contain examples of the chemical interaction of ozone with some of the other compounds found in hydroponic systems. PMID:11540210

  15. INTEK Decon Solutions: An Aqueous Based Chemical Decontamination Process

    SciTech Connect

    Durante, R.W.

    2006-07-01

    The planned construction of new nuclear power plants and fuel storage facilities and the decommissioning of nuclear weapons facilities have created a need for safer, more efficient decontamination processes. Chelant based chemical compounds present an attractive alternate to traditional means of decontamination such as acid cleaning, sandblasting, and other physical methods. There is now available a family of polydentate chelant chemical compounds, designated INTEK Decon Solutions, that is aqueous based and operates at a neutral pH that can be sprayed on and washed off with water. A major advantage of this process is that it minimizes waste volume and makes the waste easier to handle. This process has been demonstrated to produce very effective decontamination in a wide variety of situations. This paper will review the procedures used for three specific applications in projects undertaken for the DOE and industry. (authors)

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

    EPA Science Inventory

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

  17. Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed systems

    E-print Network

    Rhoads, James

    Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed, Composition Satellites, Composition Meteorites a b s t r a c t Solids of nearly solar composition have interacted with aqueous fluids on carbonaceous asteroids, icy moons, and trans-neptunian objects

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

    PubMed

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

    2015-02-01

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

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

    EPA Science Inventory

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

  20. '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...

  1. Evolution of chemical gardens in aqueous solutions of polymers

    NASA Astrophysics Data System (ADS)

    Bormashenko, Edward; Bormashenko, Yelena; Stanevsky, Oleg; Pogreb, Roman

    2006-01-01

    We report the formation of chemical gardens grown in water solutions of polymers. Evolution of the chemical garden depends dramatically on the polymer molecular weight. Solution/air interface plays an important role in the process. Inverse, down-directed growth of the chemical garden in the polymer solutions, based on polymers of high molecular weight, was observed.

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

    E-print Network

    Guo, Zhixiong "James"

    Nanofiltration and sensing of picomolar chemical residues in aqueous solution using an optical.1088/0957-4484/23/6/065502 Nanofiltration and sensing of picomolar chemical residues in aqueous solution using an optical porous resonator for integrated functions of nanofiltration and sensing of small biomolecules and chemical analytes in extremely

  3. 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

  4. Chemical and photochemical properties of chloroharmine derivatives in aqueous solutions.

    PubMed

    Rasse-Suriani, Federico A O; Paula Denofrio, M; Yañuk, Juan G; Micaela Gonzalez, M; Wolcan, Ezequiel; Seifermann, Marco; Erra-Balsells, Rosa; Cabrerizo, Franco M

    2015-12-23

    Thermal and photochemical stability (?R), room temperature UV-vis absorption and fluorescence spectra, fluorescence quantum yields (?F) and lifetimes (?F), quantum yields of hydrogen peroxide (?H2O2) and singlet oxygen (??) production, and triplet lifetimes (?T) have been obtained for the neutral and protonated forms of 6-chloroharmine, 8-chloroharmine and 6,8-dichloroharmine, in aqueous media. When it was possible, the effect of pH and oxygen concentration was evaluated. The nature of electronic transitions of protonated and neutral species of the three investigated chloroharmines was established using Time-Dependent Density Functional Theory (TD-DFT) calculations. The impact of all the foregoing observations on the biological role of the studied compounds is discussed. PMID:26648161

  5. 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...

  6. 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

  7. 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.

  8. 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).

  9. Tetrahedrally bonded carbonates and aqueous carbonate anions under extreme conditions

    NASA Astrophysics Data System (ADS)

    Pan, Ding; Galli, Giulia; Deep Carbon Observatory Collaboration

    The carbonate ion, CO32- , has a trigonal planar structure composed of carbon bonded with three oxygen atoms. The existence of tetrahedrally bonded carbonate units, CO4, analogous to SiO4 in silicates, has long been under debate. Using a combination of first-principles calculations and in situ infrared spectroscopy measurements, we provided definitive evidence that in magnesite, at pressures above 80 GPa, sp2 bonded CO3 trigonal groups transforms into sp3 bonded CO4 tetrahedral units. These units were found to be asymmetric, with two longer and two shorter C-O bonds. In addition, using first principles molecular dynamics we investigated carbonate anions in water at high temperature and pressure, corresponding to Earth's upper mantle conditions. We found significant quantities of bicarbonate ions dissolved in the liquid. The relevance of our simulation results for geophysical models of hydrous carbonates in the Earth will be discussed. Supported by the Sloan Foundation through the Deep Carbon Observatory.

  10. Selection among aqueous and off-gas treatment technologies for synthetic organic chemicals

    SciTech Connect

    Dvorak, B.I.; Herbeck, C.J.; Meurer, C.P.; Lawler, D.F.; Speitel, G.E. Jr.

    1996-07-01

    A methodology for selecting the least-cost treatment technology for waters contaminated by organic wastes was developed using performance and cost models. This methodology simplifies the selection of the least expensive treatment process(es) for a given set of conditions. Two aqueous-phase treatment options were considered: air stripping and liquid-phase adsorption (granular activated carbon). When the off-gases from air stripping must be treated, four off-gas treatment options were considered: gas-phase adsorption (with both on- and off-site regeneration of the granular activated carbon), thermal incineration, and catalytic oxidation. Methodologies were developed for rapidly selecting the least-cost off-gas treatment option [for volatile organic compound (VOC) sources such as an air stripping tower], for selecting the least-cost overall (liquid and gas phase treatment) system, and for selecting the least-cost overall system for a multicomponent mixture. The comparison methodology is based on physical parameters of the target chemical: Henry`s constant and the solute distribution parameter. The results are a set of diagrams and heuristics for rapid identification of cases for which one treatment option is significantly less expensive than the other.

  11. 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##

  12. Regioselective Fluorination of Imidazo[1,2-a]pyridines with Selectfluor in Aqueous Condition.

    PubMed

    Liu, Ping; Gao, Yongyuan; Gu, Weijin; Shen, Ziyan; Sun, Peipei

    2015-11-20

    A regioselective synthesis of 3-fluorinated imidazo[1,2-a]pyridines using 1-chloromethyl-4-fluoro-1,4-diazoniabi cyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) as the fluorinating reagent in aqueous condition is described. In the presence of DMAP, the reaction mainly gave monofluorinated product via electrophilic fluorinated process in moderate to good yields. PMID:26523829

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

    DOEpatents

    Giese, R.W.; Wang, P.

    1996-04-30

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

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

    PubMed

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

    2015-04-14

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

    Sui, Xiaonan; Bary, Solène; Zhou, Weibiao

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

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

  18. 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.

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

    SciTech Connect

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

    1995-01-01

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

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

    PubMed Central

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

    2010-01-01

    The chemical history of dust particles in the atmosphere is crucial for assessing their impact on both the Earth’s climate and ecosystem. So far, a number of studies have shown that, in the vicinity of strong anthropogenic emission sources, Ca-rich dust particles can be converted into aqueous droplets mainly by the reaction with gaseous HNO3 to form Ca(NO3)2. Here we show that other similar processes have the potential to be activated under typical remote marine atmospheric conditions. Based on field measurements at several sites in East Asia and thermodynamic predictions, we examined the possibility for the formation of two highly soluble calcium salts, Ca(NO3)2 and CaCl2, which can deliquesce at low relative humidity. According to the results, the conversion of insoluble CaCO3 to Ca(NO3)2 tends to be dominated over urban and industrialized areas of the Asian continent, where the concentrations of HNO3 exceed those of HCl ([HNO3/HCl] >  ? 1). In this regime, CaCl2 is hardly detected from dust particles. However, the generation of CaCl2 becomes detectable around the Japan Islands, where the concentrations of HCl are much higher than those of HNO3 ([HNO3/HCl] <  ? 0.3). We suggest that elevated concentrations of HCl in the remote marine boundary layer are sufficient to modify Ca-rich particles in dust storms and can play a more important role in forming a deliquescent layer on the particle surfaces as they are transported toward remote ocean regions. PMID:20921372

  1. 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...

  2. FACILITATED CHEMICAL SYNTHESIS UNDER ALTERNATE REACTION CONDITIONS

    EPA Science Inventory

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

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

    PubMed

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

    2012-07-15

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

  4. Chemical relaxation and equilibrium studies of association in aqueous solutions of bolaform detergents. Part 3

    SciTech Connect

    Zana, R.; Yiv, S.; Kale, K.M.

    1980-10-01

    Micelle formation in aqueous solutions of docasane-1,22-bis(trimethylammonium bromide) (C22ME6) has been investigated by means of conductivity, EMF (concentration cell and bromide ion and detergent ion specific electrodes), density, light scattering, fluorescence, and chemical relaxation (p-jump, t-jump, shock tube, ultrasonic absorption). The CMC, micelle ionization degree, micelle ionization degree, micelle aggregation number, and volume change upon micellization were calculated. The slope of the plot log CMC vs. number m of carbon atoms in the alkyl chain of bolaforms of the CMME6 type as well as several other results reveal that these bolaforms behave like detergents with 2 charged groups on the first carbon of the alkyl chain. The conclusion is that the bolaform alkyl chain may be somewhat folded both in aqueous solution and in the micellized state. 25 references.

  5. 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.

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

    PubMed

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

    2014-04-15

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

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

    DOEpatents

    Yates, Stephen Frederic (1539 S. Kennicott Dr., Arlington Heights, IL 60005); DeFilippi, Irene (208 E. Edgewood La., Palatine, IL 60067); Gaita, Romulus (6646 Davis Rd., Morton Grove, IL 60053); Clearfield, Abraham (Department of Chemistry, Texas A& M University, College Station, TX 77843); Bortun, Lyudmila (Department of Chemistry, Texas A& M University, College Station, TX 77843); Bortun, Anatoly (Department of Chemistry, Texas A& M University, College Station, TX 77843)

    2000-09-05

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

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

    NASA Technical Reports Server (NTRS)

    Catling, David C.

    2004-01-01

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

  9. 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

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

    SciTech Connect

    Yaman, S.; Kuecuekbayrak, S.

    1999-11-01

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

  11. Aqueous synthesis of CdTe/CdS/ZnS quantum dots and their optical and chemical properties.

    PubMed

    Li, Zhong; Dong, Chaoqing; Tang, Lichuan; Zhu, Xin; Chen, Hongjin; Ren, Jicun

    2011-01-01

    In this paper, we described a strategy for synthesis of thiol-coated CdTe/CdS/ZnS (core-shell-shell) quantum dots (QDs) via aqueous synthesis approach. The synthesis conditions were systematically optimized, which included the size of CdTe core, the refluxing time and the number of monolayers and the ligands, and then the chemical and optical properties of the as-prepared products were investigated. We found that the mercaptopropionic acid (MPA)-coated CdTe/CdS/ZnS QDs presented highly photoluminescent quantum yields (PL QYs), good photostability and chemical stability, good salt tolerance and pH tolerance and favorable biocompatibility. The characterization of high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD) and fluorescence correlation spectroscopy (FCS) showed that the CdTe/CdS/ZnS QDs had good monodispersity and crystal structure. The fluorescence life time spectra demonstrated that CdTe/CdS/ZnS QDs had a longer lifetime in contrast to fluorescent dyes and CdTe QDs. Furthermore, the MPA-stabilized CdTe/CdS/ZnS QDs were applied for the imaging of cells. Compared with current synthesis methods, our synthesis approach was reproducible and simple, and the reaction conditions were mild. More importantly, our method was cost-effective, and was very suitable for large-scale synthesis of CdTe/CdS/ZnS QDs for future applications. PMID:20878652

  12. 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.

  13. Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed systems

    NASA Astrophysics Data System (ADS)

    Zolotov, Mikhail Yu.

    2012-08-01

    Solids of nearly solar composition have interacted with aqueous fluids on carbonaceous asteroids, icy moons, and trans-neptunian objects. These processes altered mineralogy of accreted materials together with compositions of aqueous and gaseous phases. We evaluated chemistry of aqueous solutions coexisted with CI-type chondritic solids through calculations of chemical equilibria in closed water-rock-gas systems at different compositions of initial fluids, water/rock mass ratios (0.1-1000), temperatures (<350 °C), and pressures (<2 kbars). The calculations show that fluid compositions are mainly affected by solubilities of solids, the speciation of chlorine in initial water-rock mixtures, and the occurrence of Na-bearing secondary minerals such as saponite. The major species in modeled alkaline solutions are Na+, Cl-, CO32-,HCO3-, K+, OH-, H2, and CO2. Aqueous species of Mg, Fe, Ca, Mn, Al, Ni, Cr, S, and P are not abundant in these fluids owing to low solubility of corresponding solids. Typical NaCl type alkaline fluids coexist with saponite-bearing mineralogy that usually present in aqueously altered chondrites. A common occurrence of these fluids is consistent with the composition of grains emitted from Enceladus. Na-rich fluids with abundant CO32-,HCO3-, and OH- anions coexist with secondary mineralogy depleted in Na. The Na2CO3 and NaHCO3 type fluids could form via accretion of cometary ices. NaOH type fluids form in reduced environments and may locally occur on parent bodies of CR carbonaceous chondrites. Supposed melting of accreted HCl-bearing ices leads to early acidic fluids enriched in Mg, Fe and other metals, consistent with signs of low-pH alteration in chondrites. Neutralization of these solutions leads to alkaline Na-rich fluids. Sulfate species have negligible concentrations in closed systems, which remain reduced, especially at elevated pressures created by forming H2 gas. Hydrogen, CO2, and H2O dominate in the gaseous phase, though the abundance of methane cannot be fairly estimated.

  14. 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...

  15. Characterizing photochemical transformation of aqueous nC60 under environmentally relevant conditions.

    PubMed

    Hwang, Yu Sik; Li, Qilin

    2010-04-15

    Engineered nanomaterials may undergo transformation upon interactions with various environmental factors. In this study, photochemical transformation of aqueous nC60 was investigated under UVA irradiation. nC60 underwent photochemical transformation in the presence of dissolved O2, resulting in surface oxygenation and hydroxylation as demonstrated by XPS and ATR-FTIR analyses. The reaction followed a pseudo-first order rate law with the apparent reaction rate constant of 2.2 x 10(-2) h(-1). However, the core of the nanoparticles remained intact over 21 days of irradiation. Although no mineralization or dissolution of nC60 was observed, experiments using fullerol as a reference fullerene derivative suggested likely dissolution and partial mineralization of nC60 under long-term UVA exposure. Aquatic humic acid reduced nC60 transformation kinetics presumably due to scavenging of reactive oxygen species. Results from this study imply that photochemical transformation is an important factor controlling nC60 physical and chemical properties as well as its fate and transport in the natural aqueous environment. In addition, changes in nC60 surface chemistry drastically reduced C60 extraction efficiency by toluene, suggesting that the existing analytical method for C60 may not be applicable to environmental samples. PMID:20337472

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

    SciTech Connect

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

    1999-05-01

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

  17. Equilibrium conditions for carbon dioxide hydrate formation in aqueous electrolyte solutions

    SciTech Connect

    Dholabhai, P.D.; Kalogerakis, N.; Bishnoi, P.R. . Dept. of Chemical and Petroleum Engineering)

    1993-10-01

    Information on the hydrate-forming conditions for natural gas components and their mixtures is vital to the oil and gas industry. Formation of hydrates in gas pipelines and processing equipment could lead to catastrophic consequences. This information is also essential to the industry for the exploitation of the huge naturally occurring gas reserves in the form of hydrates and for drilling through the hydrate zones. Three-phase equilibrium conditions (aqueous solution + vapor + hydrate) of carbon dioxide in electrolyte solutions containing NaCl, KCl, CaCl[sub 2], and their binary mixtures and in a synthetic sea water were experimentally obtained in the temperature range of 259--281 K and in the pressure range of 0.9--4.1 MPa using a pressure search'' method. The ionic strengths of the solutions ranged from 0.41 to 6.74 m.

  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. 49 CFR 219.11 - General conditions for chemical tests.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 4 2012-10-01 2012-10-01 false General conditions for chemical tests. 219.11 Section 219.11 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to...

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

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 4 2013-10-01 2013-10-01 false General conditions for chemical tests. 219.11 Section 219.11 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to...

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

    Code of Federal Regulations, 2011 CFR

    2011-10-01

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

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

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 4 2014-10-01 2014-10-01 false General conditions for chemical tests. 219.11 Section 219.11 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD... for chemical tests. (a) Any employee who performs covered service for a railroad is deemed to...

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

    Code of Federal Regulations, 2010 CFR

    2010-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

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

    PubMed

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

    2015-01-01

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

  7. 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.

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

    NASA Astrophysics Data System (ADS)

    Grgi?, Irena; Kitanovski, Zoran; Krofli?, Ana; ?usak, Alen

    2014-05-01

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

  9. 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.

  10. pH effect on the morphology of ZnO nanostructures grown with aqueous chemical growth

    E-print Network

    pH effect on the morphology of ZnO nanostructures grown with aqueous chemical growth D. Vernardou a Available online 1 April 2007 Abstract ZnO nanostructures were grown for various pH values on Corning 7059 hexahydrate) and C6H12N4 (HMTA; hexamethylenetetramine). It was indicated that the increasing of the pH

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

    EPA Science Inventory

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

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

    SciTech Connect

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

    2007-07-01

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

  13. An in situ ATR-IR spectroscopy study of aluminas under aqueous phase reforming conditions.

    PubMed

    Koichumanova, K; Sai Sankar Gupta, K B; Lefferts, L; Mojet, B L; Seshan, K

    2015-10-01

    High temperature/pressure in situ Attenuated Total Reflection Infrared (ATR-IR) spectroscopy was used to investigate the phase transformation of support ?-Al2O3 into boehmite (AlO(OH)) under the hydrothermal conditions of aqueous phase reforming (APR). Activation energy barriers of boehmite formation in hot compressed water at temperatures between 150 and 180 °C were calculated to be 15.9 ± 4.8 kJ mol(-1) for ?-Al2O3 and 43.2 ± 4.3 kJ mol(-1) for Pt/?-Al2O3. The influence of Pt particles is suggested to slow down the phase transformation by selective blockage of the surface nucleation sites. The presence of ethylene glycol has also an inhibiting effect on the transformation due to the carbon deposits formed on the oxide surface. Post-mortem analysis using Raman spectroscopy, (1)H and (27)Al MAS NMR confirms the formation of boehmite. PMID:26305344

  14. Interactions between carbon nanotubes and sulfonamide antibiotics in aqueous solutions under various physicochemical conditions.

    PubMed

    Tian, Yuan; Gao, Bin; Chen, Hao; Wang, Yu; Li, Hui

    2013-01-01

    Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have attracted much attention recently because of their potential ecological risks. This work systematically investigated the adsorption characteristics of SMX and SPY on carbon nanotubes (CNTs), a newly introduced nano-adsorbent, under various physicochemical conditions. Laboratory batch adsorption experiments and mathematical models were used to determine the adsorption kinetics and isotherms of the two antibiotics to the CNTs. We found that SMX and SPY had very fast adsorption kinetics to the CNTs, which could be simulated with both the pseudo-second-order and the intraparticle diffusion models. These results suggest that the adsorption of the antibiotics to the CNTs were controlled by surface adsorption and intraparticle diffusion processes. Isotherm studies showed that sonication-aided dispersion slightly increased the adsorption of the antibiotics to the CNTs probably because the dispersion process might increase CNT surface area. When solution pH increased from 3.0 to 9.0, the Langmuir maximum sorption capacities of the antibiotics to the CNTs decreased from 98.0 to 18.6 mg/g (SMX) and from 108.6 to 83.2 mg/g (SPY), indicating pH is a controlling factor of the removal of the two antibiotics in aqueous solutions. We also found that the Langmuir adsorption capacity of the CNTs decreased slightly for both SMX and SPY when more adsorbents were in the solution. The findings from this study suggest that CNTs can be used as a high efficiency adsorbent to removal antibiotics from aqueous solution under various conditions. PMID:23573934

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

    EPA Science Inventory

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

  16. 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...

  17. 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

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

    PubMed Central

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

    2015-01-01

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

  19. Resistance to chemical disinfection under conditions of microgravity

    NASA Astrophysics Data System (ADS)

    Marchin, George L.

    1998-01-01

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

  20. Oxidative degradation of organic pollutants in aqueous solution using zero valent copper under aerobic atmosphere condition.

    PubMed

    Wen, Gang; Wang, Sheng-Jun; Ma, Jun; Huang, Ting-Lin; Liu, Zheng-Qian; Zhao, Lei; Xu, Jin-Lan

    2014-06-30

    Oxidative degradation of organic pollutants and its mechanism were investigated in aqueous solution using zero valent copper (ZVC) under aerobic atmosphere condition. Diethyl phthalate (DEP) was completely oxidized after 120 min reaction by ZVC at initial pH 2.5 open to the air. DEP degradation followed the pseudo-first-order kinetics after the lag period, and the degradation rate of DEP increased gradually with the increase of ZVC dosage, and the decrease of initial pH from 5.8 to 2.0. ZVC required a shorter induction time and exhibited persistent oxidation capacity compared to that of zero valent iron and zero valent aluminium. The mechanism investigation showed that remarkable amount of Cu(+)/Cu(2+) and H2O2 were formed in ZVC acidic system, which was due to the corrosive dissolution of ZVC and the concurrent reduction of oxygen. The addition of tert-butanol completely inhibited the degradation of DEP and the addition of Fe(2+) greatly enhanced the degradation rate, which demonstrated that hydroxyl radical was mainly responsible for the degradation of DEP in ZVC acidic system under aerobic atmosphere condition, and the formation of hydroxyl radical was attributed to the Fenton-like reaction of in situ formed Cu(+) with H2O2. PMID:24857902

  1. Hydrate equilibrium conditions in aqueous electrolyte solutions: Mixtures of methane and carbon dioxide

    SciTech Connect

    Dholabhai, P.D.; Bishnoi, P.R. . Dept. of Chemical and Petroleum Engineering)

    1994-01-01

    Gas hydrates play an important role in the exploitation, transportation, and processing of natural gas. There is risk of hydrate formation at all the stages of natural gas handling due to the operating conditions of pressure and temperature that favor hydrate formation. Large reserves of natural gas also exist as hydrates. In addition, natural gas may have to be drilled through a zone of hydrates. Carbon dioxide is normally present along with these hydrocarbons. CO[sub 2] emission from the various combustion processes is identified to be the major reason for the greenhouse effect, and it is suggested that it be extracted and stored in deep sea waters as hydrates. Hydrate phase equilibrium data on CO[sub 2] and its mixtures with hydrocarbons are, therefore, essential. Three-phase equilibrium conditions (aqueous solution-vapor-hydrate) of methane + carbon dioxide mixtures in electrolyte solutions containing NaCl, KCl, CaCl[sub 2], and their mixtures were measured in the temperature range of 262--285 K and in the pressure range of 1.5--10.6 MPa a using a pressure search'' method. The ionic strengths of the solutions ranged from 0.7 to 6.76 m.

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

    USGS Publications Warehouse

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

    2005-01-01

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

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

    SciTech Connect

    Blair, D.S.

    1997-04-01

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

  4. The radiolysis of aqueous acetonitrile - Compounds of interest to chemical evolution studies

    SciTech Connect

    Draganic, I.G.; Jovanovic, S.

    1980-07-01

    Oxygen free aqueous solutions of CH3CN (0.1 M, pH 6) were exposed to gamma rays from a Co-60 source, the mixtures of nonvolatile radiolytic products was fractionated and the fractions were analysed. Succinic, maleic, fumaric, malonic and pyruvic acids were identified. Glycol aldehyde, glucose and probably ribose were observed in the hydrolysate of fractionated material. It has been suggested that an oligomer is formed which has a fragment with the polyhydroxy structure and on hydrolysis releases the carbohydrates. Radiolytic products which release amino acids on hydrolysis were found in several fractions. The amino acid contents of the hydrolysates were up to about 2.8% of the fraction mass. The presence of several protein and nonprotein amino acids suggests that their origin should be in a peptidic structure, which is probably a fragment of an oligomer radiolytically produced. A direct analysis of the irradiated solution shows the presence of acetaldehyde, propionaldehyde, glyoxal and of biacetyl. Experimental findings are discussed and a free-radical mechanism is proposed to account for the chemical changes observed.

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

    PubMed

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

    2015-01-01

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

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

    PubMed Central

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

    2015-01-01

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

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2008-05-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

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

    SciTech Connect

    Robert M. Counce

    2003-05-30

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

  11. 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.

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

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2003-01-01

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

  13. Chemical cleaning of Slovak brown coal by GACL (Grinding and Aqueous Caustic Leaching)

    SciTech Connect

    Balaz, P.; Turcaniova, L.; Frommel, E.A.; Martello, D.V.; Kern, D.G.; LaCount, R.B.

    1998-12-31

    The desulfuration of coal by chemical methods is accomplished by different reagents of acid or alkaline character. The study of the processes applying hot alkaline solutions to purification of coal is not a recent development. As early as during the second World War this process was used in Germany on purpose to prepare from coal a low-ash product suited to production of electrode carbon. It has been stated in a paper published by U.S. Bureau of Mines that one can reduce the content of ash in coal from original 98% to 0.7% by using 10% NaOH at increased pressure and temperature of 225 C. The application of NaOH solutions at increased temperatures (150--250 C) and pressures (0.6--2.5 MPa) were investigated in several laboratories. Another possibility of using alkaline medium for cleaning of coal involves atmospheric pressure. Molten NaOH (or its mixture with KOH) is used and the effective temperature is about 400 C. The ability of molten NaOH to desulfurate coal has been known for more than three decades. The liberation of the pyritic sulfur starts at temperatures above 150 C while the organic sulfur is released from the coal matrix at temperatures above 200 C. The process known as MCL (Molten Caustic Leaching) was for the first time tested by TRW in cooperation with US Department of Energy in the Seventies. The objective was to remove mineral components, pyritic and organic sulfur by using the reaction of coal with a mixture of molten sodium and potassium hydroxide. For leaching time of 60--180 min and temperatures of 370--400 C the effectiveness of MCL process of removal of individual components was as follows: 90--95% of pyritic sulfur, 70--90% of organic sulfur and 90--99% of ash. The MCL process was also effectively applied for treatment of Slovak brown coal in previous work. Because of the presence of sulfidic admixtures in coal and the fact that organic sulfur is built in the matrix of coal and from the view-point of chemical cleaning also exhibits refractory character, the possibility of verifying the principle of such pretreatment offers itself for coal as well. The aim of this work is to apply the new GACL process (Grinding and Aqueous Caustic Leaching) to brown coal Novaky, and to determine how effectively this process lowers ash, sulfur and arsenic levels.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  15. 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.

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

    DOEpatents

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

    1994-11-22

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

  17. 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.

  18. 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.

  19. 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

  20. 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...

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

    E-print Network

    by ACG on both glass and ITO substrates using an equimolar (0.01 m) aqueous solution of zinc nitrate-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

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

    NASA Astrophysics Data System (ADS)

    Sett, Dipanwita; Basak, Durga

    2015-10-01

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

  3. 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

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

    SciTech Connect

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

    2013-05-15

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

  5. 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

  6. Effect of molecular weight on radiation chemical degradation yield of chain scission of ?-irradiated chitosan in solid state and in aqueous solution

    NASA Astrophysics Data System (ADS)

    Tahtat, Djamel; Mahlous, Mohamed; Benamer, Samah; Nacer Khodja, Assia; Larbi Youcef, Souad

    2012-06-01

    Chitosan A1, A2 and A3 with molecular weight of 471, 207 and 100 kDa respectively, produced from squid pen chitin was degraded by gamma rays in the solid state and in aqueous solution with various doses in air at ambient temperature. Effect of molecular weight on radiation chemical degradation yield of chain scission and degradation rate constants of ?-irradiated chitosan in solid state and in aqueous solution was investigated. The radiation chemical degradation yield G(s) and degradation rate values were calculated. The molecular weight changes were monitored by capillary viscometry method and the chemical structure changes were followed by UV analysis. The results showed that, the degradation of chitosan was faster in solution, than in solid state. The values of G(s) in solid state and in aqueous solution were respectively 1.1×10-8 mol/J and 0.074×10-7 mol/J for A1, 4.42×10-8 mol/J and 0.28×10-7 mol/J for A2 and 6.08×10-8 mol/J and 0.38×10-7 mol/J for A3. Degradation rate constants values ranged from 0.41×10-5 to 2.1×10-5 kGy-1 in solid state, whereas in solution they ranged from 13×10-5 to 68×10-5 kGy-1. The chitosan A3 was more sensitive to radiolysis than A1 and A2. The chain scission yield, G(s) and degradation rate constants seems to be greatly influenced by the initial molecular weight of the chitosan. Structural changes in irradiated chitosan are revealed by the apparition of absorption peaks at 261 and 295 nm, which could be attributed to the formation of carbonyl groups. In both conditions the peak intensity was higher in chitosan A3 than in A1 and A2, the oxidative products decreased with increasing molecular weight of chitosan.

  7. Comparison of the chemical composition and pharmacological effects of the aqueous and ethanolic extracts from a Tibetan "Snow Lotus" (Saussurea laniceps) herb.

    PubMed

    Yi, Tao; Lo, Hongwing; Zhao, Zhongzhen; Yu, Zhiling; Yang, Zhijun; Chen, Hubiao

    2012-01-01

    To understand the impacts of different processing methods on the composition and effects of the herb Saussurea laniceps (SL), the present study report the first comparison of the chemical constituents of aqueous and ethanolic SL extracts using chromatographic analysis, and to compare their pharmacological effects in a mouse anti-inflammatory, anti-nociceptive model and an in vitro anti-oxidant test. Chemical comparison demonstrated that the types of chemicals in the two extracts were identical, but the contents of the main constituents in the aqueous extract were lower than those of the ethanolic extract. A transesterification of dicaffeoylquinic acids took place in the aqueous extract during boiling. As for pharmacological effects, oral administration of aqueous and ethanolic SL extracts significantly inhibited croton oil-induced mice ear edema, and significantly inhibited acetic acid-induced mice writhings, respectively. In the DPPH anti-oxidant activity test, the IC50 values were calculated as 409.6 mg/L and 523.4 mg/L for the ethanolic and aqueous extracts, respectively. The inhibitory effects of the ethanolic extract were more potent than those of the aqueous extract in all pharmacological tests, although there was no significant difference. This study suggests that the two preparations should be distinguished when used. PMID:22692242

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

    SciTech Connect

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

    1997-04-01

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

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

    PubMed

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

    2015-12-01

    Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments. Environ Toxicol Chem 2015;34:2739-2749. © 2015 SETAC. PMID:26109238

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

    SciTech Connect

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

    1994-12-01

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

  11. Solvent effects in chemical processes. water-assisted proton transfer reaction of pterin in aqueous environment.

    PubMed

    Jaramillo, Paula; Coutinho, Kaline; Canuto, Sylvio

    2009-11-12

    Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for the isolated pterin by quantum mechanical second-order Møller-Plesset perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier. The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case, the free energy barrier is only 6.7 kcal/mol and the calculated relative Gibbs free energy for the two tautomers is -11.2 kcal/mol. This value is used to calculate the pK(a) value of 8.2 +/- 0.6 that is in excellent agreement with the experimental result of 7.9. PMID:19754044

  12. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

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

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

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

    1994-05-01

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO4/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O ‘dew point’ is typically around 192-194 K at 100 mbar.

  15. An aqueous, alkaline route to titanate nanotubes under atmospheric pressure conditions.

    PubMed

    Bavykin, Dmitry V; Cressey, Barbara A; Light, Mark E; Walsh, Frank C

    2008-07-01

    A significant reduction in the temperature for alkaline synthesis of titanate nanotubes is reported. Nanotubular titanates have been synthesized from TiO(2) at 100?°C in a mixture of concentrated, aqueous solutions of KOH and NaOH. After 48 h of refluxing, essentially complete conversion was achieved. For a given temperature, the composition of KOH and NaOH in the binary mixture was chosen to achieve a particular concentration of Ti(IV), which favoured the formation of nanotubes. The morphology, surface area and crystal structure of the titanate nanotubes produced were similar to those produced in a solution of pure NaOH at a higher temperature (?140?°C). PMID:21828711

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

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

    SciTech Connect

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

    1987-11-10

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

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2005-05-01

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

  20. 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.

  1. Chemical analysis and aqueous solution properties of Charged Amphiphilic Block Copolymers PBA-b-PAA synthesized by MADIX

    E-print Network

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

    2007-08-27

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    EPA Science Inventory

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

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

    NASA Astrophysics Data System (ADS)

    Huang, Lei; Guo, Zhixiong

    2012-02-01

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

  5. 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

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

    NASA Astrophysics Data System (ADS)

    Clobes, Jason Kenneth

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

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

    PubMed

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

    2015-12-24

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

  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. 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...

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  11. 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.

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

    PubMed

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

    2015-12-01

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

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

    PubMed Central

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

    2013-01-01

    Cl partition coefficients between forsterite, enstatite and coexisting Cl-bearing aqueous fluids were determined in a series of high pressure and temperature piston cylinder experiments at 2 GPa between 900 and 1300 °C in the system MgO–SiO2–H2O–NaCl–BaO–C±CaCl2±TiO2±Al2O3±F. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA-ICP-MS. The chlorine content of forsterite and enstatite was measured by electron microprobe, and the nature of hydrous defects was investigated by infrared spectroscopy. Partition coefficients show similar incompatibility for Cl in forsterite and enstatite, with DClfo/fl = 0.0012 ± 0.0006, DClen/fl = 0.0018 ± 0.0008 and DClfo/en = 1.43 ± 0.71. The values determined for mineral/fluid partitioning are very similar to previously determined values for mineral/melt. Applying the new mineral/fluid partition coefficients to fluids in subduction zones, a contribution between 0.15% and 20% of the total chlorine from the nominally anhydrous minerals is estimated. Infrared spectra of experimental forsterite show absorption bands at 3525 and 3572 cm?1 that are characteristic for hydroxyl point defects associated with trace Ti substitutions, and strongly suggest that the TiO2 content of the system can influence the chlorine and OH incorporation via the stabilization of Ti-clinohumite-like point defects. The water contents for coexisting forsterite and enstatite in some runs were determined using unpolarized IR spectra and calculated water partition coefficients DH2Ofo/en are between 0.01 and 0.5. PMID:25843971

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

    PubMed Central

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

    2013-01-01

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

  15. Aqueous acidities of primary benzenesulfonamides: Quantum chemical predictions based on density functional theory and SMD.

    PubMed

    Aidas, K?stutis; Lanevskij, Kiril; Kubilius, Rytis; Juška, Liutauras; Petkevi?ius, Daumantas; Japertas, Pranas

    2015-11-01

    Aqueous pKa of selected primary benzenesulfonamides are predicted in a systematic manner using density functional theory methods and the SMD solvent model together with direct and proton exchange thermodynamic cycles. Some test calculations were also performed using high-level composite CBS-QB3 approach. The direct scheme generally does not yield a satisfactory agreement between calculated and measured acidities due to a severe overestimation of the Gibbs free energy changes of the gas-phase deprotonation reaction by the used exchange-correlation functionals. The relative pKa values calculated using proton exchange method compare to experimental data very well in both qualitative and quantitative terms, with a mean absolute error of about 0.4 pKa units. To achieve this accuracy, we find it mandatory to perform geometry optimization of the neutral and anionic species in the gas and solution phases separately, because different conformations are stabilized in these two cases. We have attempted to evaluate the effect of the conformer-averaged free energies in the pKa predictions, and the general conclusion is that this procedure is highly too costly as compared with the very small improvement we have gained. © 2015 Wiley Periodicals, Inc. PMID:26154878

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

    SciTech Connect

    Vayssieres, Lionel; Guo, Jinghua; Nordgren, Joseph

    2001-06-30

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

  17. 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%.

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

    SciTech Connect

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

    1999-04-01

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

  19. Chemical processing in high-pressure aqueous environments; 3: Batch reactor process development experiments for organics destruction

    SciTech Connect

    Elliot, D.C.; Sealock, L.J. Jr.; Baker, E.G. )

    1994-03-01

    A high-pressure (20 MPa) and high-temperature (350 C) liquid water processing environment was used to treat various wastewaters and model compounds. Organics were converted to methane and carbon dioxide in the presence of catalysts. Functional types included hydrocarbons, both aliphatic and aromatic; phenolics and other oxygenates; chlorinated hydrocarbon solvents; and sodium salts of organic acids. Tests with aqueous nickel ion showed negligible catalytic activity. Noncatalytic hydrolysis of sodium cyanide, carbon tetrachloride, and chloroform was also demonstrated. Ammonium destruction was proven by reaction with nitrate at these processing conditions. Several examples of test results with actual industrial waste streams showed that this process can be effectively used with catalysts to clean wastewater and recover waste organics as useful fuel gas.

  20. '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...

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

    EPA Science Inventory

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

  2. Characterizing stability of ``click'' modified glass surfaces to common microfabrication conditions and aqueous electrolyte solutions

    E-print Network

    surface groups are exposed to various wet and dry conditions including acid, base, solvent, electrolyte,9,10 Physisorption is the adsorp- tion of a molecule to a surface where the adhesion to the surface is due to the van-cleaning surfaces,36 surface passivation37 for cell adhesion, cell migration38 in microchann

  3. 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...

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

    PubMed

    Husch, Tamara; Korth, Martin

    2015-09-21

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

  5. 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.

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

    SciTech Connect

    Leghrous, A.A.

    1989-01-01

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

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

    PubMed Central

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

    2015-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-08-01

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

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

    PubMed

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

    2015-09-01

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

  10. 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).

  11. Chemical enrichment and physical conditions in I Zw 18

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

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

    ERIC Educational Resources Information Center

    Tellinghuisen, Joel

    2006-01-01

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

  13. 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.

    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.

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

    SciTech Connect

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

    1993-01-01

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

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

    SciTech Connect

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

    1993-01-01

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

  16. 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...

  17. 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...

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

    PubMed Central

    2014-01-01

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

  19. Removal of heavy metals from aqueous phases using chemically modified waste Lyocell fiber.

    PubMed

    Bediako, John Kwame; Wei, Wei; Kim, Sok; Yun, Yeoung-Sang

    2015-12-15

    In this study, an outstanding performance of chemically modified waste Lyocell for heavy metals treatment is reported. The sorbent, which was prepared by a simple and concise method, was able to bind heavy metals such as Pb(II), Cu(II) and Cd(II), with very high efficiencies. The binding mechanisms were studied through adsorption and standard characterization tests such as scanning electron microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction analyses. Adsorption kinetics was very fast and attained equilibrium within 5min in all metals studied. The maximum single metal uptakes were 531.29±0.28mg/g, 505.64±0.21mg/g, and 123.08±0.26mg/g for Pb(II), Cd(II) and Cu(II), respectively. In ternary metal systems, Cu(II) selectivity was observed and the underlying factors were discussed. The sorbent by its nature, could be very effective in treating large volumes of wastewater with the contact of very little amount. PMID:26257295

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

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2004-01-01

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

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

    PubMed

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

    2014-09-10

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

  2. 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.

  3. 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.

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

    EPA Science Inventory

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

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Molecular hydrogen produced through iron oxidation during formation of serpentine and magnetite can sustain terrestrial subsurface ecosystems. The Fe3+ in serpentine partitions into octahedral and tetrahedral sites differently as serpentinization proceeds, and tetrahedral Fe3+ is present toward the end of serpentinization. We map Fe oxidation states in a serpentinite to determine the degree to which serpentinization progressed and where hydrogen production has been maximized to assess habitability at an abandoned chrysotile mine in Norbestos, Quebec, in association with the Canadian Space Agency's Mars Methane Analogue Mission. We also analyzed stable isotopes of carbon and oxygen in carbonates to constrain the conditions of water-rock interaction during serpentinization. Iron oxidation and coordination was determined through field imaging of rock walls with a visible hyperspectral imager (420-720 nm), and samples collected from imaged rocks and elsewhere in the mine were imaged in the laboratory (420-1100 nm). Sample chemistry, mineralogy, and oxidation state were determined with laboratory measurements of visible through mid-infrared reflectance spectra, major element chemistry, mineralogy, and Mössbauer spectroscopy. Mapping with hyperspectral imaging of outcrops and hand samples shows that tetrahedral Fe3+ is common in serpentinites at this site, and results are confirmed through other measurements. Major element chemistry and mineralogy are consistent with serpentine plus minor carbonate. Carbonate samples show an exceptional range in ?13C (-13.14 to + 16.12 ‰ VPDB) and ?18O (-15.48 to - 3.20 ‰ VPDB) that vary with location in the mine. Carbonates south of a shear zone (?13C more positive) likely formed during periods of serpentinization in a carbon-limited reservoir closed to carbon addition but open to methane escape. Carbonates in a shear zone (?13C more negative) probably formed later at low temperatures through CO2-metasomatism or atmospheric weathering, and isotopic trends are consistent with kinetic fractionation. The extensive presence of tetrahedral Fe3+ in serpentine shows the system liberally produced H2 while the isotope systematics have implications for preservation of indicators of the aqueous conditions that formed serpentinites on Mars and their habitability.

  7. 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

  8. Chemical insights, explicit chemistry, and yields of secondary organic aerosol from OH radical oxidation of methylglyoxal and glyoxal in the aqueous phase

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Tan, Y.; Turpin, B. J.

    2013-09-01

    Atmospherically abundant, volatile water-soluble organic compounds formed through gas-phase chemistry (e.g., glyoxal (C2), methylglyoxal (C3), and acetic acid) have great potential to form secondary organic aerosol (SOA) via aqueous chemistry in clouds, fogs, and wet aerosols. This paper (1) provides chemical insights into aqueous-phase OH-radical-initiated reactions leading to SOA formation from methylglyoxal and (2) uses this and a previously published glyoxal mechanism (Lim et al., 2010) to provide SOA yields for use in chemical transport models. Detailed reaction mechanisms including peroxy radical chemistry and a full kinetic model for aqueous photochemistry of acetic acid and methylglyoxal are developed and validated by comparing simulations with the experimental results from previous studies (Tan et al., 2010, 2012). This new methylglyoxal model is then combined with the previous glyoxal model (Lim et al., 2010), and is used to simulate the profiles of products and to estimate SOA yields. At cloud-relevant concentrations (~ 10-6 - ~ 10-3 M; Munger et al., 1995) of glyoxal and methylglyoxal, the major photooxidation products are oxalic acid and pyruvic acid, and simulated SOA yields (by mass) are ~ 120% for glyoxal and ~ 80% for methylglyoxal. During droplet evaporation oligomerization of unreacted methylglyoxal/glyoxal that did not undergo aqueous photooxidation could enhance yields. In wet aerosols, where total dissolved organics are present at much higher concentrations (~ 10 M), the major oxidation products are oligomers formed via organic radical-radical reactions, and simulated SOA yields (by mass) are ~ 90% for both glyoxal and methylglyoxal. Non-radical reactions (e.g., with ammonium) could enhance yields.

  9. 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.

  10. An integrated approach to optimize the conditioning chemicals for enhanced sludge conditioning in a pilot-scale sludge dewatering process.

    PubMed

    Zhai, Lin-Feng; Sun, Min; Song, Wei; Wang, Gan

    2012-10-01

    An integrated approach incorporating response surface methodology (RSM), grey relational analysis, and fuzzy logic analysis was developed to quantitatively evaluate the conditioning chemicals in sludge dewatering process. The polyacrylamide (PAM), ferric chloride (FeCl(3)) and calcium-based mineral powders were combined to be used as the sludge conditioners in a pilot-scale sludge dewatering process. The performance of conditioners at varied dosages was comprehensively evaluated by taking into consideration the sludge dewatering efficiency and chemical cost of conditioner. In the evaluation procedure, RSM was employed to design the experiment and to optimize the dosage of each conditioner. The grey-fuzzy logic was established to quantify the conditioning performance on the basis of grey relational coefficient generation, membership function construction, and fuzzy rule description. Based on the evaluation results, the optimal chemical composition for conditioning was determined as PAM at 4.62 g/kg DS, FeCl(3) at 55.4 g/kg DS, and mineral powders at 30.0 g/kg DS. PMID:22858481

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  13. One-pot synthesis of surface roughness controlled hollow silica spheres with enhanced drug loading and release profile under ambient conditions in aqueous solutions

    PubMed Central

    Li, Dong; Zhu, Ye

    2013-01-01

    A green one-pot approach is used to synthesize surface morphology controlled hollow silica spheres in aqueous solution under ambient conditions. Using cationic polystyrene particles as a template and aminopropyltriethoxysilane (APTES) as a structural directing agent, the surface roughness and wall thickness could be easily controlled by varying the concentration of tetraethoxysilane (TEOS). Smooth surface of hollow silica spheres with different wall thickness was obtained using anionic polystyrene particles. The resulted hollow silica spheres with rough surface had better performance in carrying and releasing a model drug. PMID:24244868

  14. Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

    2014-05-01

    Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared to the non reactive one. On the basis of a reaction-diffusion-convection model, we classify the various possible cases and show that the difference between the solutal expansion coefficients of the reactant and of the product governs the type of density profile building up in the aqueous solution and thus the stability of the system. By contrast to non reactive density profiles, reactive density profiles can feature a minimum that induces a delay of the buoyancy-driven convection. This work identifies the parameters that could influence the dissolution-driven convection in the aquifers, and thus impact the safety of the sequestration. In other words, this theoretical study shows that it is crucial to analyse the composition and reactivity of potential storage sites to choose those that will be most efficient for long-term CO2 sequestration.

  15. 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.

  16. 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 ...

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

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

  19. 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...

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  2. Synthesis of 3-substituted isoindolin-1-ones via a tandem desilylation, cross-coupling, hydroamidation sequence under aqueous phase-transfer conditions.

    PubMed

    Munoz, Socrates B; Aloia, Alexandra N; Moore, Alexander K; Papp, Attila; Mathew, Thomas; Fustero, Santos; Olah, George A; Surya Prakash, G K

    2016-01-01

    A simple and expedient method for the synthesis of 3-methylene-isoindolin-1-ones 4 under aqueous phase-transfer conditions has been developed. Starting from 2-iodobenzamides 1 and (silyl)alkynes, the products are obtained in high yields and short reaction times (30 min) with the use of inexpensive CuCl/PPh3 catalyst system in the presence of n-Bu4NBr (TBAB) as a phase-transfer agent. Terminal alkynes are conveniently "unmasked" upon in situ desilylation under the reaction conditions. Alkynes possessing heterocyclic moieties were also found as amenable substrates. Furthermore, a one-pot process starting from 2-iodobenzamides 1, aryl halides (bromides or iodides) and trimethylsilylacetylene (TMSA) as a convenient acetylene surrogate was also shown to be feasible under Pd/Cu catalysis. PMID:26611810

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

    USGS Publications Warehouse

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

    2007-01-01

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

  4. 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.

  5. Simultaneous quantification of carteolol and dorzolamide in rabbit aqueous humor and ciliary body by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zammataro, Alessio; Saletti, Rosaria; Civiale, Claudine; Muccilli, Vera; Cunsolo, Vincenzo; Foti, Salvatore

    2010-03-15

    A rapid, sensitive and selective method for the simultaneous quantification of carteolol and dorzolamide in rabbit aqueous humor (AH) and ciliary body (CB) has been developed and validated using reversed phase-high performance liquid chromatography (RP-HPLC) with isocratic elution coupled with atmospheric pressure chemical ionization mass spectrometry/mass spectrometry (APCI-MS/MS). The analytes and nadolol (used as internal standard, IS) were purified from AH by protein precipitation. The sample preparation from CB was based on a two steps extraction procedure at different pH, utilizing a liquid-liquid extraction with a mixture of ethyl acetate, toluene and isopropanol 50:40:10 (v/v) at pH 8, followed by a second extraction with ethyl acetate at pH 11. The combined organic extracts were then back extracted into 0.1% aqueous trifluoroacetic acid (TFA). The accuracy and precision values, calculated from three different sets of quality control samples analyzed in sestuplicate on three different days, were within the generally accepted criteria for analytical methods (<15%). The assay proved to be accurate and precise when applied to the in vivo study of carteolol and dorzolamide in rabbit AH and CB after single administration of an eye drops containing both drugs. PMID:20153987

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

    SciTech Connect

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

    1999-08-15

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

  7. 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.

  8. SONOCHEMICAL DECHLORINATION OF HAZARDOUS WASTES IN AQUEOUS SYSTEMS. (R825513C004)

    EPA Science Inventory

    Physical processes resulting from ultrasonication of aqueous solutions and suspensions produce extreme conditions that can affect the chemistry of dissolved and suspended chemicals. The purpose of this work was to explore the use of sonochemistry in treating chlorinated chemic...

  9. Chemically transferable coarse-grained potentials from conditional reversible work calculations

    NASA Astrophysics Data System (ADS)

    Brini, E.; van der Vegt, N. F. A.

    2012-10-01

    The representability and transferability of effective pair potentials used in multiscale simulations of soft matter systems is ill understood. In this paper, we study liquid state systems composed of n-alkanes, the coarse-grained (CG) potential of which may be assumed pairwise additive and has been obtained using the conditional reversible work (CRW) method. The CRW method is a free-energy-based coarse-graining procedure, which, by means of performing the coarse graining at pair level, rigorously provides a pair potential that describes the interaction free energy between two mapped atom groups (beads) embedded in their respective chemical environments. The pairwise nature of the interactions combined with their dependence on the chemically bonded environment makes CRW potentials ideally suited in studies of chemical transferability. We report CRW potentials for hexane using a mapping scheme that merges two heavy atoms in one CG bead. It is shown that the model is chemically and thermodynamically transferable to alkanes of different chain lengths in the liquid phase at temperatures between the melting and the boiling point under atmospheric (1 atm) pressure conditions. It is further shown that CRW-CG potentials may be readily obtained from a single simulation of the liquid state using the free energy perturbation method, thereby providing a fast and versatile molecular coarse graining method for aliphatic molecules.

  10. Multianalyte determination of 24 cytostatics and metabolites by liquid chromatography-electrospray-tandem mass spectrometry and study of their stability and optimum storage conditions in aqueous solution.

    PubMed

    Negreira, Noelia; Mastroianni, Nicola; López de Alda, Miren; Barceló, Damià

    2013-11-15

    A multianalyte liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS/MS) method for determination of 19 cytostatics and 5 metabolites, from 6 different therapeutic families, has been developed, and the structures of the main characteristic fragment ions have been proposed. Instrumental limits of detection and quantification are in the range 0.1-10.3 and 1.0-34.3 ng mL(-1), respectively. Moreover, the stability of the compounds in aqueous solution was investigated in order to establish the best conditions for preparation and storage of both calibration standards and water samples. Dimethylsulphoxide (DMSO) was selected as solvent for preparation of the stock solutions. At room temperature (25 °C), 11 of the 24 target compounds were shown to be unstable in water (percentage of organic solvent 4%), with concentration losses greater than 20% in less than 24 h. At 4 °C (typical storage temperature for water samples) all compounds, except MTIC and chlorambucil, were stable for 24h, but the number of stable compounds decreased to 10 after 9 days. Freezing of the aqueous solutions improved considerably the stability of various compounds: after 3 months of storage at -20 °C, 10 compounds, namely, 5-fluorouracil, carboplatin, gemcitabine, temozolomide, vincristine, vinorelbine, ifosfamide, cyclophosphamide, etoposide, and capecitabine, remained stable (in contrast to only carboplatin and capecitabine at 4 °C). The addition of acid improved the stability of methotrexate and its metabolite hydroxy-methotrexate but not that of the rest of compounds. The addition of organic solvent (50% methanol or DMSO) prevented the degradation at 4 °C of the otherwise unstable compounds oxaliplatin, methotrexate, erlotinib, doxorubicin, tamoxifen, and paclitaxel. To the authors' knowledge, five of the analytes investigated have never been searched for in the aquatic environment (imatinib, 6?-hydroxypaclitaxel, endoxifen, (Z)4-hydroxytamoxifen, and temozolomide), and for many of them the stability data provided, and even the analytical LC-MS/MS conditions, are the first ever published. PMID:24148406

  11. 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.

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

    PubMed

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

    2016-03-01

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

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

    USGS Publications Warehouse

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

    1991-01-01

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

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

    SciTech Connect

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

    2012-07-26

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

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

    NASA Astrophysics Data System (ADS)

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

    1993-08-01

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

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

    SciTech Connect

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

    1998-08-01

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

  17. Sonochemical dechlorination of hazardous wastes in aqueous systems

    SciTech Connect

    Catallo, W.J.; Junk, T.

    1995-12-31

    Physical processes resulting from ultrasonication of aqueous solutions and suspensions produce extreme conditions that can affect the chemistry of dissolved and suspended chemicals. The purpose of this work was to explore the use of sonochemistry in treating chlorinated chemicals in water. The compounds examined for susceptibility to aqueous sonochemical transformation were chlorpyrifos, 3,3{prime},4,4{prime}-tetrachloroazoxybenzene, 2-chlorobiphenyl, 2,4,8-trichlorodibenzofuran, lindane (hexachlorocyclohexane, {gamma}-isomer), hexachlorobenzene, aldrin, and a complex mixture of chlorinated olefins, paraffins, and aromatics from a Louisiana Superfund Site. It was fond that many chemicals were dechlorinated and/or otherwise transformed by sonochemical treatment under minimal conditions. Evidence for sonochemical transformation and dechlorination of the target chemicals and mixtures was obtained from controlled experiments measuring (1) increases in titratable chloride from sonochemical treatment, (2) decreases in pH, (3) changes in aqueous phase UV/visible absorption spectra, (4) changes in aqueous electrochemistry, and (5) generation of sonolysis products and/or decreases in target compounds vs appropriate control in internally standardized GC-MS analysis of extracts.

  18. 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

  19. 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

  20. Brownian dynamics simulations of an idealized chemical reaction network under spatial confinement and crowding conditions

    E-print Network

    Bellesia, Giovanni

    2015-01-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a simple, non-linear chemical network (the Willamowski-Rossler network) under spatial confinement and crowding conditions. Our results show that the presence of inert crowders has a non-nontrivial effect on the dynamics of the network and, consequently, that effective modeling efforts aiming at a general understanding of the behavior of biochemical networks in vivo should be stochastic in nature and based on an explicit representation of both spatial confinement and macromolecular crowding.

  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. 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.

  4. 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

  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. 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

  7. Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA

    NASA Technical Reports Server (NTRS)

    Kawamura, K.; Nagahama, M.; Kuranoue, K.

    2005-01-01

    The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions. c2005 COSPAR. Published by Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2015-06-01

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

  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. Behavioral response of Corophium volutator relative to experimental conditions, physical and chemical disturbances.

    PubMed

    Hellou, Jocelyne; Cheeseman, Kerri; Jouvenelle, Marie-Laure; Robertson, Sarah

    2005-12-01

    The preference/avoidance behavioral response of a widely used amphipod in toxicity tests, Corophium volutator, was investigated in relation to the presence of anthropogenic physical or chemical materials in sediments. Exposure conditions, including the density of amphipods, the depth of sediments, amount of overlying water, and exposure time, were examined for their influence on amphipods' preference for field sediments and avoidance of coarse sand. It was shown that these variables did not affect the response; thus, conditions similar to published standard toxicity tests were chosen. A gradient of sediments spiked with potential habitat disturbances that can be found on a beach or in contaminated sediments, such as those in harbors, were tested. These substances included sand, seaweed, burned wood, coal, crankcase oil, and diesel oil. To enhance the interpretation of results and decrease the variability observed when tests were conducted at different times over the summer, exposures were performed over a gradient of spike material in reference sediments. We conclude that physical obstacles added to reference sediments lead to less correlation with the behavioral response than observed with chemical interferences. Amphipods' behavior ranked harbor sediments similarly to previous studies concerning the health of intertidal mussels collected in proximity to the sediments sites. For five sites, preference of reference sediments was observed until the level of polycyclic aromatic hydrocarbons in diluted harbor sediments reached the Canadian Council of Ministers of the Environment sediment quality guidelines. PMID:16445086

  11. A continuum analysis of chemical nonequilibrium under hypersonic low-density flight conditions

    NASA Technical Reports Server (NTRS)

    Gupta, R. N.

    1986-01-01

    Results of employing the continuum model of Navier-Stokes equations under the low-density flight conditions are presented. These results are obtained with chemical nonequilibrium and multicomponent surface slip boundary conditions. The conditions analyzed are those encountered by the nose region of the Space Shuttle Orbiter during reentry. A detailed comparison of the Navier-Stokes (NS) results is made with the viscous shock-layer (VSL) and direct simulation Monte Carlo (DSMC) predictions. With the inclusion of new surface-slip boundary conditions in NS calculations, the surface heat transfer and other flowfield quantities adjacent to the surface are predicted favorably with the DSMC calculations from 75 km to 115 km in altitude. This suggests a much wider practical range for the applicability of Navier-Stokes solutions than previously thought. This is appealing because the continuum (NS and VSL) methods are commonly used to solve the fluid flow problems and are less demanding in terms of computer resource requirements than the noncontinuum (DSMC) methods.

  12. 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

  13. 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.

  14. Assessment Of Chemical Dispersant Effectiveness In A Wave Tank Under Regular Non-Breaking And Breaking Wave Conditions

    EPA Science Inventory

    Current chemical dispersant effectiveness tests for product selection are commonly performed with bench-scale testing apparatus. However, for the assessment of oil dispersant effectiveness under real sea state conditions, test protocols are required to have hydrodynamic conditio...

  15. [Extraction of alpha-cypermethrin from aqueous methanol solutions].

    PubMed

    Shormanov, V K; Chigareva, E N; Belousova, O V

    2010-01-01

    Alpha cypermethrin was extracted from aqueous methanol solutions using hydrophobic organic solvents. The efficiency of extraction was shown to depend on the chemical nature of the solvent, the water to methanol ratio, and saturation of the aqueous methanol layer with an electrolyte. Optimal extraction of alpha-cypermethrin was achieved using toluene as the solvent under desalinization conditions. The extraction factor for the removal of the sought amount of alpha-cypermethrin from the water-methanol solution (4:1) using various solvents was calculated. PMID:20734789

  16. X-ray diffraction study of the formation of solid solutions in urania-thoria prepared by aqueous chemical processes

    NASA Astrophysics Data System (ADS)

    de Lima, Nelson Batista; Imakuma, Kengo

    1985-10-01

    The formation of solid solutions of (U, Th)O 2 was studied by X-ray diffraction on specimens prepared by a hydrolytical process and by co-precipitation. The uranium-thorium compounds obtained by the two processes were calcined, followed by reduction treatments in different conditions. The crystal structures of the products obtained after calcination of the powder blends prepared by both processes are given. The different stages of homogenization that occurred during reduction, were characterized by means of the relative peak positions. The activation energy for interdiffusion during the reduction process was found to be 42 {kJ}/{mol}.

  17. Aqueous Conditions and Habitability Associated with Formation of a Serpentinite: Using Analyses of Ferric Iron and Stable Carbon Isotopes to Reconstruct Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Greenberger, R. N.; Mustard, J. F.; Cloutis, E.; Pratt, L. M.; Sauer, P. E.; Mann, P.; Turner, K.; Dyar, M. D.

    2014-12-01

    Serpentine deposits on Mars have generated significant interest because byproducts of serpentinization, H2 and CH4, can be important energy sources for subsurface microbial communities. H2 is produced through Fe2+ oxidation to form magnetite and Fe3+-bearing serpentine. In serpentine, Fe3+ goes into octahedral sites first, then tetrahedral sites [Marcaillou et al., 2011, EPSL]. We use Fe oxidation state and coordination in an Early Ordovician serpentinite in Norbestos, Quebec, as proxies for H2 production and stable isotopes of carbonates to understand past aqueous conditions at the Canadian Space Agency's 2012 Mars Methane Analogue Mission site. Rock outcrops were imaged with a visible hyperspectral imager (420-720 nm), and samples were imaged in the laboratory with the same imager and a near infrared imager (650-1100 nm). Other analyses determined major element chemistry (ICP-AES and C analyses), mineralogy (XRD), Fe phases (Mössbauer spectroscopy), and stable isotopes of carbonates. Fe oxidation state and coordination (tetrahedral vs octahedral) were mapped in samples and outcrops using imaging data. We focused on locations with tetrahedral Fe3+ in serpentine as these are the most serpentinized sites with maximum H2 production. Carbonate samples from ~100-200 m south of a shear zone are enriched in 13C (?13C up to +16.12‰ vs VPDB) resulting from production of CH4 depleted in 13C in a system closed to C addition but open to CH4 escape. This alteration occurred at elevated temperatures and low water/rock ratios. In the shear zone, lower ?13C values (most < +2‰) positively correlated with ?18O likely result from kinetic fractionation under recent low temperature conditions. Spectroscopy suggests that much of this deposit underwent advanced serpentinization to produce significant H2. Isotopic signatures of carbonates precipitated during serpentinization outside the shear zone illuminate the temperatures (elevated) and chemistries of fluids (high Ca2+, low CO2, alkaline) and gases (H2, CH4) in an ancient habitable environment. These results suggest that serpentinites identified on Mars, where there has been limited recent aqueous activity, could preserve evidence of fluid composition and levels of hydrogen production, providing a promising context to search for biosignatures.

  18. Exceedingly Low Freezing Rates of Aqueous Hno3 and Hno3/h2so4 Droplets Under Polar Stratospheric Conditions

    NASA Astrophysics Data System (ADS)

    Knopf, D. A.; Koop, T.; Luo, B.; Weers, U. G.; Peter, T.

    In the Arctic winter 1999/2000 large particles containing nitric acid were observed during in situ field measurements. These large particles are important for the deni- trification of the Arctic stratosphere. It has been proposed that such particles form by homogeneous nucleation of nitric acid hydrates from liquid stratospheric aerosol droplets. Homogeneous nucleation rates of NAT (Nitric Acid Trihydrate) and NAD (Nitric Acid Dihydrate) have been determined in laboratory experiments for binary HNO3/H2O solutions only at supersaturations much larger than observed in the stratosphere. Therefore, an extrapolation of such laboratory data is required for the modelling of stratospheric particle formation and subsequent denitrification. We will present new laboratory data of homogeneous nucleation rates of NAT and NAD from droplets consisting of both binary HNO3/H2O as well as ternary HNO3/H2O/H2SO4 solutions. Optical microscopy has been used to deduce the droplet freezing tempera- tures. The nature of the crystallized solids was identified by Raman spectroscopy. The freezing data have been analyzed within the framework of classical nucleation theory. Our results are consistent with previously published laboratory aerosol data. However, for stratospheric conditions, we infer homogeneous nucleation rates to be lower by orders of magnitude than the extrapolation currently in use. We conclude that homo- geneous nucleation of NAT and NAD is not sufficient to explain the observed number concentrations of large nitric acid containing particles in the stratosphere.

  19. Greener Syntheses and Chemical Transformations: Sustainable Alternative Methods and Applications of Nano-Catalysts

    EPA Science Inventory

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

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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 (FeCl?). 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, FeCl?and Sed CF802 improve sludge dewatering. Optimum dosages of chitosan, Sed CF802 and FeCl?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 × 10¹², 0.932 × 10¹² and 2 × 10¹² m/kg for Sed CF802, chitosan and FeCl?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 FeCl?. PMID:25812088

  5. Defect formation in aqueous environment: Theoretical assessment of boron incorporation in nickel ferrite under conditions of an operating pressurized-water nuclear reactor (PWR)

    NASA Astrophysics Data System (ADS)

    Rák, Zs.; Bucholz, E. W.; Brenner, D. W.

    2015-06-01

    A serious concern in the safety and economy of a pressurized water nuclear reactor is related to the accumulation of boron inside the metal oxide (mostly NiFe2O4 spinel) deposits on the upper regions of the fuel rods. Boron, being a potent neutron absorber, can alter the neutron flux causing anomalous shifts and fluctuations in the power output of the reactor core. This phenomenon reduces the operational flexibility of the plant and may force the down-rating of the reactor. In this work an innovative approach is used to combine first-principles calculations with thermodynamic data to evaluate the possibility of B incorporation into the crystal structure of NiFe2O4, under conditions typical to operating nuclear pressurized water nuclear reactors. Analyses of temperature and pH dependence of the defect formation energies indicate that B can accumulate in NiFe2O4 as an interstitial impurity and may therefore be a major contributor to the anomalous axial power shift observed in nuclear reactors. This computational approach is quite general and applicable to a large variety of solids in equilibrium with aqueous solutions.

  6. 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.

  7. Fluid Pressure, Thermal and Chemical Effects in Conditioning Permeability and Triggered Seismicity in Enhanced Geothermal Systems

    NASA Astrophysics Data System (ADS)

    Elsworth, D.; Izadi, G.; Zheng, B.; Taron, J.

    2011-12-01

    The evolution of permeability, heat or diffusive transfer area and triggered seismicity are intimately linked in forced-circulation systems such as EGS, CCS and unconventional hydrocarbon reservoirs where conditions are pushed far-from-equilibrium. We explore this evolution subject to coupled THMC processes in a prototypical EGS reservoir. We accommodate the influence of early-time changes in effective stress, mid-time changes in thermal stresses and ultimately incorporate long-term changes due to chemical effects. We develop a micromechanical model to represent the failure process and apply this model to represent energy release from individual critically oriented fractures. The changing stress state is calculated from the pore pressure, thermal drawdown and chemical effects for a coupled THMC model with dual porosity. This model is applied to a doublet geometry to explore the spatial and temporal migration for permeability evolution, access to reactive surface area and the triggering of seismicity as stimulation then production proceeds. Seismic activity is initially concentrated around the near-wellbore injection region. It is earliest for closely spaced fractures in reservoir rocks where the thermal drawdown of stress is largest at early times and results in numerous low-magnitude events. These observations are used to define the evolution of spatial changes within the reservoir and their migration with production, dependent on the mobilization of relic fractures.

  8. 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

  9. 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...

  10. 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.

  11. Self-association of unconjugated bilirubin-IX alpha in aqueous solution at pH 10.0 and physical-chemical interactions with bile salt monomers and micelles.

    PubMed Central

    Carey, M C; Koretsky, A P

    1979-01-01

    Spectrophotometric measurements of bilirubin-IX alpha in water and in aqueous/organic solvent mixtures at pH 10.0 as a function of bilirubin-IX alpha concentration (approx. 0.6--400 microM) are consistent with the formation of dimers (KD - 1.5 microM) in dilute (less than 10 microM) aqueous solution and further self-aggregation to multimers at higher concentrations. Added urea (to 10M) and increases in temperature (to 62 degrees C) obliterate the dimer-multimer transition at 10 microM, but added NaCl (to 0.30 M) promotes strong aggregation of dimers over a narrow concentration range, suggesting a 'micellization' phenomenon. Concentrations of dioxan or ethanol greater than 60% (v/v) in water were required to obtain the absorption spectrum of bilirubin-IX alpha monomers, suggesting that both hydrophobic and electrostatic (pi-orbital) interactions are involved in stabilizing the dimeric state in water. Micellar concentrations of sodium dodecyl sulphate induced spectrophotometric shifts in the dimer absorption spectrum of bilirubin-IX alpha consistent with progressive partitioning of bilirubin-IX alpha monomers into a relatively non-polar region of the micelles and allowed a deduction of the apparent critical micellar concentration that closely approximated the literature values. The pattern of bilirubin IX alpha association with bile salts is complex, since the absorption spectrum shifts hypsochromically below and bathochromically above the critical micellar concentration of the bile salts. Consistent with these observations, bilirubin IX alpha appears to bind to the polar face of bile salt monomers and to the polar perimeter of small bile salt micelles. At higher bile salt concentrations some-bilirubin-IX alpha monomers partition into the hydrophobic interior of the bile salt micelles. Our results suggest that under physiological conditions the natural conjugates of bilirubin-IX alpha may exhibit similar physical chemical properties in bile, in that dimers, highly aggregated multimers and bile salt-associated monomers may co-exist. PMID:38779

  12. Study of Chemical Surface Structure of Natural Sorbents Used for Removing of Pb2+ Ions from Model Aqueous Solutions (part Ii)

    NASA Astrophysics Data System (ADS)

    Bo??cka, Agnieszka; Bo??cki, Piotr; Sanak-Rydlewska, Stanis?awa

    2014-03-01

    This article presents the results of the chemical structure research of organic sorbent surface such as walnut shells, plums stones and sunflower hulls with using such methods as infrared spectrometry (FTIR) and elemental analysis. Based on the IR spectra identification of functional groups present on the surface of studied materials has been done as well as determination of their effect on the sorption mechanism of Pb2+ ions from aqueous model solutions W artykule przedstawiono wyniki bada? chemicznej struktury powierzchni sorbentów organicznych takich jak: ?upiny orzecha w?oskiego, pestki ?liwek oraz ?uski s?onecznika z wykorzystaniem metody spektrometrii w podczerwieni (FTIR) oraz analizy elementarnej. W oparciu o uzyskane widma IR dokonano identyfikacji grup funkcyjnych obecnych na powierzchni tych materia?ów i okre?lono ich wp?yw na mechanizm sorpcji jonów Pb2+ z modelowych roztworów wodnych. Analiza elementarna wykaza?a, ?e spo?ród badanych sorbentów, najwi?ksz? zawarto?? w?gla (49,91%) i wodoru (5,93%) maj? pestki ?liwek. Najwi?cej azotu (1,59%) zawieraj? ?uszczyny s?onecznika (tabela 1). Zawarto?? siarki we wszystkich badanych materia?ach jest znikoma, dlatego nie uda?o si? jej oznaczy? t? metod?. Obecno?? pozosta?ych pierwiastków mo?e ?wiadczy? o istnieniu zarówno alifatycznych jak i aromatycznych po??cze? organicznych. Potwierdzeniem tego s? równie? zarejestrowane widma IR (rysunki 1-3). W oparciu o uzyskane wyniki mo?na przypuszcza? tak?e, i? udzia? procesu wymiany jonowej w sorpcji o?owiu z roztworów wodnych jest znacz?cy. ?wiadcz? o tym m.in. intensywno?ci pasm na widmach IR dla próbek badanych materia?ów po ich kontakcie z roztworami jonów Pb2+ (rysunki 4-6).

  13. Meteorological conditions and anomalies during the Intercontinental Chemical Transport Experiment-North America

    NASA Astrophysics Data System (ADS)

    Fuelberg, Henry E.; Porter, Michael J.; Kiley, Christopher M.; Halland, Jeremy J.; Morse, Danielle

    2007-06-01

    Meteorological conditions are described during the Intercontinental Chemical Transport Experiment-North America (INTEX-NA) that was conducted over the United States during July and August 2004. Relatively zonal flow dominated the contiguous United States during the first 2 weeks of the mission, while a series of large amplitude troughs traversed the eastern half of the country during the final 4 weeks. These troughs were accompanied by cold fronts reaching the Gulf of Mexico, an uncommon occurrence during August. Frontal passages over the northeast were somewhat above average, but the short time interval between passages precluded the formation of stagnant high-pressure centers containing abundant pollution. Atmospheric chemistry during INTEX-NA was heavily influenced by record-breaking fires over Alaska and western Canada. Persistent high pressure over Alaska provided ideal conditions for the wildfires and for transporting their burning by-products southeastward toward the INTEX domain where they were sampled frequently by INTEX aircraft. Forward trajectories and satellite imagery showed that the plumes later were carried to parts of Europe, Africa, and even the Arctic. Deep convection and lightning were important factors during INTEX-NA. Cloud-to-ground (CG) lightning data show that horizontal patterns and numbers of lightning flashes during INTEX-NA are similar to those of 2003 and 2005. Statistics derived from 10 day backward trajectories indicate that the DC-8 often sampled lightning influenced air.

  14. Four chemical methods of porcelain conditioning and their influence over bond strength and surface integrity

    PubMed Central

    Stella, João Paulo Fragomeni; Oliveira, Andrea Becker; Nojima, Lincoln Issamu; Marquezan, Mariana

    2015-01-01

    OBJECTIVE: To assess four different chemical surface conditioning methods for ceramic material before bracket bonding, and their impact on shear bond strength and surface integrity at debonding. METHODS: Four experimental groups (n = 13) were set up according to the ceramic conditioning method: G1 = 37% phosphoric acid etching followed by silane application; G2 = 37% liquid phosphoric acid etching, no rinsing, followed by silane application; G3 = 10% hydrofluoric acid etching alone; and G4 = 10% hydrofluoric acid etching followed by silane application. After surface conditioning, metal brackets were bonded to porcelain by means of the Transbond XP system (3M Unitek). Samples were submitted to shear bond strength tests in a universal testing machine and the surfaces were later assessed with a microscope under 8 X magnification. ANOVA/Tukey tests were performed to establish the difference between groups (?= 5%). RESULTS: The highest shear bond strength values were found in groups G3 and G4 (22.01 ± 2.15 MPa and 22.83 ± 3.32 Mpa, respectively), followed by G1 (16.42 ± 3.61 MPa) and G2 (9.29 ± 1.95 MPa). As regards surface evaluation after bracket debonding, the use of liquid phosphoric acid followed by silane application (G2) produced the least damage to porcelain. When hydrofluoric acid and silane were applied, the risk of ceramic fracture increased. CONCLUSIONS: Acceptable levels of bond strength for clinical use were reached by all methods tested; however, liquid phosphoric acid etching followed by silane application (G2) resulted in the least damage to the ceramic surface. PMID:26352845

  15. Electric Current Activated Combustion Synthesis and Chemical Ovens Under Terrestrial and Reduced Gravity Conditions

    NASA Technical Reports Server (NTRS)

    Unuvar, C.; Fredrick, D.; Anselmi-Tamburini, U.; Manerbino, A.; Guigne, J. Y.; Munir, Z. A.; Shaw, B. D.

    2004-01-01

    Combustion synthesis (CS) generally involves mixing reactants together (e.g., metal powders) and igniting the mixture. Typically, a reaction wave will pass through the sample. In field activated combustion synthesis (FACS), the addition of an electric field has a marked effect on the dynamics of wave propagation and on the nature, composition, and homogeneity of the product as well as capillary flow, mass-transport in porous media, and Marangoni flows, which are influenced by gravity. The objective is to understand the role of an electric field in CS reactions under conditions where gravity-related effects are suppressed or altered. The systems being studied are Ti+Al and Ti+3Al. Two different ignition orientations have been used to observe effects of gravity when one of the reactants becomes molten. This consequentially influences the position and concentration of the electric current, which in turn influences the entire process. Experiments have also been performed in microgravity conditions. This process has been named Microgravity Field Activated Combustion Synthesis (MFACS). Effects of gravity have been demonstrated, where the reaction wave temperature and velocity demonstrate considerable differences besides the changes of combustion mechanisms with the different high currents applied. Also the threshold for the formation of a stable reaction wave is increased under zero gravity conditions. Electric current was also utilized with a chemical oven technique, where inserts of aluminum with minute amounts of tungsten and tantalum were used to allow observation of effects of settling of the higher density solid particles in liquid aluminum at the present temperature profile and wave velocity of the reaction.

  16. 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. 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...

  18. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the experiments run to date suggest that the cement-pozzolans used will be an effective seal for CO2, as long as the well was properly installed and is initially undamaged.

  19. 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...

  20. Conditional Toxicity Value (CTV) Predictor for Generating Toxicity Values for Data Sparse Chemicals (Poster)

    EPA Science Inventory

    Various stakeholders and expert groups, including the National Research Council in Science and Decisions, call for “default approaches to support risk estimation for chemicals lacking chemical-specific information.” This project aims to address this challenge through ...

  1. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 2011-04-01 false Arsenamide sodium aqueous injection. 522.144 Section...ANIMAL DRUGS § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name...Carbamoylphenyl) arsylene]dithio diacetic acid, sodium salt. (b) Specifications....

  2. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 2013-04-01 false Arsenamide sodium aqueous injection. 522.144 Section...ANIMAL DRUGS § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name...Carbamoylphenyl) arsylene]dithio diacetic acid, sodium salt. (b) Specifications....

  3. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 2010-04-01 false Arsenamide sodium aqueous injection. 522.144 Section...ANIMAL DRUGS § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name...Carbamoylphenyl) arsylene]dithio diacetic acid, sodium salt. (b) Specifications....

  4. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 2012-04-01 false Arsenamide sodium aqueous injection. 522.144 Section...ANIMAL DRUGS § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name...Carbamoylphenyl) arsylene]dithio diacetic acid, sodium salt. (b) Specifications....

  5. Transcriptome analysis of the phytobacterium Xylella fastidiosa growing under xylem-based chemical conditions.

    PubMed

    Ciraulo, Maristela Boaceff; Santos, Daiene Souza; Rodrigues, Ana Claudia de Freitas Oliveira; de Oliveira, Marcus Vinícius; Rodrigues, Tiago; de Oliveira, Regina Costa; Nunes, Luiz R

    2010-01-01

    Xylella fastidiosa is a xylem-limited bacterium responsible for important plant diseases, like citrus-variegated chlorosis (CVC) and grapevine Pierce's disease (PD). Interestingly, in vitro growth of X. fastidiosa in chemically defined media that resemble xylem fluid has been achieved, allowing studies of metabolic processes used by xylem-dwelling bacteria to thrive in such nutrient-poor conditions. Thus, we performed microarray hybridizations to compare transcriptomes of X. fastidiosa cells grown in 3G10-R, a medium that resembles grape sap, and in Periwinkle Wilt (PW), the complex medium traditionally used to cultivate X. fastidiosa. We identified 299 transcripts modulated in response to growth in these media. Some 3G10R-overexpressed genes have been shown to be upregulated in cells directly isolated from infected plants and may be involved in plant colonization, virulence and environmental competition. In contrast, cells cultivated in PW show a metabolic switch associated with increased aerobic respiration and enhanced bacterial growth rates. PMID:20625415

  6. [Influence of ancient glass samples surface conditions on chemical composition analysis using portable XRF].

    PubMed

    Liu, Song; Li, Qing-hui; Gan, Fu-xi

    2011-07-01

    Portable X-ray fluorescence analysis (PXRF) is one kind of surface analysis techniques, and the sample surface condition is an important factor that influences the quantitative analysis results. The ancient glass samples studied in the present paper were excavated from Xinjiang, Guangxi, Jiangsu provinces, and they belong to Na2O-CaO-SiO2, K2O-SiO2, and PbO-BaO-SiO2 system, respectively. Quantitative analysis results of weathered surface and inside of the ancient glass samples were compared. The concentration change of main fluxes in different parts of the samples was pointed out. Meanwhile, the authors studied the effect of distance between the sample and the reference plane, and curve shape of the sample on the quantitative results. The results obtained were calibrated by three methods, and the validity of these three methods was proved. Finally, the normalizing method was proved to be a better method for quantitative analysis of antiques. This paper also has guiding significance for chemical composition analysis of ancient jade samples using PXRF. PMID:21942060

  7. Conditionals

    E-print Network

    von Fintel, Kai

    2011-01-01

    This article introduces the classic accounts of the meaning of conditionals (material implication, strict implication, variably strict conditional) and discusses the difference between indicative and subjunctive/counterfactual ...

  8. Transport and Fate of Bacteria in Porous Media: Coupled Effects of Chemical Conditions and Pore Space Geometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experimental and theoretical studies were undertaken to explore the coupling effects of chemical conditions and pore space geometry on bacteria transport in porous media. The retention of Escherichia coli D21g was investigated in a series of batch and column experiments with solutions of different i...

  9. 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…

  10. Evaluating the impact of chemical boundary conditions on near surface ozone in regional climate-air quality simulations over Europe

    NASA Astrophysics Data System (ADS)

    Akritidis, D.; Zanis, P.; Katragkou, E.; Schultz, M. G.; Tegoulias, I.; Poupkou, A.; Markakis, K.; Pytharoulis, I.; Karacostas, Th.

    2013-12-01

    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 chemical lateral boundary conditions (LBCs) on near surface ozone over Europe for the period 1996-2000. The RegCM3 and CAMx simulations were performed on a 50 km × 50 km grid over Europe with RegCM3 driven by the NCEP meteorological reanalysis fields and CAMx with chemical LBCs from ECHAM5/MOZART global model. The recent past period (1996-2000) was simulated in three experiments. The first simulation was forced using time and space invariant LBCs, the second was based on ECHAM5/MOZART chemical LBCs fixed for the year 1996 and the third was based on ECHAM5/MOZART chemical LBCs with interannual variability. Anthropogenic and biogenic emissions were kept identical for the three sensitivity runs.

  11. Metabolic profiling of Lolium perenne shows functional integration of metabolic responses to diverse subtoxic conditions of chemical stress.

    PubMed

    Serra, Anne-Antonella; Couée, Ivan; Renault, David; Gouesbet, Gwenola; Sulmon, Cécile

    2015-04-01

    Plant communities are confronted with a great variety of environmental chemical stresses. Characterization of chemical stress in higher plants has often been focused on single or closely related stressors under acute exposure, or restricted to a selective number of molecular targets. In order to understand plant functioning under chemical stress conditions close to environmental pollution conditions, the C3 grass Lolium perenne was subjected to a panel of different chemical stressors (pesticide, pesticide degradation compound, polycyclic aromatic hydrocarbon, and heavy metal) under conditions of seed-level or root-level subtoxic exposure. Physiological and metabolic profiling analysis on roots and shoots revealed that all of these subtoxic chemical stresses resulted in discrete physiological perturbations and complex metabolic shifts. These metabolic shifts involved stressor-specific effects, indicating multilevel mechanisms of action, such as the effects of glyphosate and its degradation product aminomethylphosphonic acid on quinate levels. They also involved major generic effects that linked all of the subtoxic chemical stresses with major modifications of nitrogen metabolism, especially affecting asparagine, and of photorespiration, especially affecting alanine and glycerate. Stress-related physiological effects and metabolic adjustments were shown to be integrated through a complex network of metabolic correlations converging on Asn, Leu, Ser, and glucose-6-phosphate, which could potentially be modulated by differential dynamics and interconversion of soluble sugars (sucrose, trehalose, fructose, and glucose). Underlying metabolic, regulatory, and signalling mechanisms linking these subtoxic chemical stresses with a generic impact on nitrogen metabolism and photorespiration are discussed in relation to carbohydrate and low-energy sensing. PMID:25618145

  12. All-aqueous multiphase microfluidics

    PubMed Central

    Song, Yang; Sauret, Alban; Cheung Shum, Ho

    2013-01-01

    Immiscible aqueous phases, formed by dissolving incompatible solutes in water, have been used in green chemical synthesis, molecular extraction and mimicking of cellular cytoplasm. Recently, a microfluidic approach has been introduced to generate all-aqueous emulsions and jets based on these immiscible aqueous phases; due to their biocompatibility, these all-aqueous structures have shown great promises as templates for fabricating biomaterials. The physico-chemical nature of interfaces between two immiscible aqueous phases leads to unique interfacial properties, such as an ultra-low interfacial tension. Strategies to manipulate components and direct their assembly at these interfaces needs to be explored. In this paper, we review progress on the topic over the past few years, with a focus on the fabrication and stabilization of all-aqueous structures in a multiphase microfluidic platform. We also discuss future efforts needed from the perspectives of fluidic physics, materials engineering, and biology for fulfilling potential applications ranging from materials fabrication to biomedical engineering. PMID:24454609

  13. Rechargeable Aqueous Microdroplet.

    PubMed

    Phan, Chi M

    2014-04-17

    Directional and controllable transportation of microdroplets is critical for emerging micro- and nanotechnology, in which the conventional mechanical energy generation is not applicable. This Letter shows that an aqueous microdroplet can be charged for controlled motion in electrostatic potential, which was created by differentiating pH, between two oil/water interfaces. The directional motion of the droplet, <100 ?m in diameter, was obtained with a constant velocity of ?1 mm/s. The force analysis showed that the droplet surface was charged and recharged oppositely by ion transfer through interfacial layers, without significant mass transfer. The charging and recharging cycles were recorded continuously with a single droplet over 100 times. The energy for motion was generated from pH neutralization, which is the simplest aqueous reaction. This is the first time that the phenomenon is reported. The phenomenon can be employed as an efficient and robust method to convert chemical to mechanical energy for miniaturized devices and microprocesses. PMID:26269994

  14. Photolysis of oxyfluorfen in aqueous methanol.

    PubMed

    Chakraborty, Subhasish K; Chakraborty, Savitri; Bhattacharyya, Anjan; Chowdhury, Ashim

    2013-01-01

    Photolysis of oxyfluorfen, an herbicide of the nitrodiphenyl ether class, was studied in aqueous methanol under UV and sunlight. UV irradiation was carried out in a borosilicate glass photoreactor (containing 250 ppm oxyfluorfen in 50% aqueous methanol) equipped with a quartz filter and 125 watt mercury lamp (maximum output 254 nm) at 25 ± 1°C. Sunlight irradiation was conducted at 28 ± 1°C in borosilicate Erlenmeyer flasks containing 250 ppm oxyfluorfen in 50% aqueous methanol. The samples from both the irradiated conditions were withdrawn at a definite time interval and extracted to measure oxyfluorfen content by gas chromatography-flame ionization detector for rate study. The half-life values were 20 hours and 2.7 days under UV and sunlight exposure, respectively. Photolysis of oxyfluorfen yielded 13 photoproducts of which three were characterized by infrared spectrophotometer and (1)H NMR and (13)C NMR spectroscopy. The rest of the photoproducts were identified by gas chromatography-mass spectrometry (GC-MS) and thin layer chromatography (TLC). An ionization potential 70 eV was used for electron impact-mass spectrometry (EI-MS) and methane was used as reagent gas for chemical ionization-mass spectrometry (CI-MS). Two of the photoproducts were also synthesized for comparison. The main phototransformation pathways of oxyfluorfen involved nitro reduction, dechlorination, and hydrolysis as well as nucleophiles displacement reaction. PMID:23998303

  15. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions.

    PubMed

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J; Schanz, Hans-Jörg

    2015-01-01

    Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2',6'-dimethyl-4'-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  16. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

    PubMed Central

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J

    2015-01-01

    Summary Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  17. 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

    boron oxides Andrew M. Duffin,1,2 Craig P. Schwartz,1,2 Alice H. England,1,2 Janel S. Uejio,1,2 David-ray absorption fine structure (NEXAFS) spectra at the boron K-edge were measured for aqueous boric acid, borate trajectories from quantum mechanics/molecular mechanics simulations at the experimental temperature. The boron

  18. 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.

  19. Clinical vocabulary as a boundary object in multidisciplinary care management of multiple chemical sensitivity, a complex and chronic condition

    PubMed Central

    Sampalli, Tara; Shepherd, Michael; Duffy, Jack

    2011-01-01

    Background: Research has shown that accurate and timely communication between multidisciplinary clinicians involved in the care of complex and chronic health conditions is often challenging. The domain knowledge for these conditions is heterogeneous, with poorly categorized, unstructured, and inconsistent clinical vocabulary. The potential of boundary object as a technique to bridge communication gaps is explored in this study. Methods: A standardized and controlled clinical vocabulary was developed as a boundary object in the domain of a complex and chronic health condition, namely, multiple chemical sensitivity, to improve communication among multidisciplinary clinicians. A convenience sample of 100 patients with a diagnosis of multiple chemical sensitivity, nine multidisciplinary clinicians involved in the care of patients with multiple chemical sensitivity, and 36 clinicians in the community participated in the study. Results: Eighty-two percent of the multidisciplinary and inconsistent vocabulary was standardized using the Systematized Nomenclature of Medicine – Clinical Terms (SNOMED® CT as a reference terminology. Over 80% of the multidisciplinary clinicians agreed on the overall usefulness of having a controlled vocabulary as a boundary object. Over 65% of clinicians in the community agreed on the overall usefulness of the vocabulary. Conclusion: The results from this study are promising and will be further evaluated in the domain of another complex chronic condition, ie, chronic pain. The study was conducted as a preliminary analysis for developing a boundary object in a heterogeneous domain of knowledge. PMID:21594060

  20. 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.

  1. Sensitivity of the invasive bivalve Corbicula fluminea to candidate control chemicals: The role of dissolved oxygen conditions.

    PubMed

    Rosa, Inês C; Garrido, Rita; Ré, Ana; Gomes, João; Pereira, Joana L; Gonçalves, Fernando; Costa, Raquel

    2015-12-01

    The freshwater Corbicula fluminea is a major aquatic nuisance worldwide. Current pest control methods raise cost-effectiveness and environmental concerns, which motivate research into improved mitigation approaches. In this context, the susceptibility of the clams to chemicals under reduced oxygen conditions was examined. Biocides with different mechanisms of toxicity (niclosamide, polyDADMAC, ammonium nitrate, potassium chloride and dimethoate) were tested under normoxic (>7 mg L(-1) dissolved O2) and hypoxic (<2 mg L(-1) dissolved O2) conditions. Hypoxia was observed to potentiate chemical treatment, particularly when combined with non-overwhelming doses that would produce only intermediate responses by themselves. For niclosamide, ammonium nitrate and dimethoate, clam mortality enhancements up to 400% were observed under hypoxia as compared to dosing upon normal dissolved oxygen conditions. For polyDADMAC and potassium chloride, substantially lower mortality enhancements were found. The differences in the clams' sensitivity to the chemicals under hypoxia could be linked to the expected mechanisms of action. This suggests that judicious selection of the biocide is essential if optimized combined control treatments are to be designed and provides an insight into the interference of frequent hypoxia events in the response of natural clam populations to contaminant loads. PMID:26254082

  2. Chemical conversion of cisplatin and carboplatin with histidine in a model protein crystallized under sodium iodide conditions

    SciTech Connect

    Tanley, Simon W. M.; Helliwell, John R.

    2014-08-29

    Crystals of HEWL with cisplatin and HEWL with carboplatin grown in sodium iodide conditions both show a partial chemical transformation of cisplatin or carboplatin to a transiodoplatin (PtI{sub 2}X{sub 2}) form. The binding is only at the N{sup ?} atom of His15. A further Pt species (PtI{sub 3}X) is also seen, in both cases bound in a crevice between symmetry-related protein molecules. Cisplatin and carboplatin are platinum anticancer agents that are used to treat a variety of cancers. Previous X-ray crystallographic studies of carboplatin binding to histidine in hen egg-white lysozyme (HEWL) showed a partial chemical conversion of carboplatin to cisplatin owing to the high sodium chloride concentration used in the crystallization conditions. Also, the co-crystallization of HEWL with carboplatin in sodium bromide conditions resulted in the partial conversion of carboplatin to the transbromoplatin form, with a portion of the cyclobutanedicarboxylate (CBDC) moiety still present. The results of the co-crystallization of HEWL with cisplatin or carboplatin in sodium iodide conditions are now reported in order to determine whether the cisplatin and carboplatin converted to the iodo form, and whether this took place in a similar way to the partial conversion of carboplatin to cisplatin in NaCl conditions or to transbromoplatin in NaBr conditions as seen previously. It is reported here that a partial chemical transformation has taken place to a transplatin form for both ligands. The NaI-grown crystals belonged to the monoclinic space group P2{sub 1} with two molecules in the asymmetric unit. The chemically transformed cisplatin and carboplatin bind to both His15 residues, i.e. in each asymmetric unit. The binding is only at the N{sup ?} atom of His15. A third platinum species is also seen in both conditions bound in a crevice between symmetry-related molecules. Here, the platinum is bound to three I atoms identified based on their anomalous difference electron densities and their refined occupancies, with the fourth bound atom being a Cl atom (in the cisplatin case) or a portion of the CBDC moiety (in the carboplatin case)

  3. Determination of formal kinetic constants of thermal decomposition of aqueous hydrogen peroxide solution in a mixture of magnetic powder, based on experimental thermogram, obtained in adiabatic conditions

    NASA Astrophysics Data System (ADS)

    Zaripov, Jamshed; Borisov, Boris; Bondarchuk, Sergey

    2014-08-01

    Process of thermal decomposition of hydrogen peroxide aqueous solution with the addition of magnetic powder in the form of toner for printers and lanthanum manganite were considered. Obtained resulting from an experiment in the Dewar container conducted thermogram analyzed using mass balance equations and heat. Formal kinetic parameters determined, and conclude that the magnetic powder in the mixture does not have catalytic properties. The described technique is recommended as a rapid analysis of the kinetics of the various reactions to substances having predefined thermal and thermodynamic properties.

  4. Experimental studies of a single-effect absorption refrigerator using aqueous lithium-bromide: Effect of operating condition to system performance

    SciTech Connect

    Aphornratana, Satha; Sriveerakul, Thanarath

    2007-11-15

    This paper describes an experimental investigation of a single-effect absorption using aqueous lithium-bromide as working fluid. A 2 kW cooling capacity experimental refrigerator was tested with various operating temperatures. It was found that the solution circulation ratio (SCR) has a strong effect on the system performance. The measured SCR was 2-5 times greater than the theoretical prediction. This was due to the low performance of the absorber. The use of solution heat exchanger could increase the COP by up to 60%. (author)

  5. 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. 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.

  7. 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.

  8. Halogen production from aqueous tropospheric particles.

    PubMed

    Herrmann, H; Majdik, Z; Ervens, B; Weise, D

    2003-07-01

    Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values. For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986. It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations. The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br). PMID:12738274

  9. 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.

  10. Inactivation of the novel avian influenza A (H7N9) virus under physical conditions or chemical agents treatment

    PubMed Central

    2013-01-01

    Background In the spring of 2013, a novel avian-origin influenza A (H7N9) virus in Eastern China emerged causing human infections. Concerns that a new influenza pandemic could occur were raised. The potential effect of chemical agents and physical conditions on inactivation of the novel avian influenza H7N9 virus had not been assessed. Methods To determine the inactivation effectiveness of the novel avian influenza A (H7N9) virus under various physical conditions and chemical treatments, two H7N9 viruses A/Anhui/1/2013 and A/Shanghai/1/2013 were treated by varied temperatures, ultraviolet light, varied pHs and different disinfectants. The viruses with107.7 EID50 were exposed to physical conditions (temperature, ultraviolet light and pH) or treated with commercial chemical agents (Sodium Hypochlorite, Virkon®-S, and Ethanol) respectively. After these treatments, the viruses were inoculated in SPF embryonated chicken eggs, the allantoic fluid was collected after 72–96 hours culture at 35°C and tested by haemagglutination assay. Results Both of the tested viruses could tolerate conditions under 56°C for 15 minutes or 60°C for 5 minutes, but their infectivity was completely lost under 56°C for 30 minutes, 65°C for 10 minutes, 70°C, 75°C and 100°C for 1 minute. It was also observed that the H7N9 viruses lost their infectivity totally after exposure of ultraviolet light irradiation for 30 minutes or longer time. Additionally, the viruses were completely inactivated at pH less than 2 for 0.5 hour or pH 3 for 24 hours, however, viruses remained infectious under pH treatment of 4–12 for 24 hours. The viruses were totally disinfected when treated with Sodium Hypochlorite, Virkon®-S and Ethanol at recommended concentrations after only 5 minutes. Conclusions The novel avian influenza A (H7N9) virus can be inactivated under some physical conditions or with chemical treatments, but they present high tolerance to moderately acidic or higher alkali conditions. The results provided the essential information for public health intervention of novel H7N9 avian influenza outbreak. PMID:24034697

  11. State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

    SciTech Connect

    Chase, Zizwe; Kasakov, Stanislav; Shi, Hui; Vjunov, Aleksei; Fulton, John L.; Camaioni, Donald M.; Balasubramanian, Mahalingam; Zhao, Chen; Wang, Yong; Lercher, Johannes A.

    2015-11-09

    The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was determined during aqueous phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy (EXAFS). On sulfonated carbon and HZSM-5 supports, the NiO and Ni(OH)2 were readily reduced to Ni(0) under reaction conditions (~35 bar H2 in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). On the silica support, less than 70% of the Ni was converted to Ni(0) under reaction conditions, which is attributed to the formation of Ni phyllosilicates. Over a broad range of reaction conditions there was no leaching of Ni from the supports. In contrast, rapid leaching of the Ni(II) from HZSM-5 was observed, when 15 wt. % aqueous acetic acid was substituted for the aqueous phenol solution. Once the metallic state of Ni was established there was no leaching in 15 wt. % acetic acid at 473 K and 35 bar H2. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. The STEM was supported under the Laboratory Directed Research and Development Program: Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), a multi-program national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. STEM was performed at EMSL, a DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research and located at PNNL.

  12. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    SciTech Connect

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; Anastasio, Cort N.; Laskin, Julia; Zhang, Qi

    2014-01-01

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (•OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), desorption electrospray ionization mass spectrometry (DESIMS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O/C) ratios of phenolic aqSOA are in the range of 0.85-1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than •OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O/C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.

  13. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

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

    2014-12-23

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenatedmore »molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  14. Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

    DOE PAGESBeta

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

    2014-08-19

    Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol and two methoxy-phenols (syringol and guaiacol) with two major aqueous phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (·OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified,more »including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than ·OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenol had reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV-vis region, suggesting that aqueous-phase reactions of phenols are likely an important source of brown carbon in the atmosphere, especially in regions influenced by biomass burning.« less

  15. Chemical and physical studies of type 3 chondrites. IX. Thermoluminescence and hydrothermal annealing experiments and their relationship to metamorphism and aqueous alteration in type < 3. 3 ordinary chondrites

    SciTech Connect

    Guimon, R.K.; Lofgren, G.E.; Sears, D.W.G.

    1988-01-01

    Samples of four type 3 chondrites have been annealed at 400-850/sup 0/C and 0.77-1 kbar for 10-500 h in the presence of various amounts of water (0-10 wt.%) and sodium disilicate (0-2 molal) and their thermoluminescence properties measured. After annealing for > 20 h at temperatures > 600/sup 0/C, the TL sensitivity of the samples increased by factors of up to 40. After annealing at < 600/sup 0/C for 10-500 h, or relatively short periods at high temperatures (e.g., less than or equal to 20 h at 850/sup 0/C), the TL sensitivity of the samples decreased by up to 2 orders of magnitude (depending on the original value). The TL peak temperatures observed in the present experiments are consistent with a low form of feldspar (the TL phosphor) being produced at < 800/sup 0/C and a high form being produced at > 800/sup 0/C. When both high and low forms were present originally, the low-form was destroyed preferentially. The authors suggest that these data are consistent with the TL-metamorphism trends observed in type > 3.2 chondrites, being due to the formation of feldspar by the devitrification of chondrule glass during metamorphism. For types < 3.2, the TL data are equally consistent with these types experiencing lower levels of metamorphism than the higher types, or with type 3.0 being produced from higher types by aqueous alteration. The presence of water with non-terrestrial D/H ratios, and petrographic evidence for aqueous alteration in Semarkona, lead to favoring the aqueous alteration hypothesis.

  16. 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.

  17. A localized tolerance in the substrate specificity of the fluorinase enzyme enables "last-step" 18F?fluorination of a RGD peptide under ambient aqueous conditions.

    PubMed

    Thompson, Stephen; Zhang, Qingzhi; Onega, Mayca; McMahon, Stephen; Fleming, Ian; Ashworth, Sharon; Naismith, James H; Passchier, Jan; O'Hagan, David

    2014-08-18

    A strategy for last-step (18)F?fluorination of bioconjugated peptides is reported that exploits an "Achilles heel" in the substrate specificity of the fluorinase enzyme. An acetylene functionality at the C-2?position of the adenosine substrate projects from the active site into the solvent. The fluorinase catalyzes a transhalogenation of 5'-chlorodeoxy-2-ethynyladenosine (ClDEA) to 5'-fluorodeoxy-2-ethynyladenosine (FDEA). Extending a polyethylene glycol linker from the terminus of the acetylene allows the presentation of bioconjugation cargo to the enzyme for (18)F?labelling. The method uses an aqueous solution?(H2(18)O) of [(18)F]fluoride generated by the cyclotron and has the capacity to isotopically label peptides of choice for positron emission tomography (PET). PMID:24989327

  18. Constant Trace Anomaly as a Universal Condition for the Chemical Freeze-Out

    E-print Network

    A. Tawfik

    2013-08-07

    Finding out universal conditions describing the freeze-out parameters was a 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 {\\it ideal} HRG which are conjectured to take into consideration different types of interactions have been analysed. 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 of previous conditions.

  19. [Hygienic assessment of labor conditions in chemical industry sites during reconstruction].

    PubMed

    Mikha?luts, A P; Pershin, A N

    1990-01-01

    In periods of reconstruction of chemical enterprises, hazardous compounds concentrations may exceed MAC, they are also characterized by contamination of the skin with toxic substances, welding aerosols discharge into the working zone, and microclimate distabilization. The workers' health states display functional shifts with concomitant decrease of labour productivity, increase heart rates, a higher 11-oxycorticosteroids contents in saliva and peroxidase activity. Morbidity with temporary disability also increases. A range of health improving measures is needed to be performed at the stages of preventive sanitary control. PMID:2376335

  20. 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

  1. 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...

  2. Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KLII&III, KLI) x-ray absorption near-edge spectra of ?-alumina, sodium aluminate, aqueous Al³?•(H?O)?, and aqueous Al(OH)??

    SciTech Connect

    Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas; Bylaska, Eric J.; Vjunov, Aleksei; Pin, Sonia; Smurthwaite, Tricia D.

    2015-07-02

    We probe, at high energy resolution, the double electron excitation (KLII&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of ?-alumina and sodium aluminate. The two solid standards, ?-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³?•6H?O (octahedral) and Al(OH)?? (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the ?-alumina and aqueous Al³?•6H?O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&III and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (?SCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the ?-Al?O? and tetrahedral sodium aluminate (NaAlO?) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle under Contract # AC05-76RL01830.

  3. Impact of engineering flow conditions on plasmid DNA yield and purity in chemical cell lysis operations.

    PubMed

    Meacle, F J; Lander, R; Ayazi Shamlou, P; Titchener-Hooker, N J

    2004-08-01

    Chemical lysis of bacterial cells using an alkaline solution containing a detergent may provide an efficient scalable means for selectively removing covalently closed circular plasmid DNA from high-molecular-weight contaminating cellular components including chromosomal DNA. In this article we assess the chemical lysis of E. coli cells by SDS in a NaOH solution and determine the impact of pH environment and shear on the supercoiled plasmid and chromosomal DNA obtained. Experiments using a range of plasmids from 6 kb to 113 kb determined that in an unfavorable alkaline environment, where the NaOH concentration during lysis is greater than 0.15 +/- 0.03 M (pH 12.9 +/- 0.2), irreversible denaturation of the supercoiled plasmid DNA occurs. The extent of denaturation is shown to increase with time of exposure and NaOH concentration. Experiments using stirred vessels show that, depending on NaOH concentration, moderate to high mixing rates are necessary to maximize plasmid yield. While NaOH concentration does not significantly affect chromosomal DNA contamination, a high NaOH concentration is necessary to ensure complete conversion of chromosomal DNA to single-stranded form. In a mechanically agitated lysis reactor the correct mixing strategy must balance the need for sufficient mixing to eliminate potential regions of high NaOH concentrations and the need to avoid excessive breakage of the shear sensitive chromosomal DNA. The effect of shear on chromosomal DNA is examined over a wide range of shear rates (10(1)-10(5) s(-1)) demonstrating that, while increasing shear leads to fragmentation of chromosomal DNA to smaller sizes, it does not lead to significantly increased chromosomal DNA contamination except at very high shear rates (about 10(4)-10(5) s(-1)). The consequences of these effects on the choice of lysis reactor and scale-up are discussed. PMID:15281104

  4. Aqueous Geochemistry at High Pressures and High Temperatures

    SciTech Connect

    Bass, Jay D.

    2015-05-21

    This project is aimed at experimental characterization of the sound velocities, equations of state (EOS), and derived physical and chemical properties of aqueous solutions and carbon dioxide at extreme pressure and temperature conditions relevant to processes occurring in the interior of the Earth. Chemical transport, phase changes (including melting), fluid-solid reactions, and formation of magmatic liquids at convergent plat boundaries are a key motivation for this project. Research in this area has long been limited by the extreme experimental challenges and lack of data under the appropriate pressure-temperature (P-T) conditions. The vast majority of studies of aqueous geochemistry relevant to terrestrial problems of fluid-rock interactions have been conducted at 0.3 GPa or less, and the widely used Helgeson-Kirkham-Flowers equation of state for aqueous species is applicable only at ~ < 0.5 GPa. These limits are unfortunate because fluid flow and reactions plays a central role in many deeper environments. Recent efforts including our own, have resulted in new experimental techniques that now make it possible to investigate properties of homogeneous and heterogeneous equilibria involving aqueous species and minerals over a much broader range of pressure and temperature appropriate for deep crustal and upper mantle processes involving water-rich fluids. We carried out 1) Brillouin scattering measurements of the equations of state and molar volume of water and carbon dioxide to over 10 GPa and 870K using precise resistance heating of samples under pressure in the diamond anvil cell, and 2) the phase diagrams of the water and CO2, and 3) Exploring new experimental approaches, including CO2 laser heating of samples in a diamond cell, to measurements of sound velocities, EOS, and phase relations by Brillouin scattering to far greater pressures and temperatures.

  5. Influence of the synthesis conditions of silicon nanodots in an industrial low pressure chemical vapor deposition reactor

    NASA Astrophysics Data System (ADS)

    Cocheteau, V.; Scheid, E.; Mur, P.; Billon, T.; Caussat, B.

    2008-03-01

    Experiments conducted in an industrial tubular low pressure chemical vapor deposition (LPCVD) reactor have demonstrated the reproducibility and spatial uniformity of silicon nanodots (NDs) area density and mean radius. The wafer to wafer uniformity was satisfactory (density and radius standard deviations <10%) for the whole conditions tested except for low silane flow rates, high silane partial pressures and short run durations (<20 s). Original synthesis conditions have then been searched to reach both excellent wafer to wafer uniformities along the industrial load of wafers and high NDs densities. From previous results, it was deduced that the key was to markedly increase run duration in decreasing temperature and in increasing silane pressure. At 773 K, run durations as long as 180 and 240 s have thus allowed to reach NDs densities respectively equal to 9 × 10 11 and 6.5 × 10 11 NDs/cm 2 for the two highest silane pressures tested in the range 60-150 Pa.

  6. Degradation kinetics of atorvastatin under stress conditions and chemical analysis by HPLC.

    PubMed

    Oliveira, Marcelo Antonio; Yoshida, Maria Irene; Belinelo, Valdenir José; Valotto, Romanélia Spessemille

    2013-01-01

    Atorvastatin is an antilipemic drug belonging to the statins class, whose reference drug is Pfizer's Lipitor®. It is used to reduce the levels of lipoproteins rich in cholesterol and reduce the risk of coronary artery disease. It is well-known that calcium atorvastatin (ATV), C??H??CaF?N?O??•3H?O, presents polymorphism. The drug in question is commonly sought after by pharmaceutical industries that produce generic drugs, due to the fact that the drug has a high value price, it is consumed globally, and its patent expired in late 2010. Many questions concerning this drug's pharmaceutical scope demonstrate its importance regarding stability studies and the identification of degradation products of drugs and pharmaceutical formulations. ATV has been found to degrade under acid and basic conditions, including a first order kinetic degradation under acid conditions, as compared to a zero order kinetic degradation under basic conditions, which tends to be less stable when studied within acid mediums. The rate constant (k) for degradation in acid medium was 1.88 × 10?² s?¹ (first order), while for basic medium k = 2.35 × 10?? mol L?¹ s?¹ (zero order), demonstrating a lower stability of the drug within acid mediums. PMID:23348997

  7. Chemical changes exhibited by latent fingerprints after exposure to vacuum conditions.

    PubMed

    Bright, Nicholas J; Willson, Terry R; Driscoll, Daniel J; Reddy, Subrayal M; Webb, Roger P; Bleay, Stephen; Ward, Neil I; Kirkby, Karen J; Bailey, Melanie J

    2013-07-10

    The effect of vacuum exposure on latent fingerprint chemistry has been evaluated. Fingerprints were analysed using a quartz crystal microbalance to measure changes in mass, gas chromatography mass spectrometry to measure changes in lipid composition and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to determine changes in the content of water, fatty acids and their esters after exposure to vacuum. The results are compared with samples aged under ambient conditions. It was found that fingerprints lose around 26% of their mass when exposed to vacuum conditions, equivalent to around 5 weeks ageing under ambient conditions. Further exposure to vacuum causes a significant reduction in the lipid composition of a fingerprint, in particular with the loss of tetradecanoic and pentadecanoic acid, that was not observed in ambient aged samples. There are therefore implications for sequence in which fingerprint development procedures (for example vacuum metal deposition) are carried out, as well as the use of vacuum based methods such as secondary ion mass spectrometry (SIMS) and matrix-assisted laser desorption ionisation (MALDI) in the study of fingerprint chemistry. PMID:23622791

  8. 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

  9. 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.

  10. Aqueous cleaning design presentation

    NASA Technical Reports Server (NTRS)

    Maltby, Peter F.

    1995-01-01

    The phase-out of CFC's and other ozone depleting chemicals has prompted industries to re-evaluate their present methods of cleaning. It has become necessary to find effective substitutes for their processes as well as to meet the new cleaning challenges of improved levels of cleanliness and to satisfy concerns about environmental impact of any alternative selected. One of the most popular alternatives being selected is aqueous cleaning. This method offers an alternative for removal of flux, grease/oil, buffing compound, particulates and other soils while minimizing environmental impact. What I will show are methods that can be employed in an aqueous cleaning system that will make it environmentally friendly, relatively simple to maintain and capable of yielding an even higher quality of cleanliness than previously obtained. I will also explore several drying techniques available for these systems and other alternatives along with recent improvements made in this technology. When considering any type of cleaning system, a number of variables should be determined before selecting the basic configuration. Some of these variables are: (1) Soil or contaminants being removed from your parts; (2) The level of cleanliness required; (3) The environmental considerations of your area; (4) Maintenance requirements; and (5) Operating costs.

  11. A 3D microfibrous scaffold for long-term human pluripotent stem cell self-renewal under chemically defined conditions.

    PubMed

    Lu, Hong Fang; Narayanan, Karthikeyan; Lim, Sze-Xian; Gao, Shujun; Leong, Meng Fatt; Wan, Andrew C A

    2012-03-01

    Realizing the potential of human pluripotent stem cell (hPSC)-based therapy requires the development of defined scalable culture systems with efficient expansion, differentiation and isolation protocols. We report an engineered 3D microfiber system that efficiently supports long-term hPSCs self-renewal under chemically defined conditions. The unique feature of this system lies in the application of a 3D ECM-like environment in which cells are embedded, that affords: (i) uniform high cell loading density in individual cell-laden constructs (?10(7) cells/ml); (ii) quick recovery of encapsulated cells (<10min at 37°C) with excellent preservation of cell viability and 3D multicellular structure; (iii) direct cryopreservation of the encapsulated cells in situ in the microfibers with >17-fold higher cell viability compared to those cultured on Matrigel surface; (iv) long-term hPSC propagation under chemically defined conditions. Four hPSC lines propagated in the microfibrous scaffold for 10 consecutive passages were capable of maintaining an undifferentiated phenotype as demonstrated by the expression of stem cell markers and stable karyotype in vitro and the ability to form derivatives of the three germ layers both in vitro and in vivo. Our 3D microfibrous system has the potential for large-scale cultivation of transplantable hESCs and derivatives for clinical applications. PMID:22196900

  12. Composition and freezing of aqueous H[sub 2]SO[sub 4]/HNO[sub 3] solutions under polar stratospheric conditions

    SciTech Connect

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

    1994-05-15

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H[sub 2]SO[sub 4]/H[sub 2]O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO[sub 3]; however, in the presence of typical levels of HNO[sub 3] liquid sulfuric acid aerosols take up significant amounts of HNO[sub 3] and H[sub 2]O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO[sub 3] and H[sub 2]O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO[sub 3]/H[sub 2]O [open quotes]dew point[close quotes] is typically around 192-194 K at 100 mbar. 13 refs., 2 figs., 4 tabs.

  13. 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.

  14. 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.

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

    SciTech Connect

    Hata, Kuniki; Advanced Science Research Center, Japan Atomic Energy Agency, 2-4 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1195 ; Urushibara, Ayumi; Yamashita, Shinichi; Shikazono, Naoya; Yokoya, Akinari; Katsumura, Yosuke; Nuclear Professional School, School of Engineering, The University of Tokyo, 2-22 Shirakatashirane, Tokai-mura, Naka-gun, Ibaraki 319-1188

    2013-05-03

    Highlights: •We report a novel mechanism of radiation protection of DNA by chemical activity of ascorbic acid. •The “chemical repair” of DNA damage was revealed using biochemical assay and chemical kinetics analysis. •We found that ascorbic acid significantly repairs precursors of nucleobase lesions and abasic sites. •However, ascorbic acid seldom repairs precursors of DNA-strand breaks. -- Abstract: We quantified the damage yields produced in plasmid DNA by ?-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.

  16. Low-thrust chemical propulsion system propellant expulsion and thermal conditioning study

    NASA Technical Reports Server (NTRS)

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

    1982-01-01

    Thermal conditioning systems for satisfying engine net positive suction pressure (NPSP) requirements, and propellant expulsion systems for achieving propellant dump during a return-to-launch site (RTLS) abort were studied for LH2/LO2 and LCH4/LO2 upper stage propellant combinations. A state-of-the-art thermal conditioning system employing helium injection beneath the liquid surface shows the lowest weight penalty for LO2 and LCH4. A technology system incorporating a thermal subcooler (heat exchanger) for engine NPSP results in the lowest weight penalty for the LH2 tank. A preliminary design of two state-of-the-art and two new technology systems indicates a weight penalty difference too small to warrant development of a LH2 thermal subcooler. Analysis results showed that the LH2/LO2 propellant expulsion system is optimized for maximum dump line diameters, whereas the LCH4/LO2 system is optimized for minimum dump line diameter (LCH4) and maximum dump line diameter (LO2). The primary uncertainty is the accurate determination of two-phase flow rates through the dump system; experimentation is not recommended because this uncertainty is not considered significant.

  17. Meteorites and the physico-chemical conditions in the early solar nebula

    E-print Network

    Jerome Aleon

    2008-09-10

    Chondritic meteorites constitute the most ancient rock record available in the laboratory to study the formation of the solar system and its planets. Detailed investigations of their mineralogy, petrography, chemistry and isotopic composition and comparison with other primitive solar system samples such as cometary dust particles have allowed through the years to decipher the conditions of formation of their individual components thought to have once been free-floating pieces of dust and rocks in the early solar nebula. When put in the context of astrophysical models of young stellar objects, chondritic meteorites and cometary dust bring essential insights on the astrophysical conditions prevailing in the very first stages of the solar system. Several exemples are shown in this chapter, which include (1) high temperature processes and the formation of chondrules and refractory inclusions, (2) oxygen isotopes and their bearing on photochemistry and large scale geochemical reservoirs in the nebula, (3) organosynthesis and cold cloud chemistry recorded by organic matter and hydrogen isotopes, (4) irradiation of solids by flares from the young Sun and finally (5) large scale transport and mixing of material evidenced in chondritic interplanetary dust particles and samples returned from comet Wild2 by the Stardust mission.

  18. 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.

  19. 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

  20. 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

  1. Anthemis xylopoda flowers aqueous extract assisted in situ green synthesis of Cu nanoparticles supported on natural Natrolite zeolite for N-formylation of amines at room temperature under environmentally benign reaction conditions.

    PubMed

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad; Hatamifard, Arezo

    2015-12-15

    Zeolites, which are nontoxic, abundant, and cheap, are very promising supports for the design and preparation of new and environmentally benign catalysts. In this study, Cu nanoparticles (NPs) were immobilized on the surface of natural Natrolite zeolite by Anthemis xylopoda flowers aqueous extract as a reducing and stabilizing agent. Afterward, the catalytic performance of the prepared catalyst was investigated for N-formylation of amines at room temperature under environmentally benign reaction conditions. The catalyst could be reused at least 5 times without any decrease in activity. The advantages of the present protocol include the use of green catalyst, easy isolation of the products, reusability of catalyst, absence of nontoxic reagents, and excellent yield of the products. PMID:26319331

  2. Bioenhanced dissolution of dense non-aqueous phase of trichloroethylene as affected by iron reducing conditions: model systems and environmental samples.

    PubMed

    Paul, Laiby; Smolders, Erik

    2015-01-01

    The anaerobic biotransformation of trichloroethylene (TCE) can be affected by competing electron acceptors such as Fe (III). This study assessed the role of Fe (III) reduction on the bioenhanced dissolution of TCE dense non-aqueous phase liquid (DNAPL). Columns were set up as 1-D diffusion cells consisting of a lower DNAPL layer, a layer with an aquifer substratum and an upper water layer that is regularly refreshed. The substrata used were either inert sand or sand coated with 2-line ferrihydrite (HFO) or two environmental Fe (III) containing samples. The columns were inoculated with KB-1 and were repeatedly fed with formate. In none of the diffusion cells, vinyl chloride or ethene was detected while dissolved and extractable Fe (II) increased strongly during 60 d of incubation. The cis-DCE concentration peaked at 4.0 cm from the DNAPL (inert sand) while it was at 3.4 cm (sand+HFO), 1.7 cm and 2.5 cm (environmental samples). The TCE concentration gradients near the DNAPL indicate that the DNAPL dissolution rate was larger than that in an abiotic cell by factors 1.3 (inert sand), 1.0 (sand+HFO) and 2.2 (both environmental samples). This results show that high bioavailable Fe (III) in HFO reduces the TCE degradation by competitive Fe (III) reduction, yielding lower bioenhanced dissolution. However, Fe (III) reduction in environmental samples was not reducing TCE degradation and the dissolution factor was even larger than that of inert sand. It is speculated that physical factors, e.g. micro-niches in the environmental samples protect microorganisms from toxic concentrations of TCE. PMID:25460750

  3. A novel low cost non-aqueous chemical route for giant dielectric constant CaCu3Ti4O12 ceramic

    NASA Astrophysics Data System (ADS)

    Singh, Laxman; Kim, Ill Won; Woo, Won Seok; Sin, Byung Cheol; Lee, Hyung-il; Lee, Youngil

    2015-05-01

    This paper reports a simple, fast, low cost and environment-friendly route for preparing a highly crystalline giant dielectric material, CaCu3Ti4O12 (CCTO), through combustion of metal nitrates in non-aqueous precursor solution using inexpensive solid TiO2 powder. The route to producing pure phase CCTO ceramic using stable solid TiO2 is better than other several sol-gel routes reported earlier in which expensive alkoxides, oxynitrates, or chlorides of titanium are used as the titanium sources. X-ray diffraction revealed the formation of cubic perovskite CCTO. Scanning electron microscopy image showed the average grain sizes in the range of 1.5-5 ?m. At 10 kHz and room temperature, the best CCTO ceramic exhibited a high dielectric constant, ?? ?43325.24, with low dielectric loss, tan ? ?0.088. The dielectric relaxation behavior was rationalized from impedance and modulus studies and the presence of a non-Debye type of relaxation was confirmed.

  4. Capillary electrophoresis with capacitively coupled contactless conductivity detection applied to the quantitation and to the determination of physical-chemical properties of peroxycarboxylates in aqueous medium.

    PubMed

    Vidal, Denis T R; do Lago, Claudimir L

    2013-07-01

    CE with C?D (CE-C?D) was successfully applied to the investigation of performate, peracetate, and perpropionate in aqueous medium. Ionic mobilities, diffusion coefficients, and hydrodynamic radii were obtained for the first time for these species. CE-C?D was also used to estimate the pKa values of the peroxycarboxylic acids. Because the peroxycarboxylates (POCs) undergoes hydrolysis while migrating, a simple calibration curve cannot be used for quantitation. Thus, an indirect calibration approach was used. The new method was used to monitor the formation of peroxycarboxylic acids from hydrogen peroxide and the carboxylic acid as well as to the quantitation of peracetic acid in a commercial sample. The CE-C?D method compares favorably with the conventional titration method because of the possibility of speciation of the POC, the low sample consumption, and the low LOD (14, 8, and 24 ?mol/L for performate, peracetate, and perpropionate, respectively). Although POCs are structural isomers of monoalkyl carbonates, they have greater hydrodynamic radii, which suggests that the positions of the oxygen atoms in the molecules have a direct impact in the charge density and consequently on the hydration atmosphere. PMID:23595363

  5. 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.

  6. Effects of spray-drying conditions on the chemical, physical, and sensory properties of cheese powder.

    PubMed

    Koca, Nurcan; Erbay, Zafer; Kaymak-Ertekin, Figen

    2015-05-01

    Dairy powders are produced to increase the shelf life of fresh dairy products and for use as flavoring agents. In this study, 24 cheese powders produced under 7 different conditions were used to investigate the effects of spray-drying parameters (e.g., inlet air temperature, atomization pressure, and outlet air temperature) on the quality of white cheese powder. Composition, color, physical properties, reconstitution, and sensory characteristics of white cheese powders were determined. The results revealed that the white cheese powders produced in this study had low moisture content ratios and water activity values. High outlet air temperatures caused browning and enhanced Maillard reactions. Additionally, high outlet air temperatures increased wettability and dispersibility and decreased the solubility of white cheese powders. Free fat content was positively correlated with inlet air temperature and negatively correlated with outlet air temperature and atomization pressure. Sensory analyses revealed that white cheese powder samples had acceptable sensory characteristics with the exception of the sample produced at an outlet air temperature of 100°C, which had high scores for scorched flavor and color and low scores for cheese flavor. PMID:25771045

  7. 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

  8. Chemical reaction conditions in a Danish 80 MW{sub th} CFB-boiler co-firing straw and coal

    SciTech Connect

    Hansen, P.F.B.

    1997-12-31

    Future boilers to be constructed in Denmark including boilers intended for energy conversion of biomass (straw and wood chips) will be designed for Ultra Super Critical steam data. The high steam temperatures and subsequently metal temperatures in the superheaters will increase the corrosion hazard significantly. Severe superheater corrosion observed in the convective path and on test tubes inserted into the loop seal of a Danish 80 MW{sub th} Ahlstroem Pyroflow CFB boiler co-firing coal and straw initiated this study on the conditions under which the chemical reactions occur and deposits form. Load changes--caused by variations in public demand for district heating shifts the reaction conditions in the loop seal between predominantly reducing and predominantly oxidizing conditions. Furthermore the external particle circulation rate and the local temperatures are strongly affected. Deposits collected in the loop seal on temperature controlled probes reveals Cl concentrations more than Twenty Thousand times higher than found in the surrounding bed material. The results are discussed and suggestions on how to reduce high temperature corrosion and superheater fouling are presented.

  9. 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...

  10. Balancing Equations Chemical Reactions

    E-print Network

    Heller, Barbara

    Balancing Equations Chemical Reactions #12;Chemical Equations · A chemical equation describes what of the participants (solid, liquid, gas, aqueous) and the amount of each substance. #12;Balancing of Equations · To balance a chemical equation, you have to establish a mathematical relationship between the quantity

  11. A chemical kinetic model for NO{sub x} removal in an aqueous scrubber system using the additive Fe[II]{center_dot}EDTA

    SciTech Connect

    Mendelsohn, M.H.; Livengood, C.D.

    1992-09-01

    Addition of the metal chelate, ferrous{center_dot} ethylenediaminetetraacetate anion (Fe[II]{center_dot}EDTA{sup 2{minus}}), has been shown to increase the amount of gaseous nitrogen oxides absorbed from a gas stream containing sulfur dioxide, where an aqueous scrubbing process is used to treat the gas. Recently, we published data on improved systems for NO{sub x} removal that incorporate an antioxidant and/or reducing agent (A/R) in the process along with the Fe[H]{center_dot}EDTA. The purpose of the A/R is to maintain the highest possible concentration of iron in the +2 form. The major mechanism for NO removal is believed to be the equilibrium reaction of Fe[II]{center_dot}EDTA with dissolved NO to form a Fe[II]{center_dot}EDTA{center_dot}NO complex. It has been shown that both sulfite and bisulfite anions can react with Fe[II]{center_dot}EDTA{center_dot}NO to regenerate Fe[II]{center_dot}EDTA and other products. In a complex system, other oxidation and reduction mechanisms are also possible. We have chosen, therefore, to approach this problem empirically by fitting our experimental data to a model containing at most three kinetic terms, chosen from among the following: a baseline removal rate, which is equivalent to the rate of reaction of Fe[II]{center_dot}EDTA with nitric oxide; a regeneration rate, which is equivalent to decomposition of the Fe[II]{center_dot}EDTA{center_dot}NO complex to Fe[II]{center_dot}EDTA; an oxidation rate, which is a combined rate for all possible oxidation reactions involving Fe[II]{center_dot}EDTA; and a reduction rate, which is a combined rate for all possible reduction reactions involving ferric-EDTA in the system.

  12. Effect of vacuum conditions and plasma concentration on the chemical composition and adhesion of vacuum-plasma coatings

    NASA Astrophysics Data System (ADS)

    Borisov, D. P.; Kuznetsov, V. M.; Slabodchikov, V. A.

    2015-11-01

    The paper reports on the chemical composition of titanium nitride (TiN) and silicon (Si) coatings deposited with a new technological vacuum plasma setup which comprises magnetron sputtering systems, arc evaporators, and an efficient plasma generator. It is shown that due to highly clean vacuum conditions and highly clean surface treatment in the gas discharge plasma, both the coating-substrate interface and the coatings as such are almost free from oxygen and carbon. It is found that the coating-substrate interface represents a layer of thickness ? 60 nm formed through vacuum plasma mixing of the coating and substrate materials. The TiN coatings obtained on the new equipment display a higher adhesion compared to brass coatings deposited by industrial technologies via intermediate titanium oxide layers. It is concluded that the designed vacuum plasma equipment allows efficient surface modification of materials and articles by vacuum plasma immersion processes.

  13. 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.

  14. 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

  15. Well aligned ZnO nanorods growth on the gold coated glass substrate by aqueous chemical growth method using seed layer of Fe3O4 and Co3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ibupoto, Z. H.; Khun, K.; Lu, Jun; Liu, Xianjie; AlSalhi, M. S.; Atif, M.; Ansari, Anees A.; Willander, M.

    2013-04-01

    In this study, Fe3O4 and Co3O4 nanoparticles were prepared by co-precipitation method and sol-gel method respectively. The synthesised nanoparticles were characterised by X-ray diffraction [XRD] and Raman spectroscopy techniques. The obtained results have shown the nanocrystalline phase of obtained Fe3O4 and Co3O4 nanoparticles. Furthermore, the Fe3O4 and Co3O4 nanoparticles were used as seed layer for the fabrication of well-aligned ZnO nanorods on the gold coated glass substrate by aqueous chemical growth method. Scanning electron microscopy (SEM), high resolution transmission electron microscopy [HRTEM], as well as XRD and energy dispersive X-ray techniques were used for the structural characterisation of synthesised ZnO nanorods. This study has explored highly dense, uniform, well-aligned growth pattern along 0001 direction and good crystal quality of the prepared ZnO nanorods. ZnO nanorods are only composed of Zn and O atoms. Moreover, X-ray photoelectron spectroscopy was used for the chemical analysis of fabricated ZnO nanorods. In addition, the structural characterisation and the chemical composition study and the optical investigation were carried out for the fabricated ZnO nanorods and the photoluminescence [PL] spectrum have shown strong ultraviolet (UV) peak at 381 nm for Fe3O4 nanoparticles seeded ZnO nanorods and the PL spectrum for ZnO nanorods grown with the seed layer of Co3O4 nanoparticles has shown a UV peak at 382 nm. The green emission and orange/red peaks were also observed for ZnO nanorods grown with both the seed layers. This study has indicated the fabrication of well aligned ZnO nanorods using the one inorganic nanomaterial on other inorganic nanomaterial due to their similar chemistry.

  16. 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.

  17. 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

  18. The Effect of Variety and Growing Conditions on the Chemical Composition and Nutritive Value of Wheat for Broilers

    PubMed Central

    Ball, M. E. E.; Owens, B.; McCracken, K. J.

    2013-01-01

    The aim of this study was to examine the effect of variety and growing conditions of wheat on broiler performance and nutrient digestibility. One hundred and sixty-four wheat samples, collected from a wide range of different sources, locations, varieties and years, were analyzed for a range of chemical and physical parameters. Chemical and physical parameters measured included specific weight, thousand grain weight (TG), in vitro viscosity, gross energy, N, NDF, starch, total and soluble non-starch polysaccharides (NSP), lysine, threonine, amylose, hardness, rate of starch digestion and protein profiles. Ninety-four of the wheat samples were selected for inclusion in four bird trials. Birds were housed in individual wire metabolizm cages from 7 to 28 d and offered water and feed ad libitum. Dry matter intake (DMI), live weight gain (LWG) and gain:feed were determined weekly. A balance collection was carried out from 14 to 21 d for determination of apparent metabolizable energy (AME), ME:gain, DM retention, oil and NDF digestibility. At 28 d the birds were sacrificed, the contents of the jejunum removed for determination of in vivo viscosity and the contents of the ileum removed for determination of ileal DM, starch and protein digestibility. The wheat samples used in the study had wide-ranging chemical and physical parameters, leading to bird DMI, LWG, gain:feed, ME:GE, AME content and ileal starch and protein digestibility being significantly (p<0.05) affected by wheat sample. A high level of N fertilizer application to the English and NI wheat samples tended to benefit bird performance, with increases of up to 3.4, 7.2 and 3.8% in DMI, LWG and gain:feed, respectively. Fungicide application also appeared to have a positive effect on bird performance, with fungicide treated (+F) wheat increasing bird DMI, LWG and gain:feed by 6.6, 9.3 and 2.7%, over the non-fungicide treated (-F) wheats. An increase (p<0.1) of 9.3% in gain:feed was also observed at the low seed rate of 40 compared to 640 seeds/m2. It was concluded that the type of wheat sample and environmental growing conditions significantly affects bird performance when fed wheat-based diets. PMID:25049800

  19. Testing Insecticidal Activity of Novel Chemically Synthesized siRNA against Plutella xylostella under Laboratory and Field Conditions

    PubMed Central

    Gong, Liang; Chen, Yong; Hu, Zhen; Hu, Meiying

    2013-01-01

    Background Over the last 60 years, synthetic chemical pesticides have served as a main tactic in the field of crop protection, but their availability is now declining as a result of the development of insect resistance. Therefore, alternative pest management agents are needed. However, the demonstration of RNAi gene silencing in insects and its successful usage in disrupting the expression of vital genes opened a door to the development of a variety of novel, environmentally sound approaches for insect pest management. Methodology/Principal Findings Six small interfering RNAs (siRNAs) were chemically synthesized and modified according to the cDNA sequence of P. xylostella acetylcholine esterase genes AChE1 and AChE2. All of them were formulated and used in insecticide activity screening against P. xylostella. Bioassay data suggested that Si-ace1_003 and Si-ace2_001 at a concentration of 3 µg cm?2 displayed the best insecticidal activity with 73.7% and 89.0%, mortality, respectively. Additional bioassays were used to obtain the acute lethal concentrations of LC50 and LC90 for Si-ace2_001, which were 53.66 µg/ml and 759.71 µg/ml, respectively. Quantitative Real-time PCR was used to confirm silencing and detected that the transcript levels of P. xylostella AChE2 (PxAChE2) were reduced by 5.7-fold compared to the control group. Consequently, AChE activity was also reduced by 1.7-fold. Finally, effects of the siRNAs on treated plants of Brassica oleracea and Brassica alboglabra were investigated with different siRNA doses. Our results showed that Si-ace2_001 had no negative effects on plant morphology, color and growth of vein under our experimental conditions. Conclusions The most important finding of this study is the discovery that chemically synthesized and modified siRNA corresponding to P. xylostella AChE genes cause significant mortality of the insect both under laboratory and field conditions, which provides a novel strategy to control P. xylostella and to develop bio-pesticides based on the RNA interference technology. PMID:23667556

  20. 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.

  1. 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

  2. Influence of annealing conditions on the crystallographic structure, chemical composition and luminescence of ZnO thin films

    NASA Astrophysics Data System (ADS)

    Khojier, K.; Savaloni, H.; Amani, E.

    2014-01-01

    ZnO thin films have many applications in semiconductor devices, such as semiconductor lasers, amplifiers, solar cells, chemical and ultraviolet sensors. We produced ZnO thin films on Si (4 0 0) substrates, using e-beam technique and subsequently annealed them under different conditions (i.e., temperature (200-800), time (60 min and 180 min) and environment (air and oxygen flow). The ZnO (0 0 2) preferred orientation which increases in intensity with annealing temperature and annealing time is deduced from X-ray diffraction (XRD) results. Dislocation density was higher for the films annealed in air which may be caused by the impurities (nitrogen and other species in the air) embedded in the film structure. No significant change in the nano-strain of each group of the samples (annealed under different conditions) was observed. The FESEM images showed a granular structure for annealed samples at 200 °C and 800 °C and a mixed structure of nanowires and nanosheets for samples annealed at 350 °C and 500 °C. Two peaks of UV emission and green emission were observed in the photoluminescence (PL) spectra of the produced samples. The UV emission increased with annealing temperature and annealing time showing higher crystal quality while the behavior of the green emission was opposite to that of the UV emission. The ZnO films resulted from annealing in the air showed stronger green emission than those annealed with flow of oxygen indicating higher impurity concentration and oxygen vacancies in the sample.

  3. 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.

  4. 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

  5. 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

  6. Aqueous chemical growth of Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films: Air annealing and photoelectrochemical properties

    SciTech Connect

    Shinde, N.M.; Deshmukh, P.R.; Patil, S.V.; Lokhande, C.D.

    2013-05-15

    Highlights: ? Facile and efficient route for synthesis of CZTS film. ? Effect of annealing on structural, morphological and electrical properties of CZTS films. ? Solar cell study. - Abstract: In present investigation, Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films have been deposited on to glass substrates by novel chemical successive ionic layer adsorption and reaction (SILAR) method. The effect of air annealing in the temperature range between 573 and 773 K on the structural, morphological, optical and electrical properties has been studied. The X-ray diffraction studies revealed the formation of polycrystalline CZTS films. The surface morphological study showed smooth, compact and uniform film formation after annealing formation. The band gap was in between range from 1.5 to 1.8 eV depending on annealing temperature. The thermo emf measurement revealed that the CZTS exhibits p-type electrical conductivity. Further, photoactivity of CZTS thin films was tested by forming the photoelectrochemical cell.

  7. Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; Jim Fredrickson; Ken Kemner; Shelly Kelly

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. ? Elucidate the controls on the rate and extent of contaminant reactivity. (2) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  8. Aqueous Complexation Reactions Governing the Rate and Extent of Biogeochemical U(VI) Reduction

    SciTech Connect

    Scott C. Brooks; Wenming Dong; Sue Carroll; James K. Fredrickson; Kenneth M. Kemner; Shelly D. Kelly

    2006-06-01

    The proposed research will elucidate the principal biogeochemical reactions that govern the concentration, chemical speciation, and reactivity of the redox-sensitive contaminant uranium. The results will provide an improved understanding and predictive capability of the mechanisms that govern the biogeochemical reduction of uranium in subsurface environments. In addition, the work plan is designed to: (1) Generate fundamental scientific understanding on the relationship between U(VI) chemical speciation and its susceptibility to biogeochemical reduction reactions. (2) Elucidate the controls on the rate and extent of contaminant reactivity. (3) Provide new insights into the aqueous and solid speciation of U(VI)/U(IV) under representative groundwater conditions.

  9. Zwitterionic, cationic, and anionic fluorinated chemicals in aqueous film forming foam formulations and groundwater from U.S. military bases by nonaqueous large-volume injection HPLC-MS/MS.

    PubMed

    Backe, Will J; Day, Thomas C; Field, Jennifer A

    2013-05-21

    A new analytical method was developed to quantify 26 newly-identified and 21 legacy (e.g. perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and fluorotelomer sulfonates) per and polyfluorinated alkyl substances (PFAS) in groundwater and aqueous film forming foam (AFFF) formulations. Prior to analysis, AFFF formulations were diluted into methanol and PFAS in groundwater were micro liquid-liquid extracted. Methanolic dilutions of AFFF formulations and groundwater extracts were analyzed by large-volume injection (900 ?L) high-performance liquid chromatography tandem mass spectrometry. Orthogonal chromatography was performed using cation exchange (silica) and anion exchange (propylamine) guard columns connected in series to a reverse-phase (C18) analytical column. Method detection limits for PFAS in groundwater ranged from 0.71 ng/L to 67 ng/L, and whole-method accuracy ranged from 96% to 106% for analytes for which matched authentic analytical standards were available. For analytes without authentic analytical standards, whole-method accuracy ranged from 78 % to 144 %, and whole-method precision was less than 15 % relative standard deviation for all analytes. A demonstration of the method on groundwater samples from five military bases revealed eight of the 26 newly-identified PFAS present at concentrations up to 6900 ng/L. The newly-identified PFAS represent a minor fraction of the fluorinated chemicals in groundwater relative to legacy PFAS. The profiles of PFAS in groundwater differ from those found in fluorotelomer- and electrofluorination-based AFFF formulations, which potentially indicates environmental transformation of PFAS. PMID:23590254

  10. First structural characterization of Pa(iv) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(iv): the evidence of a curium break.

    PubMed

    Banik, Nidhu Lal; Vallet, Valérie; Réal, Florent; Belmecheri, Réda Mohamed; Schimmelpfennig, Bernd; Rothe, Jörg; Marsac, Rémi; Lindqvist-Reis, Patric; Walther, Clemens; Denecke, Melissa A; Marquardt, Christian M

    2015-12-22

    More than a century after its discovery the structure of the Pa(4+) ion in acidic aqueous solution has been investigated for the first time experimentally and by quantum chemistry. The combined results of EXAFS data and quantum chemically optimized structures suggest that the Pa(4+) aqua ion has an average of nine water molecules in its first hydration sphere at a mean Pa-O distance of 2.43 Å. The data available for the early tetravalent actinide (An) elements from Th(4+) to Bk(4+) show that the An-O bonds have a pronounced electrostatic character, with bond distances following the same monotonic decreasing trend as the An(4+) ionic radii, with a decrease of the hydration number from nine to eight for the heaviest ions Cm(4+) and Bk(4+). Being the first open-shell tetravalent actinide, Pa(4+) features a coordination chemistry very similar to its successors. The electronic configuration of all open-shell systems corresponds to occupation of the valence 5f orbitals, without contribution from the 6d orbitals. Our results thus demonstrate that Pa(iv) resembles its early actinide neighbors. PMID:26465740

  11. Long-term Geochemical Transport Simulation to Evaluate Ambient Chemical Conditions at Horonobe URL Site, Hokkaido, Japan

    NASA Astrophysics Data System (ADS)

    Yamamoto, H.; Shimo, M.; Fujiwara, Y.; Kunimaru, T.; Xu, T.; Laaksoharju, M.

    2005-12-01

    JNC (Japan Nuclear Cycle Development Institute) has been planning an underground research laboratory (URL) in Horonobe, northern Hokkaido, Japan. In this study, long-term evolution of groundwater chemistry was simulated to evaluate ambient chemical conditions around the Horonobe URL site. The study area is about 8km by 4km and 2km deep region centered on the URL, in which the geology mainly consists of Pliocene diatomaceous argillaceous formations. Hydro-geochemical investigations using deep boreholes in about 3km by 3km area have suggested that groundwater chemistry around the site has been formed through the mixing of shallow fresh water and deep saline water. The deep groundwater has high salinity and differs from the present seawater in that it is highly reduced and has low pH, high bicarbonate and low magnesium concentration. Prior to the simulation, a computer code M3 (Laaksoharju et al. 1999) was used to model that the groundwater composition is affected by a two end-member mixing system. Next, the simulation of chemical changes during the intrusion of fresh water from land surface into deep saline water in the past 0.1 Ma was performed. A non-isothermal multiphase reactive geochemical transport simulation code TOUGHREACT (Xu and Press, 2001) was employed to solve the complex interplay of mass transport and chemical reaction in groundwater such as mineral dissolution/precipitation and ion exchange. The simulator was applied to a site-scale 3D geological structure model in which surface topography, the structures of geologic formations and a major fault were embedded. The results suggest that: 1) the spatial patterns of salinity and major constituents observed are in the site are generally consistent with a scenario of the intrusion of the surface fresh water into the deep saline water; 2) freshening of the deep saline water increases pH by cation exchange; 3) redox front migrates as oxidized water infiltrates from surface but is strongly buffered by reducing minerals such as pyrite.

  12. Synthesis of Aqueous CdTe/CdS/ZnS Core/shell/shell Quantum Dots by a Chemical Aerosol Flow Method.

    PubMed

    Yan, Chuanmiao; Tang, Fangqiong; Li, Linlin; Li, Hongbo; Huang, Xinglu; Chen, Dong; Meng, Xianwei; Ren, Jun

    2009-01-01

    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 degrees 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 H(2)O(2). PMID:20652095

  13. 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.

  14. 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.

  15. 117 I. A. Aksay, 6.E. Hoge, andd. A. Pask Wetting under Chemical Equilibrium and Nonequilibrium Conditions

    E-print Network

    Aksay, Ilhan A.

    is defined by Young's equation in terms of the static interfacial tensions. Under chemical nonequilibrium117 I. A. Aksay, 6.E. Hoge, andd. A. Pask Wetting under Chemical Equilibrium and Nonequilibrium by U. S. Atomic Energy Commission The thermodynamics of a solid-liquid-vapor system both under chemical

  16. Chemical composition and anticancer activity of essential oils of Mediterranean sage (Salvia officinalis L.) grown in different environmental conditions.

    PubMed

    Russo, Alessandra; Formisano, Carmen; Rigano, Daniela; Senatore, Felice; Delfine, Sebastiano; Cardile, Venera; Rosselli, Sergio; Bruno, Maurizio

    2013-05-01

    Salvia officinalis L. can be found worldwide and its leaves are commonly used as ingredient in food industry. Sage essential oil is applied in the treatment of a range of diseases and has been shown to possess different biological activities. The objectives of our research were to study the effects of environment on crop, chemical composition and anticancer activity on S. officinalis essential oil. Sage was cultivated at eighteen experimental sites in south-central Italy (Molise) in different growing environments. The essential oils (S1-S18), extracted by hydrodistillation, were analyzed by GC and CG/MS. Results show that the main components were ?-thujone, camphor, borneol, ?-muurolene and sclareol for all the samples, but the percentages of these compounds varied depending on environmental factors such as altitude, water availability and pedo-climatic conditions. The growth-inhibitory and proapoptotic effects of the eighteen sage essential oils were evaluated in three human melanoma cell lines, A375, M14, and A2058. PMID:23291326

  17. Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals.

    PubMed

    Lee, Minju; Zimmermann-Steffens, Saskia G; Arey, J Samuel; Fenner, Kathrin; von Gunten, Urs

    2015-08-18

    Second-order rate constants (kO3) for the reaction of ozone with micropollutants are essential parameters for the assessment of micropollutant elimination efficiency during ozonation in water and wastewater treatment. Prediction models for kO3 were developed for aromatic compounds, olefins, and amines by quantum chemical molecular orbital calculations employing ab initio Hartree-Fock (HF) and density functional theory (B3LYP) methods. The kO3 values for aromatic compounds correlated well with the energy of a delocalized molecular orbital first appearing on an aromatic ring (i.e., the highest occupied molecular orbital (HOMO) or HOMO-n (n ? 0) when the HOMO is not located on the aromatic ring); the number of compounds tested (N) was 112, and the correlation coefficient (R(2)) values were 0.82-1.00. The kO3 values for olefins and amines correlated well with the energy of a localized molecular orbital (i.e., the natural bond orbital (NBO)) energy of the carbon-carbon ? bond of olefins (N = 45, R(2) values of 0.82-0.85) and the NBO energy of the nitrogen lone-pair electrons of amines (N = 59, R(2) values of 0.81-0.83), respectively. Considering the performance of the kO3 prediction model and the computational costs, the HF/6-31G method is recommended for all aromatic groups and olefins investigated herein, whereas the HF/MIDI!, HF/6-31G*, or HF/6-311++G** methods are recommended for amines. Based on their mean absolute errors, the above models could predict kO3 within a factor of 4, on average, relative to the experimentally determined values. Overall, good correlations were also observed (R(2) values of 0.77-0.96) between kO3 predictions by quantum molecular orbital descriptors in this study and by the Hammett (?) and Taft (?*) constants from previously developed quantitative structure-activity relationship (QSAR) models. Hence, the quantum molecular orbital descriptors are an alternative to ? and ?*-values in QSAR applications and can also be utilized to estimate unknown ? or ?*-values. ?. PMID:26121114

  18. 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.

  19. 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.

  20. 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.

  1. Geochemical Modeling Of Aqueous Systems

    Energy Science and Technology Software Center (ESTSC)

    1995-09-07

    EQ3/6 is a software package for geochemical modeling of aqueous systems. This description pertains to version 7.2b. It addresses aqueous speciation, thermodynamic equilibrium, disequilibrium, and chemical kinetics. The major components of the package are EQ3NR, a speciation-solubility code, and EQ6 a reaction path code. EQ3NR is useful for analyzing groundwater chemistry data, calculating solubility limits, and determining whether certain reactions are in states of equilibrium or disequilibrium. It also initializes EQ6 calculations. EQ6 models themore »consequences of reacting an aqueous solution with a specified set of reactants (e.g., minerals or waste forms). It can also model fluid mixing and the effects of changes in temperature. Each of five supporting data files contain both standard state and activity coefficient-related data. Three support the use of the Davies or B-dot equations for the activity coefficients; the other two support the use of Pitzer''s equations. The temperature range of the thermodynamic data on the data files varies from 25 degrees C only to 0-300 degrees C.« less

  2. Microbiological and sensory shelf lives vs. volatile chemical spoilage indexes of raw Atlantic salmon (Salmo salar) stored under aerobic storage condition

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The purpose of this investigation was to identify and quantify the volatile chemical spoilage indexes (CSIs) for raw Atlantic salmon (Salmo salar) fillets stored under aerobic storage conditions at 4, 10 and 21 degrees C in relation to the determined microbial and sensory shelf lives. The volatile o...

  3. Norepinephrine stimulates progesterone production in highly estrogenic bovine granulosa cells cultured under serum-free, chemically defined conditions

    PubMed Central

    2012-01-01

    Background Since noradrenergic innervation was described in the ovarian follicle, the actions of the intraovarian catecholaminergic system have been the focus of a variety of studies. We aimed to determine the gonadotropin-independent effects of the catecholamine norepinephrine (NE) in the steroid hormone profile of a serum-free granulosa cell (GC) culture system in the context of follicular development and dominance. Methods Primary bovine GCs were cultivated in a serum-free, chemically defined culture system supplemented with 0.1% polyvinyl alcohol. The culture features were assessed by hormone measurements and ultrastructural characteristics of GCs. Results GCs produced increasing amounts of estradiol and pregnenolone for 144h and maintained ultrastructural features of healthy steroidogenic cells. Progesterone production was also detected, although it significantly increased only after 96h of culture. There was a highly significant positive correlation between estradiol and pregnenolone production in high E2-producing cultures. The effects of NE were further evaluated in a dose–response study. The highest tested concentration of NE (10 (?7) M) resulted in a significant increase in progesterone production, but not in estradiol or pregnenolone production. The specificity of NE effects on progesterone productio n was further investigated by incubating GCs with propranolol (10 (?8) M), a non-selective beta-adrenergic antagonist. Conclusions The present culture system represents a robust model to study the impact of intrafollicular factors, such as catecholamines, in ovarian steroidogenesis and follicular development. The results of noradrenergic effects in the steroidogenesis of GC have implications on physiological follicular fate and on certain pathological ovarian conditions such as cyst formation and anovulation. PMID:23171052

  4. Aqueous foam toxicology evaluation and hazard review

    SciTech Connect

    Archuleta, M.M.

    1995-10-01

    Aqueous foams are aggregates of bubbles mechanically generated by passing air or other gases through a net, screen, or other porous medium that is wetted by an aqueous solution of surface-active foaming agents (surfactants). Aqueous foams are important in modem fire-fighting technology, as well as for military uses for area denial and riot or crowd control. An aqueous foam is currently being developed and evaluated by Sandia National Laboratories (SNL) as a Less-Than-Lethal Weapon for the National Institute of Justice (NIJ). The purpose of this study is to evaluate the toxicity of the aqueous foam developed for the NIJ and to determine whether there are any significant adverse health effects associated with completely immersing individuals without protective equipment in the foam. The toxicity of the aqueous foam formulation developed for NIJ is determined by evaluating the toxicity of the individual components of the foam. The foam is made from a 2--5% solution of Steol CA-330 surfactant in water generated at expansion ratios ranging from 500:1 to 1000:1. SteoI CA-330 is a 35% ammonium laureth sulfate in water and is produced by Stepan Chemical Company and containing trace amounts (<0.1%) of 1,4-dioxane. The results of this study indicate that Steol CA-330 is a non-toxic, mildly irritating, surfactant that is used extensively in the cosmetics industry for hair care and bath products. Inhalation or dermal exposure to this material in aqueous foam is not expected to produce significant irritation or systemic toxicity to exposed individuals, even after prolonged exposure. The amount of 1,4-dioxane in the surfactant, and subsequently in the foam, is negligible and therefore, the toxicity associated with dioxane exposure is not significant. In general, immersion in similar aqueous foams has not resulted in acute, immediately life-threatening effects, or chronic, long-term, non-reversible effects following exposure.

  5. Aqueous SOA formation from radical oligomerization of methyl vinyl ketone (MVK) and methacrolein (MACR)

    NASA Astrophysics Data System (ADS)

    Renard, P.; Siekmann, F.; Ravier, S.; Temime-Roussel, B.; Clément, J.; Ervens, B.; Monod, A.

    2013-12-01

    It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from ?-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. We have investigated the aqueous phase photooxidation of MACR and MVK, which are biogenic organic compounds derived from isoprene. Aqueous phase photooxidation of MVK and MACR was investigated in a photoreactor using photolysis of H2O2 as OH radical source. Electrospray high resolution mass spectrometry analysis of the solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1800 Da within less than 15 minutes of reaction. Highest oligomer formation rates were obtained under conditions of low dissolved oxygen, highest temperature (T = 298 K) and highest precursor initial concentrations ([MVK]0 = 20 mM). A radical mechanism of oligomerization is proposed to explain the formation of the high molecular weight products. Furthermore, we quantified the total amount of carbon present in oligomers. Kinetic parameters of the proposed oligomerization mechanism are constrained by means of a box model that is able to reproduce the temporal evolution of intermediates and products as observed in the laboratory experiments. Additional model simulations for atmospherically-relevant conditions will be presented that show the extent to which these radical processes contribute to SOA formation in the atmospheric multiphase system as compared to other aqueous phase as well as traditional SOA sources. MVK time profile (as measured by UV Spectroscopy) and mass spectra (obtained using UPLC-ESI-MS for the retention time range 0-5 min in the positive mode) at 5, 10 and 50 min of reaction (MVK 20 mM, 25° C, under supersaturated O2 initial conditions).

  6. Solubility of Aragonite in Aqueous Fluids at High Pressure and High Temperature

    NASA Astrophysics Data System (ADS)

    Facq, Sébastien; Daniel, Isabelle; Petitgirard, Sylvain; Cardon, Hervé; Sverjensky, Dimitri

    2014-05-01

    Deep crustal and mantle aqueous fluids play a crucial role in geologic processes occurring in the Earth's interior, especially at high PT conditions. Dissolved carbon appears to be a major element constituting these aqueous fluids, occurring under the form of molecular species (CO2, CO, CH4), ionic species such as carbonate or bicarbonate ions or some more complex organic compounds [1]. However, the nature and the content of the chemical species constituting these C-bearing aqueous fluids may strongly be affected by the environmental geologic conditions such as the pressure and the temperature range. If fluid speciation and solubility of carbonate minerals are well characterized at HT and relatively low pressure, less is evident at pressure above 2 GPa where experimental challenges make trickier speciation and solubility measurements. Thanks to recent advances in theoretical aqueous geochemistry [1-3], combined experimental and theoretical efforts allow now the investigation of speciation and solubility of carbonate minerals with pure water at higher PT conditions than previously feasible [4]. However, direct measurements of solubility of carbonate minerals at HP-HT conditions are still needed to help to the development of quantitative models of carbon transport by aqueous fluids in subduction zones and validate existing aqueous speciation model. In this study, we present recent X-ray fluorescence measurements and thermodynamic model of solubility of carbonate in aqueous fluids at pressure up to 5 GPa. The amount of dissolved aragonite in the fluid has been measured from the intensity of the Ca K-lines at the ESRF-ID27 using an externally-heated membrane-type diamond anvil cell and an incident monochromatic focused X-Ray beam at 20 keV. The combination of the XRF data on dissolution of CaCO3mineral combined to previous speciation results permits now to calculate the solubility KS of aragonite a pressure in excess of 2 GPa. [1] Manning, C. E. et al., Review in Mineralogy & Geochemistry, 75, 109 (2013). [2] Sverjensky, D. A et al., Geochimica et Cosmochimica Acta (2014, in press). [3] Pan et al., Proceedings of the National Academy of Sciences, 110, 6646 (2013) [4] Facq et al, Geochimica et Cosmochimica Acta (2014, submitted).

  7. 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

  8. A Systematic Comparative Study of Hydrogen-Evolving Molecular Catalysts in Aqueous Solutions.

    PubMed

    Roy, Souvik; Bacchi, Marine; Berggren, Gustav; Artero, Vincent

    2015-11-01

    We describe here a systematic, reliable, and fast screening method that allows the comparison of H2 -forming catalysts that work under aqueous conditions with two readily prepared chemical reductants and two commonly used photosensitizers. This method uses a Clark-type microsensor for H2 detection and complements previous methods based on rotating disk electrode measurements. The efficiencies of a series of H2 -producing catalysts based on Co, Ni, Fe, and Pt were investigated in aqueous solutions under thermal conditions with europium(II) reductants and under photochemical conditions in the presence of two different photosensitizers {[Ru(bipy)3 ]Cl2 (bipy=2,2-bipyridine) and eosin-Y} and sacrificial electron donors (ascorbate and triethanolamine, respectively). The majority of catalysts tested were active only under specific conditions. However, our results also demonstrate the impressive versatility of a group of Co catalysts, which were able to produce H2 under different reducing conditions and at various pH values. In particular, a cobaloxime, [Co(dmgH)2 (H2 O)2 ] (dmgH2 =dimethylglyoxime), and a cobalt tetraazamacrocyclic complex, {Co(CR)Cl2 }(+) [CR=2,12-dimethyl-3,7,11,17-tetraazabicylo(11.3.1)heptadeca-1(17),2,11,13,15-pentaene], displayed excellent catalytic rates under the studied conditions, and the best rates were observed under thermal conditions. PMID:26383700

  9. AQUEOUS Pb REDUCTION IN Pb-CONTAMINATED SOILS BY FLORIDA PHOSPHATE ROCKS

    E-print Network

    Ma, Lena

    Florida phosphate rocks (PR) to immobilize aqueous Pb from Pb-contaminated soils. Occidental Chemical PR: Occidental Chemical > CF Chemical > Nu Gulf Industries > Agri-Chemical > IMC > Agrico Chemical. Phosphate concentrations in garden soils ranges from 13 to 14 100 mg kg-1 (Cotter-Howells and Thornton, 1991). A soil

  10. 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

  11. Radiolysis of Bicarbonate and Carbonate Aqueous Solutions: Product Analysis and Simulation of Radiolytic Processes

    SciTech Connect

    Cai Zhongli; Li Xifeng; Katsumura, Yosuke; Urabe, Osamu

    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.

  12. 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

  13. 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.

  14. 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.

  15. Evaluating crude oil chemical dispersion efficacy in a flow-through wave tank under regular non-breaking wave and breaking wave conditions.

    PubMed

    Li, Zhengkai; Lee, Kenneth; King, Thomas; Boufadel, Michel C; Venosa, Albert D

    2009-05-01

    Testing dispersant effectiveness under conditions similar to that of the open environment is required for improvements in operational procedures and the formulation of regulatory guidelines. To this end, a novel wave tank facility was fabricated to study the dispersion of crude oil under regular non-breaking and irregular breaking wave conditions. This wave tank facility was designed for operation in a flow-through mode to simulate both wave- and current-driven hydrodynamic conditions. We report here an evaluation of the effectiveness of chemical dispersants (Corexit EC9500A and SPC 1000) on two crude oils (Medium South American [MESA] and Alaska North Slope [ANS]) under two different wave conditions (regular non-breaking and plunging breaking waves) in this wave tank. The dispersant effectiveness was assessed by measuring the water column oil concentration and dispersed oil droplet size distribution. In the absence of dispersants, nearly 8-19% of the test crude oils were dispersed and diluted under regular wave and breaking wave conditions. In the presence of dispersants, about 21-36% of the crude oils were dispersed and diluted under regular waves, and 42-62% under breaking waves. Consistently, physical dispersion under regular waves produced large oil droplets (volumetric mean diameter or VMD > or = 300 microm), whereas chemical dispersion under breaking waves created small droplets (VMD < or = 50 microm). The data can provide useful information for developing better operational guidelines for dispersant use and improved predictive models on dispersant effectiveness in the field. PMID:19157465

  16. Comparison of alkaline industrial wastes for aqueous mineral carbon sequestration through a parallel reactivity study.

    PubMed

    Noack, Clinton W; Dzombak, David A; Nakles, David V; Hawthorne, Steven B; Heebink, Loreal V; Dando, Neal; Gershenzon, Michael; Ghosh, Rajat S

    2014-10-01

    Thirty-one alkaline industrial wastes from a wide range of industrial processes were acquired and screened for application in an aqueous carbon sequestration process. The wastes were evaluated for their potential to leach polyvalent cations and base species. Following mixing with a simple sodium bicarbonate solution, chemistries of the aqueous and solid phases were analyzed. Experimental results indicated that the most reactive materials were capable of sequestering between 77% and 93% of the available carbon under experimental conditions in four hours. These materials - cement kiln dust, spray dryer absorber ash, and circulating dry scrubber ash - are thus good candidates for detailed, process-oriented studies. Chemical equilibrium modeling indicated that amorphous calcium carbonate is likely responsible for the observed sequestration. High variability and low reactive fractions render many other materials less attractive for further pursuit without considering preprocessing or activation techniques. PMID:24735991

  17. 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).

  18. Morphological and chemical stability of silicon nanostructures and their molecular overlayers under physiological conditions: towards long-term implantable nanoelectronic biosensors

    PubMed Central

    2014-01-01

    Background The detection of biological and chemical species is of key importance to numerous areas of medical and life sciences. Therefore, a great interest exists in developing new, rapid, miniature, biocompatible and highly sensitive sensors, capable to operate under physiological conditions and displaying long-term stabilities (e.g. in-body implantable sensors). Silicon nanostructures, nanowires and nanotubes, have been extensively explored as building blocks for the creation of improved electrical biosensing devices, by virtue of their remarkably high surface-to-volume ratios, and have shown exceptional sensitivity for the real time label-free detection of molecular species adsorbed on their surfaces, down to the sensitivity of single molecules. Yet, till this date, almost no rigorous studies have been performed on the temporal morphological stability of these nanostructures, and their resulting electrical devices, under physiological conditions (e.g. serum, blood), as well as on the chemical stability of the molecular recognition over-layers covering these structures. Results Here, we present systematic time-resolved results on the morphological stability of bare Si nanowire building blocks, as well on the chemical stability of siloxane-based molecular over-layers, under physiological conditions. Furthermore, in order to overcome the observed short-term morpho-chemical instabilities, we present on the chemical passivation of the Si nanostructures by thin metal oxide nanoshells, in the range of 3–10 nm. The thickness of the metal oxide layer influences on the resulting electrical sensitivity of the fabricated FETs (field effect transistors), with an optimum thickness of 3–4 nm. Conclusions The core-shell structures display remarkable long-term morphological stability, preventing both, the chemical hydrolytic dissolution of the silicon under-structure and the concomitant loss of the siloxane-based chemical over-layers, for periods of at least several months. Electrical devices constructed from these nanostructures display excellent electrical characteristics and detection sensitivities, with exceptionally high morphological and functional stabilities. These results pave the road for the creation of long-term implantable biosensing devices in general, and nanodevices in particular. PMID:24606762

  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. PHYSICAL, CHEMICAL AND BIOLOGICAL CONDITIONS OF THE SAGAVANIRKTOK RIVER AND NEARBY CONTROL STREAMS, SHAVIOVIK AND CANNING RIVERS

    EPA Science Inventory

    Biological, physical and chemical data were collected from 28 stations on the Sagavanirktok River and five of its tributaries, the Canning River, Shaviovik River, two tundra lakes and Galbraith Lake. These stations are located on the North Slope of Alaska and in the area impacted...

  1. 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 ...

  2. PHOTOREACTION OF VALEROPHENONE IN AQUEOUS SOLUTION

    EPA Science Inventory

    Kinetics and products of the photoreaction of the phenyl ketone valerophenone were investigated as a function of temperature, pH, and wavelength in aqueous solution. Under these conditions (<10-4M), the photoreactions are pseudo-first-order with respect to valerophenone concentra...

  3. Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

    NASA Astrophysics Data System (ADS)

    Seewald, Jeffrey S.

    2001-05-01

    Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low molecular weight hydrocarbons and the production of methane-rich ("dry") natural gas. Evaluation of aqueous reaction products generated during the experiments within a thermodynamic framework indicates that alkane-alkene, alkene-ketone, and alkene-alcohol reactions attained metastable thermodynamic equilibrium states. This equilibrium included water and iron-bearing minerals, demonstrating the direct involvement of inorganic species as reactants during organic transformations. The high reactivity of water and iron-bearing minerals suggests that they represent abundant sources of hydrogen and oxygen available for the formation of hydrocarbons and oxygenated alteration products. Thus, variations in elemental kerogen composition may not accurately reflect the timing and extent of hydrocarbon, carbon dioxide, and organic acid generation in sedimentary basins. This study demonstrates that the stabilities of aqueous hydrocarbons are strongly influenced by inorganic sediment composition at elevated temperatures. Incorporation of such interactions into geochemical models will greatly improve prediction of the occurrence of hydrocarbons in natural environments over geologic time.

  4. 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.

  5. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    NASA Astrophysics Data System (ADS)

    Huang, D.; Zhang, X.; Chen, Z. M.; Zhao, Y.; Shen, X. L.

    2011-08-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR), methyl vinyl ketone (MVK), methyl glyoxal (MG), and glyoxal (GL). We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4) × 1010 M-1 s-1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 %) to MACR (10.9 ± 1.1%) in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3)(O2)CH = CH2) produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0.8 % at 6 h. The observed carbon balance accounted for ~50 % of the consumed isoprene. The presence of high-molecular-weight compounds may have accounted for a large portion of the missing carbons, but they were not quantified in this study. In summary, our work has provided experimental evidence that the availably abundant water could affect the distribution of oxygenated organic compounds produced in the oxidation of volatile organic compounds.

  6. Light-initiated transformations of fullerenol in aqueous media.

    PubMed

    Kong, Lingjun; Tedrow, O'Niell; Chan, Yau Fong Kyle; Zepp, Richard G

    2009-12-15

    We provide the first evidence that a fullerene derivative can be extensively mineralized under environmental conditions by direct photolysis. Dissolved inorganic carbon (DIC) was identified as a major photoproduct of fullerenol, a hydroxylated C(60) molecule and the ratio of moles DIC produced to moles of fullerenol reacted reached 28 or approximately 47% of complete mineralization on extensive irradiation by simulated solar radiation. The direct photoreaction kinetics of fullerenol in dilute aqueous solution can be described by pH-dependent biexponential rate expressions. This photoreaction slowed by a factor of 2 in nitrogen-saturated water. The oxygen dependence is attributed to photoinduced electron or hydrogen atom transfer from fullerenol to oxygen to produce superoxide ions with a quantum yield of 6.2 x 10(-4). Fullerenol can photosensitize the production of singlet oxygen ((1)O(2)) in dilute aqueous solution with quantum yields ranging from 0.10 in acidic water to 0.05 in neutral and basic solution. However our results indicate that chemical reactions involving diffusive encounters between (1)O(2) or superoxide and fullerenol are too slow to significantly contribute to the fast component of fullerenol photoreaction in sunlight. The pH dependence of the direct and sensitized photoreactions is attributed to changes in intramolecular hemiketal formation in fullerenol. PMID:20000505

  7. Hadron multiplicities and chemical freeze-out conditions in proton-proton and nucleus-nucleus collisions

    E-print Network

    Vovchenko, V; Gorenstein, M I

    2015-01-01

    New results of the NA61/SHINE Collaboration at the CERN SPS on mean hadron multiplicities in proton-proton (p+p) interactions are analyzed within the transport models and the hadron resonance gas (HRG) statistical model. The chemical freeze-out parameters in p+p interactions and central Pb+Pb (or Au+Au) collisions are found and compared with each other in the range of the center of mass energy of the nucleon pair $\\sqrt{s_{NN}}=3.2-17.3$~GeV. The canonical ensemble formulation of the HRG model is used to describe mean hadron multiplicities in p+p interactions and the grand canonical ensemble in central Pb+Pb and Au+Au collisions. The chemical freeze-out temperatures in p+p interactions are found to be larger than the corresponding temperatures in central nucleus-nucleus collisions.

  8. Experimental paradigm for in-laboratory proxy aquatic studies under conditions of static, non-flow-through chemical exposures.

    PubMed

    Reddy, Tirumuru V; Flick, Robert; Lazorchak, James M; Smith, Mark E; Wiechman, Barry; Lattier, David L

    2015-12-01

    Endocrine-disrupting chemicals (EDCs) such as 17?-ethynylestradiol, 17?-estradiol, estrone, and para-nonylphenol have been measured in wastewater-treatment plant effluents, surface waters, sediments, and sludge and have been shown to induce liver-specific vitellogenin (vtg) messenger RNA in male fathead minnows (Pimephales promelas). The purpose of the present study was to establish minimal concentrations of select EDCs necessary to induce transcription of vtg in 48-h static renewal exposures, as measured by quantitative real-time thermal cycle amplification. Adult males were exposed to 17?-ethynylestradiol, 17?-estradiol, estrone, and para-nonylphenol. Dose-dependent increases in vtg expression were significant with all chemicals tested. The lowest concentrations of these chemicals to induce measurable vtg expression, with significant difference from respective controls, were 17?-ethynylestradiol, 2.2?ng?L(-1) ; para-nonylphenol, 13.9??g?L(-1) ; 17?-estradiol, 42.7?ng?L(-1) ; and estrone, 46.7?ng?L(-1) , measured as 48-h average concentrations. The present experiments were designed to frame a commonly acceptable approach for investigators who conduct static, in-laboratory proxy environmental aquatic exposures. The present study highlights the need for investigators to report in peer-reviewed submissions the observed concentration values for minimal induction levels when measuring molecular responses to chemical exposures by means of real-time polymerase chain reaction, quantitative polymerase chain reaction, or other "omic" technologies. Environ Toxicol Chem 2015;34:2796-2802. Published 2015 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US Government work and is in the public domain in the United States of America. PMID:26088724

  9. Crystal Engineering of an nbo Topology Metal-?Organic Framework for Chemical Fixation of CO? under Ambient Conditions

    SciTech Connect

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J.; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2014-03-03

    Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu?(Cu-tactmb)(H?O)?(NO?)?]. This MOF demonstrates high catalytic activity for the chemical fixation of CO? into cyclic carbonates at room temperature under 1 atm pressure.

  10. 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...

  11. 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.

  12. 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.

  13. Heterogeneous Aqueous Alteration in the CR2 Chondrite Renazzo

    NASA Astrophysics Data System (ADS)

    Jilly, C. E.; Huss, G. R.

    2012-03-01

    We examine the aqueous alteration of CR2 chondrites and report on phosphates, sulfides, and other phases present in Renazzo. Various styles of alteration present in close proximity may suggest localized variations in conditions on the CR parent body.

  14. Water-stable organic transistors and their application in chemical and biological sensors

    PubMed Central

    Roberts, Mark E.; Mannsfeld, Stefan C. B.; Queraltó, Núria; Reese, Colin; Locklin, Jason; Knoll, Wolfgang; Bao, Zhenan

    2008-01-01

    The development of low-cost, reliable sensors will rely on devices capable of converting an analyte binding event to an easily read electrical signal. Organic thin-film transistors (OTFTs) are ideal for inexpensive, single-use chemical or biological sensors because of their compatibility with flexible, large-area substrates, simple processing, and highly tunable active layer materials. We have fabricated low-operating voltage OTFTs with a cross-linked polymer gate dielectric, which display stable operation under aqueous conditions over >104 electrical cycles using the p-channel semiconductor 5,5?-bis-(7-dodecyl-9H-fluoren-2-yl)-2,2?-bithiophene (DDFTTF). OTFT sensors were demonstrated in aqueous solutions with concentrations as low as parts per billion for trinitrobenzene, methylphosphonic acid, cysteine, and glucose. This work demonstrates of reliable OTFT operation in aqueous media, hence opening new possibilities of chemical and biological sensing with OTFTs. PMID:18711145

  15. Corrosion inhibitor for aqueous ammonia absorption system

    DOEpatents

    Phillips, B.A.; Whitlow, E.P.

    1998-09-22

    A method is described for inhibiting corrosion and the formation of hydrogen and thus improving absorption in an ammonia/water absorption refrigeration, air conditioning or heat pump system by maintaining the hydroxyl ion concentration of the aqueous ammonia working fluid within a selected range under anaerobic conditions at temperatures up to 425 F. This hydroxyl ion concentration is maintained by introducing to the aqueous ammonia working fluid an inhibitor in an amount effective to produce a hydroxyl ion concentration corresponding to a normality of the inhibitor relative to the water content ranging from about 0.015 N to about 0.2 N at 25 C. Also, working fluids for inhibiting the corrosion of carbon steel and resulting hydrogen formation and improving absorption in an ammonia/water absorption system under anaerobic conditions at up to 425 F. The working fluids may be aqueous solutions of ammonia and a strong base or aqueous solutions of ammonia, a strong base, and a specified buffer. 5 figs.

  16. Corrosion inhibitor for aqueous ammonia absorption system

    DOEpatents

    Phillips, Benjamin A. (Benton Harbor, MI); Whitlow, Eugene P. (St. Joseph, MI)

    1998-09-22

    A method of inhibiting corrosion and the formation of hydrogen and thus improving absorption in an ammonia/water absorption refrigeration, air conditioning or heat pump system by maintaining the hydroxyl ion concentration of the aqueous ammonia working fluid within a selected range under anaerobic conditions at temperatures up to 425.degree. F. This hydroxyl ion concentration is maintained by introducing to the aqueous ammonia working fluid an inhibitor in an amount effective to produce a hydroxyl ion concentration corresponding to a normality of the inhibitor relative to the water content ranging from about 0.015 N to about 0.2 N at 25.degree. C. Also, working fluids for inhibiting the corrosion of carbon steel and resulting hydrogen formation and improving absorption in an ammonia/water absorption system under anaerobic conditions at up to 425.degree. F. The working fluids may be aqueous solutions of ammonia and a strong base or aqueous solutions of ammonia, a strong base, and a specified buffer.

  17. 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.

  18. Rheology of aqueous foams

    NASA Astrophysics Data System (ADS)

    Dollet, Benjamin; Raufaste, Christophe

    2014-10-01

    Aqueous foams are suspensions of bubbles inside aqueous phases. Their multiphasic composition leads to a complex rheological behavior that is useful in numerous applications, from oil recovery to food/cosmetic processing. Their structure is very similar to the one of emulsions, so that both materials share common mechanical properties. In particular, the presence of surfactants at the gas-liquid interfaces leads to peculiar interfacial and dissipative properties. Foam rheology has been an active research topics and is already reported in several reviews, most of them covering rheometry measurements at the scale of the foam, coupled with interpretations at the local scale of bubbles or interfaces. In this review, we start following this approach, then we try to cover the multiscale features of aqueous foam flows, emphasizing regimes where intermediate length scales need to be taken into account or regimes fast enough regarding internal time scales so that the flow goes beyond the quasi-static limit. xml:lang="fr"

  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

    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...

  20. Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions.

    PubMed

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2014-03-01

    Crystal engineering of the nbo metal-organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1?atm pressure. PMID:24497432

  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. Atomistic insights into aqueous corrosion of copper

    NASA Astrophysics Data System (ADS)

    Jeon, Byoungseon; Sankaranarayanan, Subramanian K. R. S.; van Duin, Adri C. T.; Ramanathan, Shriram

    2011-06-01

    Corrosion is a fundamental problem in electrochemistry and represents a mode of failure of technologically important materials. Understanding the basic mechanism of aqueous corrosion of metals such as Cu in presence of halide ions is hence essential. Using molecular dynamics simulations incorporating reactive force-field (ReaxFF), the interaction of copper substrates and chlorine under aqueous conditions has been investigated. These simulations incorporate effects of proton transfer in the aqueous media and are suitable for modeling the bond formation and bond breakage phenomenon that is associated with complex aqueous corrosion phenomena. Systematic investigation of the corrosion process has been carried out by simulating different chlorine concentration and solution states. The structural and morphological differences associated with metal dissolution in the presence of chloride ions are evaluated using dynamical correlation functions. The simulated atomic trajectories are used to analyze the charged states, molecular structure and ion density distribution which are utilized to understand the atomic scale mechanism of corrosion of copper substrates under aqueous conditions. Increased concentration of chlorine and higher ambient temperature were found to expedite the corrosion of copper. In order to study the effect of solution states on the corrosion resistance of Cu, partial fractions of proton or hydroxide in water were configured, and higher corrosion rate at partial fraction hydroxide environment was observed. When the Cl- concentration is low, oxygen or hydroxide ion adsorption onto Cu surface has been confirmed in partial fraction hydroxide environment. Our study provides new atomic scale insights into the early stages of aqueous corrosion of metals such as copper.

  3. Atomistic insights into aqueous corrosion of copper.

    SciTech Connect

    Jeon, B.; Sankaranarayanan, S. K. R. S.; van Duin, A. C. T.; Ramanathan, S.

    2011-06-21

    Corrosion is a fundamental problem in electrochemistry and represents a mode of failure of technologically important materials. Understanding the basic mechanism of aqueous corrosion of metals such as Cu in presence of halide ions is hence essential. Using molecular dynamics simulations incorporating reactive force-field (ReaxFF), the interaction of copper substrates and chlorine under aqueous conditions has been investigated. These simulations incorporate effects of proton transfer in the aqueous media and are suitable for modeling the bond formation and bond breakage phenomenon that is associated with complex aqueous corrosion phenomena. Systematic investigation of the corrosion process has been carried out by simulating different chlorine concentration and solution states. The structural and morphological differences associated with metal dissolution in the presence of chloride ions are evaluated using dynamical correlation functions. The simulated atomic trajectories are used to analyze the charged states, molecular structure and ion density distribution which are utilized to understand the atomic scale mechanism of corrosion of copper substrates under aqueous conditions. Increased concentration of chlorine and higher ambient temperature were found to expedite the corrosion of copper. In order to study the effect of solution states on the corrosion resistance of Cu, partial fractions of proton or hydroxide in water were configured, and higher corrosion rate at partial fraction hydroxide environment was observed. When the Cl{sup -} concentration is low, oxygen or hydroxide ion adsorption onto Cu surface has been confirmed in partial fraction hydroxide environment. Our study provides new atomic scale insights into the early stages of aqueous corrosion of metals such as copper.

  4. Chemical composition and physical quality characteristics of Ghanaian cocoa beans as affected by pulp pre-conditioning and fermentation.

    PubMed

    Afoakwa, Emmanuel Ohene; Quao, Jennifer; Takrama, Jemmy; Budu, Agnes Simpson; Saalia, Firibu Kwesi

    2013-12-01

    Investigations were conducted to evaluate the effects of pod storage (as a means of pulp preconditioning) and fermentation on the chemical composition and physical characteristics of Ghanaian cocoa beans. A 4?×?2 full factorial design with factors as pod storage (0, 7, 14, 21 days) and cocoa treatment (fermented and unfermented) were conducted. Samples were analyzed for their chemical composition (moisture, crude fat, crude protein, ash and carbohydrate content) and mineral content using standard analytical methods. The physical qualities of the beans were analyzed for their proportions of cocoa nibs, shells and germ. Fermentation and increasing pod storage resulted in significant (P?

  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. Assessment of groundwater chemical evolution for a spent nuclear fuel repository under prolonged temperate conditions: an application of efficient coupled groundwater flow and reactive transport simulation

    NASA Astrophysics Data System (ADS)

    Gylling, B.; Hartley, L. J.; Joyce, S. J.; Woollard, H.; Marsic, N.; Sidborn, M.; Puigdomenech, I.; Selroos, J. O.

    2014-12-01

    SKB has submitted a license application for a spent nuclear fuel repository at Forsmark sited in crystalline rocks of the Fennoscandian shield. In support of this application various quantitative assessments were made to demonstrate the long-term safety of the proposed repository. One such assessment involved simulation of groundwater chemical evolution to quantify impacts on safety functions for the disposal system related to the geochemical conditions, particularly salinity, pH and redox conditions. In the reference case the current temperate period lasts until 12,000 AD. A case of prolonged meteoric infiltration to 60,000 AD is also considered resulting from e.g. global warming. This is to fulfil a regulatory request to assess whether extended dilute water infiltration might lead to a rise in redox potential and also to an increase in erosion of the bentonite barrier due to formation of colloids. In order to perform long transient simulations of groundwater flow and solute transport with water-solute-rock interactions, new tools have been developed to closely couple geochemical, groundwater flow and transport calculations, and perform these efficiently using parallel computing techniques. In assessing this case, sensitivities are tested to the geochemical reaction schemes appropriate to the site. The results of this work predict that the chemical environment at repository depth stabilises at around 20,000 AD and shows little change beyond that. The salinity of the groundwater is governed by the low permeability (c. 10-19 m2) of the bedrock and by rock matrix diffusion, resulting in relatively shallow and slow circulation of groundwater. The chemical reactions influence concentrations of reactive species, the calculated pH and redox potential. In particular, the redox reactions thought to be relevant for the Forsmark site maintain reducing conditions at repository depth, even with infiltration at the ground surface of meteoric water with relatively high redox potential.

  7. Body Condition Affects Blood Alkaloid and Monoterpene Kinetics and Voluntary Intake of Chemically-Defended Plants by Livestock

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Poisonous plants are a substantial component of grazinglands worldwide. Higher losses to poisonous plants are often observed in times of drought or at high stocking rates. Increased incidences of fatal poisoning may occur because plants can be more toxic under these conditions or because limited acc...

  8. [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

  9. 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...

  10. 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.

  11. On the in situ aqueous alteration of soils on Mars

    USGS Publications Warehouse

    Amundson, Ronald; Ewing, S.; Dietrich, W.; Sutter, B.; Owen, J.; Chadwick, O.; Nishiizumi, K.; Walvoord, M.; McKay, C.

    2008-01-01

    Early (>3 Gy) wetter climate conditions on Mars have been proposed, and it is thus likely that pedogenic processes have occurred there at some point in the past. Soil and rock chemistry of the Martian landing sites were evaluated to test the hypothesis that in situ aqueous alteration and downward movement of solutes have been among the processes that have transformed these portions of the Mars regolith. A geochemical mass balance shows that Martian soils at three landing sites have lost significant quantities of major rock-forming elements and have gained elements that are likely present as soluble ions. The loss of elements is interpreted to have occurred during an earlier stage(s) of weathering that may have been accompanied by the downward transport of weathering products, and the salts are interpreted to be emplaced later in a drier Mars history. Chemical differences exist among the sites, indicating regional differences in soil composition. Shallow soil profile excavations at Gusev crater are consistent with late stage downward migration of salts, implying the presence of small amounts of liquid water even in relatively recent Martian history. While the mechanisms for chemical weathering and salt additions on Mars remain unclear, the soil chemistry appears to record a decline in leaching efficiency. A deep sedimentary exposure at Endurance crater contains complex depth profiles of SO4, Cl, and Br, trends generally consistent with downward aqueous transport accompanied by drying. While no model for the origin of Martian soils can be fully constrained with the currently available data, a pedogenic origin is consistent with observed Martian geology and geochemistry, and provides a testable hypothesis that can be evaluated with present and future data from the Mars surface. ?? 2008 Elsevier Ltd.

  12. 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

  13. 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.

  14. 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.

  15. Mars Aqueous Chemistry Experiment (MACE)

    NASA Astrophysics Data System (ADS)

    Benton, Clark C.

    1995-12-01

    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 design 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.

  16. 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.

  17. 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.

  18. Monolayer culturing and cloning of human pluripotent stem cells on laminin-521-based matrices under xeno-free and chemically defined conditions.

    PubMed

    Rodin, Sergey; Antonsson, Liselotte; Hovatta, Outi; Tryggvason, Karl

    2014-10-01

    A robust method for culturing human pluripotent stem (hPS) cells under chemically defined and xeno-free conditions is an important tool for stem cell research and for the development of regenerative medicine. Here, we describe a protocol for monolayer culturing of Oct-4-positive hPS cells on a specific laminin-521 (LN-521) isoform, under xeno-free and chemically defined conditions. The cells are dispersed into single-cell suspension and then plated on LN-521 isoform at densities higher than 5,000 cells per cm², where they attach, migrate and survive by forming small monolayer cell groups. The cells avidly divide and expand horizontally until the entire dish is covered by a confluent monolayer. LN-521, in combination with E-cadherin, allows cloning of individual hPS cells in separate wells of 96-well plates without the presence of rho-associated protein kinase (ROCK) inhibitors or any other inhibitors of anoikis. Characterization of cells maintained for several months in culture reveals pluripotency with a minimal degree of genetic abnormalities. PMID:25211513

  19. Method of conditional moments (MCM) for the Chemical Master Equation: a unified framework for the method of moments and hybrid stochastic-deterministic models.

    PubMed

    Hasenauer, J; Wolf, V; Kazeroonian, A; Theis, F J

    2014-09-01

    The time-evolution of continuous-time discrete-state biochemical processes is governed by the Chemical Master Equation (CME), which describes the probability of the molecular counts of each chemical species. As the corresponding number of discrete states is, for most processes, large, a direct numerical simulation of the CME is in general infeasible. In this paper we introduce the method of conditional moments (MCM), a novel approximation method for the solution of the CME. The MCM employs a discrete stochastic description for low-copy number species and a moment-based description for medium/high-copy number species. The moments of the medium/high-copy number species are conditioned on the state of the low abundance species, which allows us to capture complex correlation structures arising, e.g., for multi-attractor and oscillatory systems. We prove that the MCM provides a generalization of previous approximations of the CME based on hybrid modeling and moment-based methods. Furthermore, it improves upon these existing methods, as we illustrate using a model for the dynamics of stochastic single-gene expression. This application example shows that due to the more general structure, the MCM allows for the approximation of multi-modal distributions. PMID:23918091

  20. Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

    SciTech Connect

    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 {sup 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 {sup 1}H/{sup 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.

  1. Behaviour of polydiacetylene vesicles under different conditions of temperature, pH and chemical components of milk.

    PubMed

    Oliveira, Cristiane Patrícia de; Soares, Nilda de Fátima Ferreira; Fontes, Edimar Aparecida Filomeno; Oliveira, Taíla Veloso de; Filho, Antônio Manoel Maradini

    2012-12-01

    Blue polydiacetylene vesicles were studied with regard to their behaviour under variations in storage temperature, heating, potentiometric titration and in the presence of chemical components of milk, to evaluate their application as a sensor in the food industry. Vesicles were prepared using 10,12-pentacosadienoic acid (PCDA)/1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC). Their changes were monitored using UV-Vis absorption. Temperatures not exceeding 25°C did not cause colour change in PCDA/DMPC vesicles for a period of up to 60days of storage. Heating for 10min at 60 and 90°C, exposure to pH higher than 9.0 and the simulant solutions of the whey proteins, ?-lactoglobulin and ?-lactalbumin, promoted colour change from blue to red for the vesicles studied. The effects of routine factors on the characteristics and stability of polydiacetylene vesicles is important in defining the parameters related to their application as a sensor for the food industry. PMID:22953823

  2. Passaging and colony expansion of human pluripotent stem cells by enzyme-free dissociation in chemically defined culture conditions

    PubMed Central

    Beers, Jeanette; Gulbranson, Daniel R.; George, Nicole; Siniscalchi, Lauren I.; Jones, Jeffrey; Thomson, James A.; Chen, Guokai

    2013-01-01

    This protocol describes an EDTA-based passaging procedure to be used with chemically defined E8 medium that serves as a tool for basic and translational research into human pluripotent stem cells (iPSCs). In this protocol, passaging one six-well or 10 cm plate of cells takes about 6–7 min. This enzyme-free protocol achieves maximum cell survival without enzyme neutralization, centrifugation, or drug treatment. It also allows for higher throughput, requires minimal material and limits contamination. Here we describe how to produce a consistent E8 medium for routine maintenance and reprogramming and how to incorporate the EDTA-based passaging procedure into human induced PSC (iPSC) derivation, colony expansion, cryopreservation and teratoma formation. This protocol has been successful in routine cell expansion, and efficient for expanding large-volume cultures or a large number of cells with preferential dissociation of PSCs. Effective for all culture stages, this procedure provides a consistent and universal approach to passaging human pluripotent stem cells in E8 medium. PMID:23099485

  3. Assay of antioxidant potential of two Aspergillus isolates by different methods under various physio-chemical conditions.

    PubMed

    Arora, Daljit Singh; Chandra, Priyanka

    2010-07-01

    The objective of this work was to screen fungi isolated from soil of different areas of Punjab, India for antioxidant activity by dot blot assay and around 45% of fungal isolates demonstrated antioxidant potential. Two selected strains of Aspergillus spp (Aspergillus PR78 and Aspergillus PR66) showing quantitatively best antioxidant activity by DPPH assay were further tested for their reducing power, ferrous ion and nitric oxide ion scavenging activity, FRAP assay and total phenolic content. Different physio-chemical parameters were optimized for enhancement of the activity. This revealed stationary culture grown for 10 days at 25 (o)C at pH 7 to be the best for antioxidant activity. Sucrose in the medium as carbon source resulted in highest antioxidant activity. Sodium nitrate, yeast extract, and peptone were good sources of nitrogen but sodium nitrate was the best among these. The extraction of the broth culture filtrates with different solvents revealed ethyl acetate extract to possess the best antioxidant activity. The activity as expressed by ethyl acetate extract of Aspergillus PR78 was equally effective as that of commonly used antioxidant standard, ascorbic acid. PMID:24031554

  4. 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.

  5. Tribological efficacy and stability of phospholipid-based membrane lubricants in varying pH chemical conditions.

    PubMed

    Pawlak, Zenon; Urbaniak, Wieslaw; Afara, Isaac O; Yusuf, Kehinde Q; Banaszak-Piechowska, Agnieszka; Oloyede, Adekunle

    2016-01-01

    In this study, the authors examine the influence of joint chemical environment by measuring changes in the tribological properties (friction coefficient and charge density) of contacting surfaces of normal and degenerated cartilage samples in bath solutions of varying pH (2.0-9.0). Bovine articular cartilage samples (n?=?54) were subjected to several surface measurements, including interfacial energy, contact angle, and friction coefficient, at varying pH. The samples were delipidized and then subjected to the same measurement protocols. Our results reveal that the interfacial energy and charge density, which have been shown to be related to friction coefficient, decrease with pH in the acidic range and approach constant values at physiological (or synovial fluid) pH of 7.4 and beyond it, i.e., toward basic pH domain. The authors conclude that this rather complex response explains the long-term efficacy with respect to ageing and associated pH changes, of the phospholipid layers that facilitate the almost frictionless, hydration-lubrication involving contact in the mammalian musculoskeletal system. PMID:26727914

  6. Effects of chlorine on freshwater fish under various time and chemical conditions: toxicity of chlorine to freshwater fish. Final report

    SciTech Connect

    Brooks, A.S.; Bartos, J.M.; Danos, P.T.

    1982-07-01

    Laboratory bioassays to determine the acute toxicity of monochloramine, dichloramine, hypochlorous acid, and hypochlorite ion to emerald shiners, channel catfish, and rainbow trout were conducted. Four exposure regimes typical of chlorination schedules at operating steam electric power plants were used. Fish were exposed to single 15-minute, 30-minute, 120-minute, and quadruple 30-minute periods. No mortality or LC50 values were determined for each species of fish and chemical species of chlorine. Hypochlorous acid was the most toxic form of chlorine studied, followed closely by dichloramine. Monochloramine and hypochlorite ion were three to four times less toxic than hypochlorous acid and dichloramine. On the average, emerald shiners were 1.8 times more sensitive to chlorine than channel catfish and 3.3 times more sensitive than rainbow trout to the four forms of chlorine. The fish were more tolerant of chlorine during short duration exposures and most sensitive during the continuous 120-minute exposures. The significant differences in toxicity noted among the various chlorine species suggest that careful attention should be paid not only to total residual chlorine but to both the chlorine and fish species present and the duration of exposure expected in establishing chlorination regimes.

  7. Effects of chemical composition and test conditions on the dynamic tensile response of Zr-based metallic glasses

    NASA Astrophysics Data System (ADS)

    Wang, F.; Laws, K. J.; Trujillo, C. P.; Brown, A. D.; Cerreta, E. K.; Hazell, P. J.; Quadir, M. Z.; Ferry, M.; Escobedo, J. P.

    2015-06-01

    The effects of impact velocity and temperature on the dynamic mechanical behavior of two bulk metallic glasses (BMG) with slightly different elemental compositions (Zr55Cu30Ni5Al30 and Zr46Cu38Ag8Al38) have been investigated. Bullet-shaped samples were accelerated by a gas gun to speeds in the 400 ~ 600m/s range and tested at room temperature and 250 °C. The specimens impacted a steel extrusion die which subjected them to high strains at high strain-rates. The extruded samples were subsequently soft recovered by using low density foams. The deformed specimens were examined by optical and electron microscopy, x-ray diffraction and hardness measurements. The characterization results aided to assess the effect of chemical composition on the microstructural evolution, i.e. phase changes or crystallization, which might influence the ductility on the nominally brittle amorphous BMGs. The most significant results from this study will be presented. School of Engineering and Information Technology, UNSW Canberra.

  8. Roller milling fractionation of green gram (Vigna radiata): optimization of milling conditions and chemical characterization of millstreams.

    PubMed

    Sakhare, Suresh D; Inamdar, Aashitosh A; Gaikwad, Shwetha B; D, Indrani; G, Vekateswara Rao

    2014-12-01

    In the view of recent growing interest in utilization of grain fractions as food ingredient, present investigation was carried out to evaluate the roller milling potential of green gram. The effect of conditioning moistures on green gram roller milling were studied. The results showed decrease in flour yield from 85.56 to 58.74 % with increase in conditioning moisture from 10 to 16 %. Higher yield of flour was observed from the first (C1), second (C2) and third (C3) reduction passages; whereas, the first (B1), second (B2) and third (B3) break passages produced less flour. The distribution of protein, dietary fiber, ash and fat in different flour streams and by-products from roller milled fractions of green gram showed wide variation. The protein content increased with increasing numbers of breaks and reductions in the flour streams. The highest protein content of 30.16 % was found in bran duster flour and lowest (11.32 %) in fine seed coat. The protein content of break streams was found lower than reduction streams. The dietary fiber content of coarse seed coat was highest (71.17 %) followed by the fine seed coat (57.22 %). The microstructure studies of milled fractions of green gram showed more deformed and damaged starch granules in reduction flour streams than break flour streams. PMID:25477653

  9. 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.

  10. Thin-Layer Spectroelectrochemistry on an Aqueous Microdrop

    SciTech Connect

    Schroll, Cynthia A.; Chatterjee, Sayandev; Heineman, William R.; Bryan, Samuel A.

    2012-05-01

    In this paper, we report a technique for conducting spectroelectrochemistry on an aqueous micro-drop containing an analyte in a bulk electrolysis system, as an easy, rapid and economic way of investigating spectroelectrochemical behavior and correlating spectroscopic properties with thermodynamic potentials on a small scale. The chemical systems used to demonstrate the aqueous micro-drop technique are an absorbance based molecular probe [Fe(CN)6]3-/4- and an emission based molecular probe [Re(dmpe)3]2+/+ . These chemical systems in a micro-drop are evaluated using cyclic voltammetry, UV-visable absorbance spectroscopy, and fluorescence spectrometry.

  11. Relationships between octanol-water partition coefficient and aqueous solubility

    SciTech Connect

    Miller, M.M.; Waslk, S.P.; Huang, G.L.; Shiu, W.Y.; Mackay, D.

    1985-06-01

    The thermodynamic relationship between octanol-water partition coefficient and aqueous solubility is discussed in the light of recently measured data for highly hydrophobic chemicals. Experimental data indicate that the presence of dissolved octanol in water has little effect on the solubility of chemicals in water and that the presence of dissolved water in octanol has little effect on the solubility of chemicals in octanol. The activity coefficients of hydrophobic chemicals in aqueous solution and in octanol solution both increase with increased chemical molar volume. An approximately linear relationship between log activity coefficient and molar volume is suggested in both phases, a consequence of which is that a plot of log octanol-water partition coefficient vs. log liquid or subcooled liquid solubility has a slope of approximately -0.8. A molecular thermodynamic interpretation of the data is presented, and some environmental implications are discussed.

  12. Carbon dioxide solubility in aqueous solutions of sodium chloride at geological conditions: Experimental results at 323.15, 373.15, and 423.15 K and 150 bar and modeling up to 573.15 K and 2000 bar

    NASA Astrophysics Data System (ADS)

    Zhao, Haining; Fedkin, Mark V.; Dilmore, Robert M.; Lvov, Serguei N.

    2015-01-01

    A new experimental system was designed to measure the solubility of CO2 at pressures and temperatures (150 bar, 323.15-423.15 K) relevant to geologic CO2 sequestration. At 150 bar, new CO2 solubility data in the aqueous phase were obtained at 323.15, 373.15, and 423.15 K from 0 to 6 mol kg-1 NaCl(aq) for the CO2-NaCl-H2O system. A ? - ? (activity coefficient - fugacity coefficient) type thermodynamic model is presented for the calculation of both the solubility of CO2 in the aqueous phase and the solubility of H2O in the CO2-rich phase for the CO2-NaCl-H2O system. Validation of the model calculations against literature data and other models (MZLL2013, AD2010, SP2010, DS2006, and OLI) show that the proposed model is capable of predicting the solubility of CO2 in the aqueous phase for the CO2-H2O and CO2-NaCl-H2O systems with a high degree of accuracy (AAD <3.9%) at temperatures from 273.15 to 573.15 K and pressures up to 2000 bar. A comparison of modeling results with experimental values revealed a pressure-bounded “transition zone” in which the CO2 solubility decreases to a minimum then increases as the temperature increases. CO2 solubility is not a monotonic function of temperature in the transition zone but outside of that transition zone, the CO2 solubility is decrease or increase monotonically in response to increased temperature. A link of web-based CO2 solubility computational tool can be provided by sending a message to Haining Zhao at hzz5047@gmail.com.

  13. Chemical and physical structures of proteinoids and related polyamino acids

    NASA Astrophysics Data System (ADS)

    Mita, Hajime; Kuwahara, Yusuke; Nomoto, Shinya

    Studies of polyamino acid formation pathways in the prebiotic condition are important for the study of the origins of life. Several pathways of prebiotic polyamino acid formation have been reported. Heating of monoammonium malate [1] and heating of amino acids in molten urea [2] are important pathways of the prebiotic peptide formation. The former case, globular structure called proteinoid microsphere is formed in aqueous conditions. The later case, polyamino acids are formed from unrestricted amino acid species. Heating of aqueous aspargine is also interesting pathway for the prebiotic polyamino acid formation, because polyamino acid formation proceeds in aqueous condition [3]. In this study, we analyzed the chemical structure of the proteinoids and related polyamino acids formed in the above three pathways using with mass spectrometer. In addition, their physical structures are analyzed by the electron and optical microscopes, in order to determine the self-organization abilities. We discuss the relation between the chemical and the physical structures for the origins of life. References [1] Harada, K., J. Org. Chem., 24, 1662 (1959), Fox, S. W., Harada, K., and Kendrick, J., Science, 129, 1221 (1959). [2] Terasaki, M., Nomoto, S., Mita, H., and Shimoyama, A., Chem. Lett., 480 (2002), Mita, H., Nomoto, S., Terasaki, M., Shimoyama, A., and Yamamoto, Y., Int. J. Astrobiol., 4, 145 (2005). [3] Kovacs, K and Nagy, H., Nature, 190, 531 (1961), Munegumi, T., Tanikawa, N., Mita, H. and Harada, K., Viva Origino, 22, 109 (1994).

  14. EVOLUTION OF CHEMICAL CONDITIONS AND ESTIMATED SOLUBILITY CONTROLS ON RADIONUCLIDES IN THE RESIDUAL WASTE LAYER DURING POST-CLOSURE AGING OF HIGH-LEVEL WASTE TANKS

    SciTech Connect

    Denham, M.; Millings, M.

    2012-08-28

    This document provides information specific to H-Area waste tanks that enables a flow and transport model with limited chemical capabilities to account for varying waste release from the tanks through time. The basis for varying waste release is solubilities of radionuclides that change as pore fluids passing through the waste change in composition. Pore fluid compositions in various stages were generated by simulations of tank grout degradation. The first part of the document describes simulations of the degradation of the reducing grout in post-closure tanks. These simulations assume flow is predominantly through a water saturated porous medium. The infiltrating fluid that reacts with the grout is assumed to be fluid that has passed through the closure cap and into the tank. The results are three stages of degradation referred to as Reduced Region II, Oxidized Region II, and Oxidized Region III. A reaction path model was used so that the transitions between each stage are noted by numbers of pore volumes of infiltrating fluid reacted. The number of pore volumes to each transition can then be converted to time within a flow and transport model. The bottoms of some tanks in H-Area are below the water table requiring a different conceptual model for grout degradation. For these simulations the reacting fluid was assumed to be 10% infiltrate through the closure cap and 90% groundwater. These simulations produce an additional four pore fluid compositions referred to as Conditions A through D and were intended to simulate varying degrees of groundwater influence. The most probable degradation path for the submerged tanks is Condition C to Condition D to Oxidized Region III and eventually to Condition A. Solubilities for Condition A are estimated in the text for use in sensitivity analyses if needed. However, the grout degradation simulations did not include sufficient pore volumes of infiltrating fluid for the grout to evolve to Condition A. Solubility controls for use in a flow and transport model were estimated for 27 elements in each of the chemical stages generated in the grout simulations plus local groundwater. The grout simulations were run with the initial infiltrating fluid in equilibrium with atmospheric oxygen to account for degradation of the reduction capacity of the grout. However, a lower Eh was used in pore fluids in the oxidizing conditions used to estimate solubilities to be more consistent with measured Eh values and natural systems. Solubilities of plutonium are affected by this decision, but those of other elements are not. In addition, the baseline for H-Area tanks is that they will be washed with oxalic acid prior to being filled with grout. Hence, oxalate was included in the pore fluids by assuming equilibrium with calcium oxalate. Solubility estimates were done by equilibrating a solubility controlling phase for each element with the pore fluid compositions using The Geochemist’s Workbench®. Condition B pore fluids are similar to Condition D. Therefore, solubilities for Condition B were not estimated, but assumed to be the same as in Condition D. In general solubility controlling phases were selected to bias solubilities to higher values. Several elements had no solubility controls and solubility estimates for other elements were omitted because the elements had short half-lives or were present in residual waste in very low amounts. For these it is recommended that release from the tank be instantaneous when the tank liner is breached. There is considerable uncertainty in this approach to enabling a flow and transport model to account for variable waste release. Yet, it is also flexible and requires much less computing time than a fully coupled reactive transport model. This allows some of the uncertainty to be addressed by multiple flow and transport sensitivity cases. Some of the uncertainties are addressed within this document. These include uncertainty in infiltrate composition, grout mineralogy, and disposition of certain components during the simulations. Uncertainty in the solubility estima

  15. Aluminoborosilicate Waste Glass Dissolution under Alkaline Conditions at 40°C: Implications for a Chemical Affinity-Based Rate Equation

    SciTech Connect

    Pierce, Eric M.; Richards, Emily L.; Davis, Aaron M.; Reed, Lunde R.; Cordova, Elsa A.

    2008-02-25

    Single-pass flow-through (SPFT) experiments were conducted with aluminoborosilicate waste glasses to evaluate how changes in solution composition affect the dissolution rate (r) at 40°C and pH(23°C) = 9.0. The three prototypic low-activity waste (LAW) glasses; LAWE-1A, -95A, and -290A, used in these experiments span a wide range covering the expected processing composition of candidate immobilized low-activity waste (ILAW) glasses. Results suggest incongruent release of Al, B, Na, and Si at low flow-rate (q) to sample surface area (S) [log10 (q/S) < -8.9 (m s-1)] whereas congruent release was observed at high q/S [log10 (q/S) > -7.9 (m s-1)]. Dissolution rates increase from log10 (q/S) ? -9.3 to -8.0 (m s-1) and then become constant at log10 (q/S) > -7.9 (m s-1). Forward (maximum) dissolution rates, based on B release, are the same irrespective of glass composition, evident by the dissolution rates being within the experimental error of one another (r1A = 0.0301 ±0.0153 g m-2 d-1, r95A = 0.0248 ±0.0125 g m-2 d-1, and r290A = 0.0389 ±0.0197 g m-2 d-1). Finally these results support the use of a chemical affinity based rate law to describe glass dissolution as a function of solution composition.

  16. Assessment of silicone as support to investigate the transformation routes of organic chemicals under environmental conditions and UV exposure. Application to selected fungicides.

    PubMed

    Rodríguez-Cabo, T; Rodríguez, I; Ramil, M; Cela, R

    2013-05-01

    The suitability of bulk silicone as support to follow the degradation of chemical compounds under environmental conditions and UV radiation is illustrated selecting three fungicides (fenhexamid, FEN; triadimenol, TRI and difenoconazole, DIF) as model compounds. These precursor species were first absorbed in silicone supports (10 mm length × 2 mm i.d. and 0.5 mm thickness) and then kept outdoors for several days (up to 2 months) or exposed to UV radiation (254 nm), from a low pressure mercury lamp, in the laboratory. Degradation of precursor fungicides and by-products formation was followed by liquid chromatography (LC) quadrupole time-of-flight (QTOF) mass spectrometry (MS), after desorption of silicone supports using 0.5 mL of acetonitrile. Half-lives (t(1/2)) measured under UV exposure varied from 5 to 100 min. As regards environmental conditions, the most stable fungicide was DIF, degraded by just 15 % after 2 months; whereas, t(1/2) values of 30 and 83 h were calculated for FEN during summer and autumn, respectively. Supports contained by-products arising from precursor species through de-chlorination, cleavage, hydroxylation, intra-molecular cyclation and oligomerization reactions. Most of them have been previously identified in soil surface, vegetable leaves and water after application of fungicides in agriculture fields. The low cost of silicone tubes (ca. 0.4 Euros), added to their excellent chemical stability and capability to retain precursor species and their by-products, make them ideal supports to follow the transformation routes of organic compounds under environmental and simulated conditions, even for relatively stable species with t(1/2) in the range of weeks or months. PMID:23436168

  17. 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.

  18. Tunable Aqueous Virtual Micropore

    SciTech Connect

    Park, Jae Hyun nmn; Guan, Weihau; Reed, Mark A; Krstic, Predrag S

    2012-01-01

    A charged microparticle can be trapped in an aqueous environment by forming a narrow virtual pore - a cylindrical space region in which the particle motion in the radial direction is limited by forces emerging from dynamical interactions of the particle charge and dipole moment with an external radiofrequency quadrupole electric field. If the particle satisfies the trap stability criteria, its mean motion is reduced exponentially with time due to the viscosity of the aqueous environment; thereafter the long-time motion of particle is subject only to random, Brownian fluctuations, whose magnitude, influenced by the electrophoretic and dielectrophoretic effects and added to the particle size, determines the radius of the virtual pore, which is demonstrated by comparison of computer simulations and experiment. The measured size of the virtual nanopore could be utilized to estimate the charge of a trapped micro-object.

  19. Carboxymethylcellulose from recycled newspaper in aqueous medium.

    PubMed

    Unlü, Cüneyt H

    2013-08-14

    Recycled paper cellulose has some drawbacks, for example loss in mechanical strength, to use in paper industry alone. However, derivatives of cellulose can find applications in other industrial areas. Carboxymethylcellulose (CMC) is one of the most used cellulose derivatives and can be obtained by heterogeneous modification of cellulose. In general carboxymethylation of cellulose achieved in alkaline alcoholic dispersions. In this work modification of cellulose from recycled newspaper in aqueous alkaline solution was aimed. First cellulose was recovered from newspaper under oxidative alkaline conditions. Cellulose recovery was determined as 75-90% (w/w) of starting material. Carboxymethylation reactions were carried out to find optimum conditions for derivatization, changing concentrations of components and reaction temperature. Obtained CMC samples had a DS of 0.3-0.7% and 84-94% CMC content. As a result, carboxymethylation of cellulose from recycled newspaper was achieved in aqueous alkaline dispersion giving commercial grade CMC for industrial use. PMID:23769532

  20. Aqueous alteration on main belt primitive asteroids: Results from visible spectroscopy

    NASA Astrophysics Data System (ADS)

    Fornasier, S.; Lantz, C.; Barucci, M. A.; Lazzarin, M.

    2014-05-01

    This work focuses on the study of the aqueous alteration process which acted in the main belt and produced hydrated minerals on the altered asteroids. Hydrated minerals have been found mainly on Mars surface, on main belt primitive asteroids and possibly also on few TNOs. These materials have been produced by hydration of pristine anhydrous silicates during the aqueous alteration process, that, to be active, needed the presence of liquid water under low temperature conditions (below 320 K) to chemically alter the minerals. The aqueous alteration is particularly important for unraveling the processes occurring during the earliest times of the Solar System history, as it can give information both on the asteroids thermal evolution and on the localization of water sources in the asteroid belt. To investigate this process, we present reflected light spectral observations in the visible region (0.4-0.94 ?m) of 80 asteroids belonging to the primitive classes C (prevalently), G, F, B and P, following the Tholen (Tholen, D.J. [1984]. Ph.D. Dissertation, University of Arizona, Tucson). classification scheme. We find that about 65% of the C-type and all the G-type asteroids investigated reveal features suggesting the presence of hydrous materials, mainly a band centered around 0.7 ?m, while we do not find evidence of hydrated materials in the other low albedo asteroids (B, F, and P) investigated. We combine the present observations with the visible spectra of asteroids available in the literature for a total of 600 primitive main belt asteroids. We analyze all these spectra in a similar way to characterize the absorption band parameters (band center, depth and width) and spectral slope, and to look for possible correlations between the aqueous alteration process and the asteroids taxonomic classes, orbital elements, heliocentric distances, albedo and sizes. Our analysis shows that the aqueous alteration sequence starts from the P-type objects, practically unaltered, and increases through the P ? F ? B ? C ? G asteroids, these last being widely aqueous altered, strengthening thus the results previously obtained by Vilas (Vilas, F. [1994]. Icarus 111, 456-467). Around 50% of the observed C-type asteroids show absorption feature in the visible range due to hydrated silicates, implying that more than ?70% of them will have a 3 ?m absorption band and thus hydrated minerals on their surfaces, based on correlations between those two absorptions (Howell, E.S. et al. [2011]. EPSC-DPS Joint Meeting 2011, vol. 6. Abstracts, 637). We find that the aqueous alteration process dominates in primitive asteroids located between 2.3 and 3.1 AU, that is at smaller heliocentric distances than previously suggested by Vilas et al. (Vilas, F., Hatch, E.C., Larson, S.M., Sawyer, S.R., Gaffey, M.J. [1993]. Icarus 102, 225-231). The percentage of hydrated asteroids is strongly correlated with their size. The aqueous alteration process is less effective for bodies smaller than 50 km, while it dominates in the 50-240 km sized primitive asteroids. No correlation is found between the aqueous alteration process and the asteroids albedo or orbital elements. Comparing the ?0.7 ?m band parameters of hydrated silicates and CM2 carbonaceous chondrites, the meteorites that have aqueous altered asteroids as parent bodies, we see that the band center of meteorites is at longer wavelengths than that of asteroids. This difference on center positions may be attributed to different minerals abundances, and to the fact that CM2 available on Earth might not be representative of the whole aqueous altered asteroids population.

  1. 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.

  2. 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.

  3. Influence of irrigation with lagooned urban wastewater on chemical and microbiological soil parameters in a citrus orchard under Mediterranean condition.

    PubMed

    Meli, Salvatore; Porto, Maurizio; Belligno, Adalgisa; Bufo, Sabino A; Mazzatura, Angelo; Scopa, Antonio

    2002-02-21

    The reduced availability of water resources in semi-arid Mediterranean regions requires an efficient use of supply sources. Urban wastewater, after treatment to minimise health hazards, may constitute an important resource for irrigation in areas characterised by intensive agriculture. These considerations have motivated an investigation (during the irrigation season 1996) of the dynamics of microbial biomass in the soil of a citrus orchard in eastern Sicily, which has been irrigated for 15 years with lagooned urban wastewater, to evaluate the effects of this practice on soil fertility. The analyses of parameters regarding soil microbial biomass (microbial carbon and microbial nitrogen, soluble carbon and nitrogen, cumulative respiration, respiratory quotient and enzymatic activity in the soil) have confirmed that the evolution of soil microflora is directly conditioned by the type of water used for irrigation and climatic conditions. Just before the beginning of the irrigation season (May), microbial biomass carbon (MBC), soluble C, cumulative respiration and enzymatic activity were significantly higher in the soil irrigated with wastewater with respect to the same soil irrigated with 'clear' water; the qCO2 was significantly lower. In June, after 1 month of irrigation, both soils showed an increase of all microbial parameters except for enzymatic activity and qCO2 which showed a significant reduction. In September, at the end of the irrigation period, there was a decrease of almost all investigated parameters in both plots, which was more evident in the soil irrigated with 'clear' water. The microbial biomass of the soil irrigated with wastewater, during the irrigation period, did not undergo any negative effects, having an evolution analogous to the plot irrigated with 'clear' water. The use of lagooned wastewater after three lustrums has shown, particularly in the dry season, an increase in quantity of easily available nutrients, with an improvement of the metabolic efficiency of soil microflora coupled with a more marked activity of total hydrolase and phosphatases. The variations of the parameters related to the soil microflora were strongly influenced by the seasonal climatic trend. PMID:11874049

  4. 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

  5. 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

  6. Seasonal behavior and long-term trends of tropospheric ozone, its precursors and chemical conditions over Iran: A view from space

    NASA Astrophysics Data System (ADS)

    Choi, Yunsoo; Souri, Amir Hossein

    2015-04-01

    To identify spatial and temporal variations over the Iranian region, this study analyzed tropospheric formaldehyde (HCHO) and nitrogen dioxide (NO2) columns from Ozone Monitoring Instrument (OMI), carbon monoxide (CO) columns from the Measurement of Pollution in the Troposphere (MOPITT), and tropospheric column O3 (TCO) from OMI/MLS (Microwave Limb Sounder) satellites from 2005 to 2012. The study discovered high levels of HCHO (?12 × 1015 molec./cm2) from plant isoprene emissions in the air above parts of the northern forest of Iran during the summer and from the oxidation of HCHO precursors emitted from petrochemical industrial facilities and biomass burning in South West Iran. This study showed that maximum NO2 levels (?18 × 1015 molec./cm2) were concentrated in urban cities, indicating the predominance of anthropogenic sources. The results indicate that maximum concentrations were found in the winter, mainly because of weaker local winds and higher heating fuel consumption, in addition to lower hydroxyl radicals (OH). The high CO concentrations (?2 × 1018 molec./cm2) in the early spring were inferred to mainly originate from a strong continental air mass from anthropogenic CO "hotspots" including regions around Caspian Sea, Europe, and North America, although the external sources of CO were partly suppressed by the Arabian anticyclone and topographic barriers. Variations in the TCO were seen to peak during the summer (?40 DU), due to intensive solar radiation and stratospheric sources. This study also examined long-term trends in TCO and its precursors over a period of eight years in five urban cities in Iran. To perform the analysis, we estimated seasonal changes and inter-seasonal variations using least-squares harmonic estimation (LS-HE), which reduced uncertainty in the trend by 5-15%. The results showed significant increases in the levels of HCHO (?0.08 ± 0.06 × 1015 molec./cm2 yr-1), NO2 (?0.08 ± 0.02 × 1015 molec./cm2 yr-1), and peak annual TCO (?0.59 ± 0.56 DU yr-1) but decreases in minimum annual TCO (?-0.42 ± 0.60 DU yr-1) caused by an increase in NO2 species and annual CO (?-0.95 ± 0.41 × 1016 molec./cm2 yr-1) partly resulting from the transport of reduced CO. The time series of the HCHO/NO2 column ratio (a proxy for the chemical conditions) indicated that during the last decade, the cities of Tehran, Ahvaz, and Isfahan exhibited steady chemical conditions while Tabriz and Mashhad exhibited a change from NOx-saturated/mixed to more NOx-sensitive chemical conditions.

  7. Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated martian surface ultraviolet radiation conditions.

    PubMed

    Poch, Olivier; Jaber, Maguy; Stalport, Fabien; Nowak, Sophie; Georgelin, Thomas; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

    2015-03-01

    Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe(3+)-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 tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of 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 were reduced by a factor of 5 when mixed at a concentration of 2.6 × 10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also 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. PMID:25734356

  8. Effects of chemical speciation in growth media on the toxicity of mercury(II)

    SciTech Connect

    Farrell, R.E.; Germida, J.J.; Huang, P.M. )

    1993-05-01

    The bioavailability and toxicity of trace metals to aquatic microbiota are influenced by the chemical form (aqueous species) of the metal. However, the interpretation of bioassay results, and the extrapolation of these results to in situ conditions, is often complicated by the inclusion of complex soluable organics in the bioassay media. This investigation (1) evaluates the effects of complex soluable organics on the acute toxicity of mercury (II) to a Pseudomonas fluorescens isolate in a chemically well-defined synthetic growth media, (2) computes the effects of these organics on the aqueous speciation of mercury (II) in the media, and (3) ascertains the dependence of toxicity on the chemical speciation of mercury (II). 25 refs., 3 figs., 6 tabs.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. Engineered Barrier System: Physical and Chemical Environment

    SciTech Connect

    P. Dixon

    2004-04-26

    The conceptual and predictive models documented in this Engineered Barrier System: Physical and Chemical Environment Model report describe the evolution of the physical and chemical conditions within the waste emplacement drifts of the repository. The modeling approaches and model output data will be used in the total system performance assessment (TSPA-LA) to assess the performance of the engineered barrier system and the waste form. These models evaluate the range of potential water compositions within the emplacement drifts, resulting from the interaction of introduced materials and minerals in dust with water seeping into the drifts and with aqueous solutions forming by deliquescence of dust (as influenced by atmospheric conditions), and from thermal-hydrological-chemical (THC) processes in the drift. These models also consider the uncertainty and variability in water chemistry inside the drift and the compositions of introduced materials within the drift. This report develops and documents a set of process- and abstraction-level models that constitute the engineered barrier system: physical and chemical environment model. Where possible, these models use information directly from other process model reports as input, which promotes integration among process models used for total system performance assessment. Specific tasks and activities of modeling the physical and chemical environment are included in the technical work plan ''Technical Work Plan for: In-Drift Geochemistry Modeling'' (BSC 2004 [DIRS 166519]). As described in the technical work plan, the development of this report is coordinated with the development of other engineered barrier system analysis model reports.

  14. 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).

  15. In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars

    NASA Technical Reports Server (NTRS)

    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.

  16. In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars.

    PubMed

    Squyres, S W; Grotzinger, J P; Arvidson, R E; Bell, J F; Calvin, W; Christensen, P R; Clark, B C; Crisp, J A; Farrand, W H; Herkenhoff, K E; Johnson, J R; Klingelhöfer, G; Knoll, A H; McLennan, S M; McSween, H Y; Morris, R V; Rice, J W; Rieder, R; Soderblom, L A

    2004-12-01

    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. PMID:15576604

  17. Characterization of aqueous phase from the hydrothermal liquefaction of Chlorella pyrenoidosa.

    PubMed

    Gai, Chao; Zhang, Yuanhui; Chen, Wan-Ting; Zhou, Yan; Schideman, Lance; Zhang, Peng; Tommaso, Giovana; Kuo, Chih-Ting; Dong, Yuping

    2015-05-01

    This study investigated the characteristics of aqueous phase from hydrothermal liquefaction of low-lipid microalgae Chlorella pyrenoidosa. The interactions of operating conditions, including reaction temperature, retention time and total solid ratio were evaluated by response surface methodology. The chemical oxygen demand, total nitrogen and total phosphorus were selected as indicators of the property of AP. Results indicated that total solid ratio was found to be the dominant factor affecting the nutrient recovery efficiencies of AP. Based on energy recovery, GC-MS indicated that the AP at two optimized operating conditions (280 °C, 60 min, 35 wt.% and 300 °C, 60 min, 25 wt.%) were observed to have a higher concentration of organic acids (10.35% and 8.34%) while the sample (260 °C, 30 min, 35 wt.%) was observed to have the highest concentration of N&O-heterocyclic compounds (36.16%). PMID:25466993

  18. Long-term geochemical evolution of acidic mine wastes under anaerobic conditions.

    PubMed

    Lu, Wenzhou; Lin, Chuxia; Ma, Yingqun

    2013-08-01

    A nearly 5-year anaerobic incubation experiment was conducted to observe the geochemical evolution of an acidic mine waste. Long-term storage of the mine waste under strict anaerobic conditions caused marked increase in aqueous sulfur, while aqueous iron showed no remarkable change. Co-existing oxidation and reduction of elemental sulfur appeared to play a central role in controlling the evolutionary trends of aqueous sulfur and iron. Addition of organic matter increased the aqueous Fe concentration, possibly due to enhanced iron mobilization by microbial iron reduction and increased iron solubility by forming organically complexed Fe species. Further addition of CaCO3 resulted in immobilization of aqueous iron and sulfur due to elevated pH and gypsum formation. The chemical behaviors of environmentally significant metals were markedly affected by the added organic matter; Al, Cr, Cu, Ni and Zn tended to be immobilized probably due to elevated pH and complexation with insoluble organic molecules, while As and Pb tended to be mobilized. Jarosite exhibited high stability after nearly 5 years of anaerobic incubation and even under circumneutral pH conditions. Long-term weathering of aluminosilicate through acid attack raised pH, while continuous reaction between the added CaCO3 and mine waste-borne stored acid decreased pH. PMID:23529626

  19. Absorption of Carbon Dioxide in Aqueous Piperazine/Methyldiethanolamine

    E-print Network

    Rochelle, Gary T.

    Absorption of Carbon Dioxide in Aqueous Piperazine/Methyldiethanolamine Sanjay Bishnoi and Gary T .piperazine in 1.5 to 4.5 M MDEA Appl et al., 1982 . These solvents are widely used in the removal of carbon. Rochelle Dept. of Chemical Engineering, The University of Texas at Austin, Austin, TX 78712 ( )Carbon

  20. Aqueous Ferrofluid of Magnetite Nanoparticles: Fluorescence Labeling and Magnetophoretic Control

    E-print Network

    Swihart, Mark T.

    of nanometers making them smaller than or comparable in size to important biological entities such as cells (10Aqueous Ferrofluid of Magnetite Nanoparticles: Fluorescence Labeling and Magnetophoretic Control, and Paras N. Prasad*, Department of Chemistry, Department of Chemical and Biological Engineering, Institute

  1. 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...

  2. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name. dithio diacetic acid, sodium salt. (b... intravenously at 0.1 milliliter per pound of body weight (1.0 milliliter for every 10 pounds) twice a day for 2... conservative dosage schedule of 0.1 milliliter per pound of body weight daily for 15 days is recommended....

  3. 21 CFR 522.144 - Arsenamide sodium aqueous injection.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... § 522.144 Arsenamide sodium aqueous injection. (a) Chemical name. dithio diacetic acid, sodium salt. (b... intravenously at 0.1 milliliter per pound of body weight (1.0 milliliter for every 10 pounds) twice a day for 2... conservative dosage schedule of 0.1 milliliter per pound of body weight daily for 15 days is recommended....

  4. 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.

  5. Decomposition Studies of Triphenylboron, Diphenylborinic Acid and Phenylboric Acid in Aqueous Alkaline Solutions Containing Copper

    SciTech Connect

    Crawford, C.L.; Peterson, R. A.

    1997-02-11

    This report documents the copper-catalyzed chemical kinetics of triphenylboron, diphenylborinic acid and phenylboric acid (3PB, 2PB and PBA) in aqueous alkaline solution contained in carbon-steel vessels between 40 and 70 degrees C.

  6. 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...

  7. Anion-catalyzed dissolution of NO2 on aqueous microdroplets.

    PubMed

    Yabushita, A; Enami, S; Sakamoto, Y; Kawasaki, M; Hoffmann, M R; Colussi, A J

    2009-04-30

    Fifty-seven years after NO(x) (NO + NO(2)) were identified as essential components of photochemical smog, atmospheric chemical models fail to correctly predict *OH/HO(2)* concentrations under NO(x)-rich conditions. This deficiency is due, in part, to the uncertain rates and mechanism for the reactive dissolution of NO(2)(g) (2NO(2) + H(2)O = NO(3)(-) + H(+) + HONO) in fog and aerosol droplets. Thus, state-of-the-art models parametrize the uptake of NO(2) by atmospheric aerosol from data obtained on "deactivated tunnel wall residue". Here, we report experiments in which NO(3)(-) production on the surface of microdroplets exposed to NO(2)(g) for approximately 1 ms is monitored by online thermospray mass spectrometry. NO(2) does not dissolve in deionized water (NO(3)(-) signals below the detection limit) but readily produces NO(3)(-) on aqueous NaX (X = Cl, Br, I) microdroplets with NO(2) uptake coefficients gamma that vary nonmonotonically with electrolyte concentration and peak at gamma(max) approximately 10(-4) for [NaX] approximately 1 mM, which is >10(3) larger than that in neat water. Since I(-) is partially oxidized to I(2)(*-) in this process, anions seem to capture NO(2)(g) into X-NO(2)(*-) radical anions for further reaction at the air/water interface. By showing that gamma is strongly enhanced by electrolytes, these results resolve outstanding discrepancies between previous measurements in neat water versus NaCl-seeded clouds. They also provide a general mechanism for the heterogeneous conversion of NO(2)(g) to (NO(3)(-) + HONO) on the surface of aqueous media. PMID:19331373

  8. 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

  9. Absorption Optics of Aqueous Foams

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, Ranjini; Gittings, Alex; Durian, D. J.

    2002-11-01

    Aqueous foams are composed of gas bubbles packed together in a small volume of soapy water. The large number of gas-liquid interfaces in foams results in very strong scattering of light, which explains the opaque nature of conventional aqueous foams such as shaving foams and mousse. For dry foams, the interfaces can take the following three forms: the soap films where two bubbles meet, the triangular plateau borders where three soap films meet and the vertices where four plateau borders meet. Previous experiments have shown that most of the scattering occurs from the plateau borders 2,3 and the transport mean free path of light (l*), the bubble radius (R) and the liquid fraction of foam (epsilon) is related through the relation l*=R/(epsilon0.5). To understand the reflection and scattering of light at the gas-bubble interfaces, we study the absorption of photons in the liquid network as a function of the foam absorptivity. We do this to confirm if the time spent by the photons in the liquid phase is proportional to the liquid fraction of the foam. Our results indicate that for a specific range of liquid fractions (0.05 is less than e is less than 0.1), the photons seem to get trapped in the liquid network. This result is independent of the absorptivity of the foam and leads us to conclude that under appropriate conditions, an aqueous foam behaves very much like an optical fiber network. Aqueous foam is generated in the lab by the method of turbulent mixing of N2 gas with a jet of alpha-olefin-sulfonate (AOS) solution. The foam has been made absorbing by dissolving small quantities of rhodamine dye (R = 0.005 g/l, R = 0.01 g/l and R = 0.0124 g/l) in the AOS solution. The transmission of photons through the foams of liquid fractions 0.0297 is less than e is less than 0.35 has been studied using Diffuse Transmission Spectroscopy (DTS). For each liquid fraction, the transport mean free path l* (the length over which the photon travels before it gets completely randomized) has been estimated from DTS experiments on foams with R = 0.0 g/l. In the liquid fraction range 0.05 is less than epsilon is less than 0.1, the ratio is found to be lower than the theoretical prediction. The deviation of the experimental estimates of (la)foam/(la)soln from the solid line leads us to conclude that at 0.05 is less than e is less than 0.1, the foam behaves like an optical fiber network with the photons getting trapped in and then channeled through the plateau borders. We believe that our results may be explained quantitatively by relating the reflectance of light at liquid-gas and gas-liquid interfaces to the average angles of incidence at these interfaces. Additional information is included in the original extended abstract.

  10. Chemical Changes in Pore Water Composition due to CO2 Injection Under In-Situ P-T Condition of the Altmark Gas Reservoir, Germany

    NASA Astrophysics Data System (ADS)

    Huq, F.; Nowak, M.; Haderlein, S.; Grathwohl, P.

    2012-12-01

    CO2 storage in depleted gas reservoir combined with enhanced gas recovery may be an economically feasible option to mitigate global warming. The Altmark gas field, located in the western part of the Northeast German Basin, is being considered as a potential candidate for this purpose. Under reservoir conditions (50 bars and 125°C), the CO2 saturated water causes dissolution and subsequent precipitation of minerals of the surrounding rock matrix. Therefore, the main objective of the current study was to investigate the chemical changes in fluid composition due to dissolution/precipitation of minerals under controlled laboratory conditions. A dry sandstone plug from the Altmark reservoir was mounted in a newly designed autoclave system and flushed by a pre-equilibrated mixture of water saturated with CO2 at a constant flow rate of 0.25 cm/h for 12 days at reservoir conditions. Fluid samples were taken at regular intervals for major and trace element analysis and pH was measured simultaneously in the partially de-gassed samples. Fluid analysis showed an increased concentration of Na, K and Cl ions at the beginning indicating early leaching of halite and sylvite which initially inhibited the dissolution of alkali feldspars. Feldspar dissolution occurred later and slower indicated by lower concentrations of Na and K reflecting the lower solubility and slow dissolution kinetics of feldspar. Dissolution of anhydrite was predominantly observed from the increased concentration of Ca and SO4 at earlier time periods. However, the Ca/SO4 molar ratio (>1) indicated the concurrent dissolution of both calcite and anhydrite. The presence of carbonates buffered the pH until day 6. Moreover, the mobilization of Mn, Mg, Ba and Fe might be derived from carbonate impurities. Thermodynamic calculations of mineral saturation indices enabled an evaluation of the CO2-water-rock interactions during the experiment and highlighted the dissolution of the Ca-bearing minerals in the studied solution.

  11. Aqueous and air-compatible fabrication of high-performance conductive textiles.

    PubMed

    Wang, Xiaolong; Yan, Casey; Hu, Hong; Zhou, Xuechang; Guo, Ruisheng; Liu, Xuqing; Xie, Zhuang; Huang, Zhifeng; Zheng, Zijian

    2014-08-01

    This paper describes a fully aqueous- and air-compatible chemical approach to preparing high-performance conductive textiles. In this method, the surfaces of textile materials are first modified with an aqueous solution of double-bond-containing silane molecules to form a surface-anchoring layer for subsequent in situ free-radical polymerization of [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC) in the air. Thin layers of poly-METAC (PMETAC) are therefore covalently grafted on top of the silane-modified textile surface. Cu- or Ni-coated textiles are finally fabricated by electroless deposition (ELD) onto the PMETAC-modified textiles. Parameters including polymerization time, temperature, and ELD conditions are studied to optimize the whole fabrication process. The as-made conductive textiles exhibit sheet resistance as low as 0.2???sq(-1) , which makes them highly suitable for use as conductive wires and interconnects in flexible and wearable electronic devices. More importantly, the chemical method is fully compatible with the conventional "pad-dry-cure" fabrication process in the textile manufacturing industry, thus indicating that it is very promising for high-throughput and roll-to-roll fabrication of high-performance metal-coated conductive textiles in the future. PMID:24867263

  12. Direct transformation of xylan-type hemicelluloses to furfural via SnCl? catalysts in aqueous and biphasic systems.

    PubMed

    Wang, Wenju; Ren, Junli; Li, Huiling; Deng, Aojie; Sun, Runcang

    2015-05-01

    Direct catalytic transformation of xylan-type hemicelluloses to furfural in the aqueous system and the biphasic system were comparatively investigated under mild conditions. Screening of several promising chlorides for conversion of beech xylan in the aqueous system revealed the Lewis acid SnCl4 was the most effective catalyst. Comparing to the single aqueous system, the bio-based 2-methyltetrahydrofuran (2-MTHF)/H2O biphasic system was more conducive to the synthesis of furfural, in which the highest furfural yield of 78.1% was achieved by using SnCl4 as catalysts under the optimized reaction conditions (150°C, 120 min). Additionally, the influences of xylan-type hemicelluloses with different chemical and structural features from beech, corncob and bagasse on the furfural production were studied. It was found that furfural yield to some extent was determined by the xylose content in hemicelluloses and also had relationships with the molecular weight of hemicelluloses and the degree of crystallization. PMID:25742750

  13. 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

  14. The acute toxicity of chemically and physically dispersed crude oil to key arctic species under arctic conditions during the open water season

    PubMed Central

    Gardiner, William W; Word, Jack Q; Word, Jack D; Perkins, Robert A; McFarlin, Kelly M; Hester, Brian W; Word, Lucinda S; Ray, Collin M

    2013-01-01

    The acute toxicity of physically and chemically dispersed crude oil and the dispersant Corexit 9500 were evaluated for key Arctic species. The copepod Calanus glacialis, juvenile Arctic cod (Boreogadus saida), and larval sculpin (Myoxocephalus sp.) were tested under conditions representative of the Beaufort and Chukchi Seas during the ice-free season. The toxicity of 3 water-accommodated fractions (WAF) of Alaska North Slope crude oil was examined with spiked, declining exposures. A dispersant-only test was conducted with the copepod C. glacialis. Each preparation with oil (WAF, breaking wave WAF [BWWAF], and chemically enhanced WAF [CEWAF]) produced distinct suites of hydrocarbon constituents; the total concentrations of oil were lowest in WAF and highest in CEWAF preparations. The relative sensitivity for the different species and age classes was similar within each WAF type. Median lethal concentration values based on total petroleum hydrocarbons ranged from 1.6?mg/L to 4.0?mg/L for WAF and BWWAF treatments and from 22?mg/L to 62?mg/L for CEWAF. For Corexit 9500 exposures, median lethal concentration values ranged from 17?mg/L to 50?mg/L. The differences in the relative toxicity among the accommodated fractions indicated that the majority of petroleum hydrocarbons in the CEWAF are in less acutely toxic forms than the components that dominate the WAF or BWWAF. Further evaluation showed that the parent polycyclic aromatic hydrocarbon compounds, specifically naphthalene, were highly correlated to acute toxicity. Environ Toxicol Chem 2013;32:2284–2300. PMID:23765555

  15. Chemical gardens, an example of pattern formation in geophysics

    NASA Astrophysics Data System (ADS)

    Escribano, B.; Cartwright, J. H. E.; Sainz-Diaz, C. I.

    2009-04-01

    Chemical gardens are biomimetic plantlike growths formed by a mixture of salts which precipitate by a combination of the fluid dynamics of convection forced by osmosis, free convection and chemical reactions. Chemical gardens may be implicated in other phenomena which involve precipitation across a colloidal gel membrane that separates two different aqueous solutions, for example, in the context of geophysical pattern formation in geothermal vents, as well as in cement technology and metal corrosion processes. However, the variation in chemical composition, morphology and mechanical properties of the different surfaces of these formations is not well known. Several salts in different concentrations and conditions have been explored under terrestrial gravity and microgravity. The chemical garden structures have been characterized by morphology analysis, scanning electron microscopy, chemical analysis and X-ray diffraction, correlating these data with the biomimetic growth and the physical-chemical nanoprocesses involved in it. Chemical gardens are a very interesting example of pattern formation in geophysics, combining fluid dynamics and chemical reactions to produce a variety of structures.

  16. Aqueous shunts for glaucoma

    PubMed Central

    Minckler, Don; Vedula, Satyanarayana S; Li, Tianjing; Mathew, Milan; Ayyala, Ramesh; Francis, Brian

    2014-01-01

    Background Aqueous shunts are employed for intraocular pressure (IOP) control in primary and secondary glaucomas that fail medical, laser, and other surgical therapies. Objectives This review compares aqueous shunts for IOP control and safety. Search strategy We searched CENTRAL, MEDLINE, PubMed, EMBASE, NRR in January 2006, LILACS to February 2004 and reference lists of included trials. Selection criteria We included all randomized and quasi-randomized trials in which one arm of the study involved shunts. Data collection and analysis Two authors independently extracted data for included studies and a third adjudicated discrepancies. We contacted investigators for missing information. We used fixed-effect models and summarized continuous outcomes using mean differences. Main results We included fifteen trials with a total of 1153 participants with mixed diagnoses. Five studies reported details sufficient to verify the method of randomization but only two had adequate allocation concealment. Data collection and follow-up times were variable. Meta-analysis of two trials comparing Ahmed implant with trabeculectomy found trabeculectomy resulted in lower mean IOPs 11 to 13 months later (mean difference 3.81 mm Hg, 95% CI 1.94 to 5.69 mm Hg). Meta-analysis of two trials comparing double-plate Molteno implant with the Schocket shunt was not done due to substantial heterogeneity. One study comparing ridged with standard double-plate Molteno implants found no clinically significant differences in outcome. Two trials investigating the effectiveness of adjunctive mitomycin (MMC) with the Molteno and Ahmed implants found no evidence of benefit with MMC. Two trials that investigated surgical technique variations with the Ahmed found no benefit with partial tube ligation or excision of Tenon's capsule. One study concluded there were outcome advantages with a double versus a single-plate Molteno implant and one trial comparing the 350 mm2 and 500 mm2 Baerveldt shunts found no clinically significant advantage of the larger device but neither of these trials included all patients randomized. One study suggested improved clinical outcome when MMC was employed with a newly described shunt including ultrasound supporting the conclusion. One small study did not demonstrate an outcome advantage to systemic steroid use postoperatively with single-plate Molteno shunts. One study comparing endocyclophotocoagulation (ECP) with Ahmed implant in complicated glaucomas found no evidence of better IOP control with Ahmed implant over ECP. Authors' conclusions Relatively few randomized trials have been published on aqueous shunts and methodology and data quality among them is poor. To date there is no evidence of superiority of one shunt over another. PMID:16625616

  17. 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.

  18. Flow of Aqueous Humor

    MedlinePLUS

    ... Deadlines & Guidelines Apply for a Grant Terms & Conditions Patent & Intellectual Property Policy For Current Awardees FAQs Our ... Deadlines & Guidelines Apply for a Grant Terms & Conditions Patent & Intellectual Property Policy For Current Awardees FAQs Our ...

  19. Efficacy of aqueous extract of Hippophae rhamnoides and its bio-active flavonoids against hypoxia-induced cell death

    PubMed Central

    Tulsawani, Rajkumar; Gupta, Rashmi; Misra, Kshipra

    2013-01-01

    Objectives: To investigate the protective efficacy of aqueous extract of Hippophae rhamnoides against chronic hypoxic injury using primary rat hepatocytes. Materials and Methods: The extract was prepared using maceration method and characterized by its phenolic and flavonoid content and chemical antioxidant capacity using ferric reducing antioxidant power assay. Hepatocytes were maintained in hypoxia chamber (3% and 1% oxygen) for 72 h. The cells kept under normoxic condition served as control. The cells were treated with the extract and flavonoids; isorhamentin, kaempferol or qurecetin-3-galactoside. After the end of exposure period; cell survival, reactive oxygen species (ROS), leakage of lactate dehydrogenase (LDH), alanine aminotransferase (ALT), aspartate aminotransferase (AST), reduced glutathione (GSH), glutathione peroxidase (GPx), and superoxide dismutase (SOD) levels were measured. Results: The extract showed presence of high phenolic and flavonoid content with significant antioxidant activity in chemical assay. The cell exposed to hypoxia showed concentration dependent cell death and harbored higher reactive oxygen species. In addition, these cells showed significant leakage of intracellular LDH, ALT, and AST accompanied by the diminished levels/activities of GSH, GPx, and SOD. The treatment of cells with aqueous extract of H. rhamnoides reduced hypoxia-induced cell death and prevented increase in ROS levels and leakage of intracellular LDH, ALT, and AST from cells. Moreover, these cells maintained better levels/activities of GSH, GPx, and SOD in comparison to the respective controls. The major flavonoids present in aqueous extract of H. rhamnoides; quercetin-3-galactoside, kaempferol, and isorhamentin also prevented hypoxia induced cell injury individually or in combination, however, the protection offered by these compounds taken together could not match to that of the extract. Conclusions: Overall the findings reveal significance of aqueous extract of H. rhamnoides in controlling ROS-meditated hypoxic injury in cells and can be useful in many hepatic complications. PMID:23833369

  20. Adsorption of bisphenol-A from aqueous solution onto minerals and carbon adsorbents.

    PubMed

    Tsai, Wen-Tien; Lai, Chi-Wei; Su, Ting-Yi

    2006-06-30

    The adsorption behaviors of bisphenol-A, which has been listed as one of endocrine disrupting chemicals, from aqueous solution onto four minerals including andesite, diatomaceous earth, titanium dioxide, and activated bleaching earth, and two activated carbons with coconut-based and coal-based virgins were examined in this work. Based on the adsorption results at the specified conditions, the adsorption capacities of activated carbons are significantly larger than those of mineral adsorbents, implying that the former is effective for removal of the highly hydrophobic adsorbate from the aqueous solution because of its high surface area and low surface polarity. The adsorption capacities of bisphenol-A onto these mineral adsorbents with different pore properties are almost similar in magnitude mainly due to the weakly electrostatic interaction between the mineral surface with negative charge and the target adsorbate with hydrophobic nature. Further, a simplified kinetic model, pseudo-second-order, was tested to investigate the adsorption behaviors of bisphenol-A onto the two common activated carbons at different solution conditions. It was found that the adsorption process could be well described with the pseudo-second-order model. The kinetic parameters of the model obtained in the present work are in line with the pore properties of the two adsorbents. PMID:16343748

  1. Insights into perfluorooctane sulfonate photodegradation in a catalyst-free aqueous solution

    PubMed Central

    Lyu, Xian-Jin; Li, Wen-Wei; Lam, Paul K. S.; Yu, Han-Qing

    2015-01-01

    Photodegradation in the absence of externally added chemicals could be an attractive solution for the removal of perfluorooctane sulfonate (PFOS) in aqueous environment, but the low decomposition rate presents a severe challenge and the underlying mechanisms are unclear. In this study, we demonstrated that PFOS could be effectively degraded in a catalyst-free aqueous solution via a reduction route. Under appropriate pH and temperature conditions, a rapid PFOS photodegradation, with a pseudo-first-order decomposition rate constant of 0.91?h?1, was achieved. In addition, hydrated electrons were considered to be the major photo-generated reductive species responsible for PFOS photodegradation in this system. Its production and reduction ability could be significantly affected by the environmental conditions such as pH, temperature and presence of oxidative species. This study gives insights into the PFOS photodegradation process and may provide useful information for developing catalyst-free photodegradation systems for decomposing PFOS and other persistent water contaminants. PMID:25879866

  2. Depositional conditions for the Kuna Formation, Red Dog Zn-PB-Ag-Barite District, Alaska, inferred from isotopic and chemical proxies

    USGS Publications Warehouse

    Johnson, Craig A.; Dumoulin, Julie A.; Burruss, Robert A.; Slack, John F.

    2015-01-01

    Water column redox conditions, degree of restriction of the depositional basin, and other paleoenvironmental parameters have been determined for the Mississippian Kuna Formation of northwestern Alaska from stratigraphic profiles of Mo, Fe/Al, and S isotopes in pyrite, C isotopes in organic matter, and N isotopes in bulk rock. This unit is important because it hosts the Red Dog and Anarraaq Zn-Pb-Ag ± barite deposits, which together constitute one of the largest zinc resources in the world. The isotopic and chemical proxies record a deep basin environment that became isolated from the open ocean, became increasingly reducing, and ultimately became euxinic. The basin was ventilated briefly and then became isolated again just prior to its demise as a discrete depocenter with the transition to the overlying Siksikpuk Formation. Ventilation corresponded approximately to the initiation of bedded barite deposition in the district, whereas the demise of the basin corresponded approximately to the formation of the massive sulfide deposits. The changes in basin circulation during deposition of the upper Kuna Formation may have had multiple immediate causes, but the underlying driver was probably extensional tectonic activity that also facilitated fluid flow beneath the basin floor. Although the formation of sediment-hosted sulfide deposits is generally favored by highly reducing conditions, the Zn-Pb deposits of the Red Dog district are not found in the major euxinic facies of the Kuna basin, nor did they form during the main period of euxinia. Rather, the deposits occur where strata were permeable to migrating fluids and where excess H2S was available beyond what was produced in situ by decomposition of local sedimentary organic matter. The known deposits formed mainly by replacement of calcareous strata that gained H2S from nearby highly carbonaceous beds (Anarraaq deposit) or by fracturing and vein formation in strata that produced excess H2S by reductive dissolution of preexisting barite (Red Dog deposits).

  3. Chemical and physical studies of type 3 chondrites. IX - Thermoluminescence and hydrothermal annealing experiments and their relationship to metamorphism and aqueous alteration in type below 3.3 ordinary chondrites

    NASA Technical Reports Server (NTRS)

    Guimon, R. Kyle; Sears, Derek W. G.; Lofgren, Gary E.

    1988-01-01

    Thermoluminescence (TL) properties were measured in samples of four type-3.0 chondrites annealed at 400-850 C and 0.77-1 kbar in the presence of various amounts of water and sodium disilicate. Several changes recorded in TL characteristics, such as the lowering of TL sensitivity in certain samples, its increase in other samples, and changes in the peak position and peak width of TL suggested the occurrence of metamorphic processes in these samples. It is suggested that, for the chondrite types above 3.2, the observed changes in TL are consistent with the TL-metamorphism trends, being due to the formation of feldspar by the devitrification of chondrule glass during metamorphism. For types below 3.2, the TL data are consistent with the hypothesis that these chondrules experienced lower levels of metamorphism than the higher types or, alternatively, with the hypothesis that the type 3.0 chondrules are being produced from higher types by aqueous alteration.

  4. Thermal conductivity of aqueous foam

    SciTech Connect

    Drotning, W.D.; Ortega, A.; Havey, P.E.

    1982-05-01

    Thermal conductivity plays an important part in the response of aqueous foams used as geothermal drilling fluids. The thermal conductivity of these foams was measured at ambient conditions using the thermal conductivity probe technique. Foam densities studied were from 0.03 to 0.2 g/cm/sup 3/, corresponding to liquid volume fractions of the same magnitude. Microscopy of the foams indicated bubble sizes in the range 50 to 300 ..mu..m for nitrogen foams, and 30 to 150 ..mu..m for helium foams. Bubble shapes were observed to be polyhedral at low foam densities and spherical at the higher densities. The measured conductivity values ranged from 0.05 to 0.12 W/m-K for the foams studied. The predicted behavior in foam conductivity caused by a change in the conductivity of the discontinuous gas phase was observed using nitrogen or helium gas in the foams. Analysis of the probe response data required an interpretation using the full intergral solution to the heat conduction equation, since the thermal capacity of the foam was small relative to the thermal mass of the probe. The measurements of the thermal conductivity of the foams were influenced by experimental effects such as the probe input power, foam drainage, and the orientation of the probe and test cell. For nitrogen foams, the thermal conductivity vs liquid volume fraction was observed to fall between predictions based on the parallel ordering and Russell models for thermal conduction in heterogeneous materials.

  5. AlN thin films prepared by ArF plasma assisted PLD. Role of process conditions on electronic and chemical-morphological properties

    NASA Astrophysics Data System (ADS)

    Cappelli, E.; Trucchi, D. M.; Orlando, S.; Valentini, V.; Mezzi, A.; Kaciulis, S.

    2014-02-01

    Aluminium nitride thin films were deposited on n-Si <100> substrates by RF plasma activated reactive pulsed laser deposition (PLD). An ArF excimer pulsed laser, 10 Hz and 2.5 J/cm2 energy fluence, has been used to ablate a pure Al target in a reactive atmosphere of N2 plasma (generated by a RF source), at varying processing parameters (substrate temperature, time, and N2 plasma configuration). We studied the dependence and correlation of structural and electronic properties with the experimental conditions. The chemical composition of deposited material has been determined by both Raman and X-ray photoelectron spectroscopy (XPS). Electrical resistivity has been evaluated by the sheet resistance method. Both spectroscopic characterizations (Raman and XPS) show a strong dependence in the formation of AlN on the deposition temperature. At low temperatures, there is little formation of nitride, with a prevalence of aluminium oxide, while at higher temperatures the N uptake increases, with AlN formation. Raman analysis also highlights the formation of nano-structures, for temperatures ?400?C. These material characteristics have a fundamental influence on the electronic properties. Indeed, electrical resistivity properties have been found to be strongly dependent on the film structure, nitrogen incorporation, and presence of mixed oxide compounds, closely related to deposition temperature.

  6. A Nontoxic Polypeptide Oligomer with a Fungicide Potency under Agricultural Conditions Which Is Equal or Greater than That of Their Chemical Counterparts

    PubMed Central

    Monteiro, Sara; Carreira, Alexandra; Freitas, Regina; Pinheiro, Ana Margarida; Ferreira, Ricardo Boavida

    2015-01-01

    There are literally hundreds of polypeptides described in the literature which exhibit fungicide activity. Tens of them have had attempted protection by patent applications but none, as far as we are aware, have found application under real agricultural conditions. The reasons behind may be multiple where the sensitivity to the Sun UV radiation can come in first place. Here we describe a multifunctional glyco-oligomer with 210 kDa which is mainly composed by a 20 kDa polypeptide termed Blad that has been previously shown to be a stable intermediary product of ?-conglutin catabolism. This oligomer accumulates exclusively in the cotyledons of Lupinus species, between days 4 and 12 after the onset of germination. Blad-oligomer reveals a plethora of biochemical properties, like lectin and catalytic activities, which are not unusual per si, but are remarkable when found to coexist in the same protein molecule. With this vast range of chemical characteristics, antifungal activity arises almost as a natural consequence. The biological significance and potential technological applications of Blad-oligomer as a plant fungicide to agriculture, its uniqueness stems from being of polypeptidic in nature, and with efficacies which are either equal or greater than the top fungicides currently in the market are addressed. PMID:25849076

  7. Spectroscopic studies of the effect of aerobic conditions on the chemical characteristics of humic acid in landfill leachate and its implication for the environment.

    PubMed

    Xiaoli, Chai; Yongxia, Hao; Guixiang, Liu; Xin, Zhao; Youcai, Zhao

    2013-05-01

    Humic acids (HAs) that extracted from leachates from semi-aerobic and anaerobic landfills test field at different stabilization times were characterized by elemental composition, Fourier transform infrared spectroscopy (FTIR), and Carbon-13 Cross-Polarization Magic-Angle-Spinning Nuclear Magnetic Resonance ((13)C CP/MAS NMR). The higher sulfur (S) content of HA in the anaerobic landfill leachate after a short stabilization time showed that the S released from the organic matter degradation was more easily stabilized under anaerobic conditions, which indicate that HA from anaerobic landfill leachate was more chemically reactive and played a more important role in mobilizing heavy metal, especially mercury, at early landfill stabilization times. However, the S content of HA from the semi-aerobic landfill increased over time, suggesting that more S was stabilized in HA as the landfill stabilization time was extended. The analytical results for the FTIR and NMR showed that the HA from the anaerobic landfill contained more aromatic groups, while HA from the semi-aerobic landfill had more oxygen-containing groups. The aromatic components of the HA from both the anaerobic and semi-aerobic landfills increased over time, suggesting that the maturity and humification degree of HA increased during the stabilization process. PMID:23461837

  8. 129Xe NMR chemical shift in Xe@C60 calculated at experimental conditions: essential role of the relativity, dynamics, and explicit solvent.

    PubMed

    Standara, Stanislav; Kulhánek, Petr; Marek, Radek; Straka, Michal

    2013-08-15

    The isotropic (129)Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the (129)Xe NMR CS. The (129)Xe shielding constant was obtained by averaging the (129)Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit-Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated (129)Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental (129)Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of (129)Xe NMR parameters in different Xe atom guest-host systems. PMID:23703381

  9. Polymerization of amino acids under primitive earth conditions.

    NASA Technical Reports Server (NTRS)

    Flores, J. J.; Ponnamperuma, C.

    1972-01-01

    Small amounts of peptides were obtained when equal amounts of methane and ammonia were reacted with vaporized aqueous solutions of C14-labeled glycine, L-alanine, L-aspartic acid, L-glutamic acid and L-threonine in the presence of a continuous spark discharge in a 24-hr cyclic process. The experiment was designed to demonstrate the possibility of peptide synthesis under simulated primeval earth conditions. It is theorized that some dehydration-condensation processes may have taken place, with ammonium cyanide, the hydrogencyanide tetramer or aminonitriles as intermediate products, during the early chemical evolution of the earth.

  10. Aqueous activity and sources of water on the chondrite parent asteroids

    NASA Astrophysics Data System (ADS)

    Krot, A.; Alexander, C.; Nagashima, K.; Ciesla, F.; Fujiya, W.

    2014-07-01

    Ages of aqueous alteration of asteroids: Most chondrite parent asteroids experienced aqueous alteration resulting in the formation of secondary minerals, including phyllosilicates, magnetite, Fe,Ni-sulfides, carbonates [(Ca,Mg,Fe,Mn)CO_3)], and fayalite [(Fe,Mn)_2SiO_4] [1]. Mineralogical observations and thermodynamic analysis suggest that the alteration of the various chondrite groups occurred under different physico-chemical conditions (temperature, redox conditions, pH, water/rock ratio). The chronology of aqueous activity on the chondrite parent asteroids can be inferred from ^{53}Mn-^{53}Cr dating (^{53}Mn decays to ^{53}Cr with half-life of 3.7 Myr) of aqueously-formed carbonates and fayalite measured with secondary ion mass-spectrometry. Recently reported ^{53}Mn-^{53}Cr ages of carbonates in CM [2,3], CI [4], CR [5] chondrites, and fayalite in CV [6], CO [6], and LL [7] chondrites indicate that aqueous alteration on the ordinary and carbonaceous chondrite (CC) parent asteroids occurred nearly contemporaneously, ˜3-5 Myr after formation of Ca,Al-rich inclusions (CAIs), the earliest Solar System solids dated [8]. Accretion ages of chondrite parent asteroids: Assuming uniform distribution of a short-lived radionuclide ^{26}Al (decays to ^{26}Mg with half-life of ˜0.7 Myr) in the disk at the canonical level (^{26}Al/^{27}Al ˜5×10^{-5}), the timing of aqueous alteration combined with estimates of peak metamorphic temperatures and thermal modelling of the ordinary and CC parent asteroids suggest that these bodies accreted ˜2-3 Myr after CAI formation [2,3,7]. The inferred accretion ages of ordinary and CC parent asteroids are generally consistent with average ^{26}Al-^{26}Mg ages (^{26}Al decays to ^{26}Mg with half-life of ˜0.7 Myr) of their chondrules [9,10], suggesting that chondrule formation was rapidly followed by accretion and that ^{26}Al was the major heating source of aqueous alteration and thermal metamorphism on these bodies. The observed variations in the degree of aqueous alteration within a chondrite group may indicate that water ices accreted heterogeneously or that there was a fluid flow in their parent bodies. Sources of water on the chondrite parent asteroids: According to the Grand Tack and Nice models, the extensively hydrated (C-, D-, and P-type) asteroids formed between and beyond the giant planets and were scattered into the main asteroid belt during a period of giant planet migration [11,12]. Bulk D/H ratio of chondrite water ices can potentially be used for testing this model, but cannot be measured directly. Alexander et al. [13] used the bulk hydrogen and carbon isotopic compositions of chondrites to estimate the water D/H ratio for a number of chondrite groups. The estimated D/H ratio of water in the extensively hydrated CI, CM, CR and ungrouped carbonaceous chondrite Tagish Lake (spectrally similar to D-type asteroids) are significantly lower than in the measured comets from Oort Cloud comets; the D/H ratio of water in CRs, however, is similar to that in the Jupiter Family Comet Hartley 2 [14]. Alexander et al. [13] concluded that CC parent asteroids accreted ˜3-7 au from the Sun. These data provide important constraints on the Grand Tack and Nice models.

  11. Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen

    NASA Astrophysics Data System (ADS)

    Renard, P.; Siekmann, F.; Gandolfo, A.; Socorro, J.; Salque, G.; Ravier, S.; Quivet, E.; Clément, J.-L.; Traikia, M.; Delort, A.-M.; Voisin, D.; Vuitton, V.; Thissen, R.; Monod, A.

    2013-07-01

    It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from ?-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. Methyl vinyl ketone (MVK) was chosen in the present study as it is an ?,?-unsaturated carbonyl that can undergo radical oligomerization in the aerosol aqueous phase. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under various conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights in our experiments the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the dominance of oligomerization reactions after several minutes of reaction. These processes, together with the large range of initial concentrations investigated show the fundamental role that radical oligomerization processes likely play in polluted fogs and atmospheric aerosol.

  12. Determination of chemical-constituent loads during base-flow and storm-runoff conditions near historical mines in Prospect Gulch, upper Animas River watershed, southwestern Colorado

    USGS Publications Warehouse

    Wirt, Laurie; Leib, K.J.; Bove, D.J.; Mast, M.A.; Evans, J.B.; Meeker, G.P.

    1999-01-01

    Prospect Gulch is a major source of iron, aluminum, zinc, and other metals to Cement Creek. Information is needed to prioritize remediation and develop strategies for cleanup of historical abandoned mine sites in Prospect Gulch. Chemical-constituent loads were determined in Prospect Gulch, a high-elevation alpine stream in southwestern Colorado that is affected by natural acid drainage from weathering of hydro-thermally altered igneous rock and acidic metal-laden discharge from historical abandoned mines. The objective of the study was to identify metal sources to Prospect Gulch. A tracer solution was injected into Prospect Gulch during water-quality sampling so that loading of geochemical constituents could be calculated throughout the study reach. A thunderstorm occurred during the tracer study, hence, metal loads were measured for storm-runoff as well as for base flow. Data from different parts of the study reach represents different flow conditions. The beginning of the reach represents background conditions during base flow immediately upstream from the Lark and Henrietta mines (samples PG5 to PG45). Other samples were collected during storm runoff conditions (PG100 to PG291); during the first flush of metal runoff following the onset of rainfall (PG303 to PG504), and samples PG542 to PG700 were collected during low-flow conditions. During base-flow conditions, the percentage increase in loads for major constituents and trace metals was more than an order of magnitude greater than the corresponding 36 % increase in stream discharge. Within the study reach, the highest percentage increases for dissolved loads were 740 % for iron (Fe), 465 % for aluminum (Al), 500 % for lead (Pb), 380 % for copper (Cu), 100 % for sulfate (SO4), and 50 % for zinc (Zn). Downstream loads near the mouth of Prospect Gulch often greatly exceeded the loads generated within the study reach but varied by metal species. For example, the study reach accounts for about 6 % of the dissolved-Fe load, 13 % of the dissolved-Al load, and 18 % of the dissolved-Zn load; but probably contributes virtually all of the dissolved Cu and Pb. The greatest downstream gains in dissolved trace-metal loads occurred near waste-rock dumps for the historical mines. The major sources of trace metals to the study reach were related to mining. The major source of trace metals in the reach near the mouth is unknown, however is probably related to weathering of highly altered igneous rocks, although an unknown component of trace metals could be derived from mining sources The late-summer storm dramatically increased the loads of most dissolved and total constituents. The effects of the storm were divided into two distinct periods; (1) a first flush of higher metal concentrations that occurred soon after rainfall began and (2) the peak discharge of the storm runoff. The first flush contained the highest loads of dissolved Fe, total and dissolved Zn, Cu, and Cd. The larger concentrations of Fe and sulfate in the first flush were likely derived from iron hydroxide minerals such as jarosite and schwertmanite, which are common on mine dumps in the Prospect Gulch drainage basin. Peak storm runoff contained the highest measured loads of total Fe, and of total and dissolved calcium, magnesium, silica and Al, which were probably derived from weathering of igneous rocks and clay minerals in the drainage basin.

  13. Aqueous alteration on main-belt asteroids

    NASA Astrophysics Data System (ADS)

    Fornasier, S.; Lantz, C.; Barucci, M.; Lazzarin, M.

    2014-07-01

    The study of aqueous alteration is particularly important for unraveling the processes occurring during the earliest times in Solar System history, as it can give information both on the thermal processes and on the localization of water sources in the asteroid belt, and for the associated astrobiological implications. The aqueous alteration process produces the low temperature (< 320 K) chemical alteration of materials by liquid water which acts as a solvent and produces materials like phyllosilicates, sulphates, oxides, carbonates, and hydroxides. This means that liquid water was present in the primordial asteroids, produced by the melting of water ice by heating sources, very probably by ^{26}Al decay. Hydrated minerals have been found mainly on Mars surface, on primitive main-belt asteroids (C, G, B, F, and P-type, following the classification scheme by Tholen, 1984) and possibly also on few transneptunian objects. Reflectance spectroscopy of aqueous altered asteroids shows absorption features in the 0.6-0.9 and 2.5-3.5-micron regions, which are diagnostic of, or associated with, hydrated minerals. In this work, we investigate the aqueous alteration process on a large sample of 600 visible spectra of C-complex asteroids available in the literature. We analyzed all these spectra in a similar way to characterize the absorption-band parameters (band center, depth, and width) and spectral slope, and to look for possible correlations between the aqueous alteration process and the asteroids taxonomic classes, orbital elements, heliocentric distances, albedo, and sizes. We find that 4.6 % of P, 7.7 % of F, 9.8 % of B, 50.5 % of C, and 100 % of the G-type asteroids have absorption bands in the visible region due to hydrated silicates. Our analysis shows that the aqueous alteration sequence starts from the P-type objects, practically unaltered, and increases through the P ? F ? B ? C ? G asteroids, these last being widely aqueously altered, strengthening thus the results previously obtained by Vilas (1994). We confirm the strong correlation between the 0.7-?m band and the 3-? m band, the deepest feature associated with hydrated minerals, as 95 % of the asteroids showing the 0.7-? m band have also the 3-? m feature. 45 % of the asteroids belonging to the C-complex (the F, B, C, and G classes) have signatures of aqueously altered materials in the visible range. It must be noted that this percentage represents a lower limit in the number of hydrated asteroids, simply because the 3-? m band, the main absorption feature produced by hydrated silicates, may be present in the spectra of primitive asteroids when no bands are detected in the visible range. All this considered, we estimate that 70 % of the C-complex asteroids might have the 3-? m signature in the IR range and thus were affected by the aqueous alteration process in the past. We find that the aqueous alteration process dominates in primitive asteroids located between 2.3 and 3.1 au, that is, at smaller heliocentric distances than previously suggested by Vilas et al. (1993). The percentage of hydrated asteroids is strongly correlated with their size (Fornasier et al. 2014). The aqueous alteration process is less effective for bodies smaller than 50 km, while it dominates in the 50-240-km sized primitive asteroids. No correlation is found between the aqueous alteration process and the asteroid albedo or orbital elements. Aqueously altered asteroids are the plausible parent bodies of CM2 meteorites. Nevertheless, we see a systematic difference in the 0.7-? m band center position, the CM2 meteorites having a band centered at longer wavelengths (0.71-0.75 ? m) compared to that of hydrated asteroids. Moreover, the hydrated asteroids are more clustered in spectral slope and band depth than the CM meteorites. All these spectral differences may be attributed to different mineral abundances (CM2 meteorites being more serpentine rich than the asteroids), and/or to grain-size effects, or simply to the fact the CM2 collected on the Earth might not be representative

  14. Mars Aqueous Processing System

    NASA Technical Reports Server (NTRS)

    Berggren, Mark; Wilson, Cherie; Carrera, Stacy; Rose, Heather; Muscatello, Anthony; Kilgore, James; Zubrin, Robert

    2012-01-01

    The goal of the Mars Aqueous Processing System (MAPS) is to establish a flexible process that generates multiple products that are useful for human habitation. Selectively extracting useful components into an aqueous solution, and then sequentially recovering individual constituents, can obtain a suite of refined or semi-refined products. Similarities in the bulk composition (although not necessarily of the mineralogy) of Martian and Lunar soils potentially make MAPS widely applicable. Similar process steps can be conducted on both Mars and Lunar soils while tailoring the reaction extents and recoveries to the specifics of each location. The MAPS closed-loop process selectively extracts, and then recovers, constituents from soils using acids and bases. The emphasis on Mars involves the production of useful materials such as iron, silica, alumina, magnesia, and concrete with recovery of oxygen as a byproduct. On the Moon, similar chemistry is applied with emphasis on oxygen production. This innovation has been demonstrated to produce high-grade materials, such as metallic iron, aluminum oxide, magnesium oxide, and calcium oxide, from lunar and Martian soil simulants. Most of the target products exhibited purities of 80 to 90 percent or more, allowing direct use for many potential applications. Up to one-fourth of the feed soil mass was converted to metal, metal oxide, and oxygen products. The soil residue contained elevated silica content, allowing for potential additional refining and extraction for recovery of materials needed for photovoltaic, semiconductor, and glass applications. A high-grade iron oxide concentrate derived from lunar soil simulant was used to produce a metallic iron component using a novel, combined hydrogen reduction/metal sintering technique. The part was subsequently machined and found to be structurally sound. The behavior of the lunar-simulant-derived iron product was very similar to that produced using the same methods on a Michigan iron ore concentrate, which demonstrates that lunar-derived material can be used in a manner similar to conventional terrestrial iron. Metallic iron was also produced from the Mars soil simulant. The aluminum and magnesium oxide products produced by MAPS from lunar and Mars soil simulants exhibited excellent thermal stability, and were shown to be capable of use for refractory oxide structural materials, or insulation at temperatures far in excess of what could be achieved using unrefined soils. These materials exhibited the refractory characteristics needed to support iron casting and forming operations, as well as other thermal processing needs. Extraction residue samples contained up to 79 percent silica. Such samples were successfully fused into a glass that exhibited high light transmittance.

  15. Chemical comparisons of liquid fuel produced by thermochemical liquefaction of various biomass materials

    SciTech Connect

    Russell, J.A.; Molton, P.M.; Landsman, S.D.

    1980-12-01

    Liquefaction of biomass in aqueous alkali at temperatures up to 350/sup 0/C is an effective way to convert solid wastes into liquid fuels. The liqefaction oils of several forms of biomass differing in proportions of cellulose, hemi-cellulose, lignin, protein, and minerals were studied and their chemical composition compared. It was that the proportions of chemical components varied considerably depending on the type of biomass liquefied. However, all the oils, even those produced from cellulose, had similar chemical characteristics due to the presence of significant quantities of phenols. These phenols are at least partially responsible for the corrosivity and viscosity commonly associated with biomass oils. The differences in chemical component distribution in the various biomass oils might successfully be exploited if the oil is to be used as a chemical feedstock. If the oil is to be used as a fuel, however, then reaction conditions will be a more important consideration than the source of biomass.

  16. The chemical conditions of the late Archean Hamersley basin inferred from whole rock and pyrite geochemistry with ?33S and ?34S isotope analyses

    NASA Astrophysics Data System (ADS)

    Gregory, Daniel D.; Large, Ross R.; Halpin, Jacqueline A.; Steadman, Jeffery A.; Hickman, Arthur H.; Ireland, Trevor R.; Holden, Peter

    2015-01-01

    The well-preserved late Archean sedimentary rocks of the Fortescue and Hamersley Basins in Western Australia offer fascinating insights into early earth ocean chemistry prior to the Great Oxidation Event (GOE). In this study, we use a combination of whole rock geochemistry, LA-ICPMS trace element analysis of sedimentary pyrite and pyrrhotite and SHRIMP-SI sulfur isotope analyses to elucidate the chemical changes in these sedimentary rocks. These proxies are used to examine chemical conditions of the ocean during the late Archean. Two to three periods of oxygen enrichment prior to the deposition of banded iron formations (BIF) can be identified. One minor stage of general increase in whole rock enrichment factors and trace element content of pyrite is observed up stratigraphy in the Jeerinah Formation, Fortescue Basin and a more substantial stage is present in the Paraburdoo and Bee Gorge Members of the Wittenoom Formation, Hamersley Basin. Some of the trace element enrichments indicate organic matter burial flux (Ni, Cr, Zn, Co and Cu) which suggests an increase in biological productivity. If the increased biological activity reflects an increase in cyanobacteria activity then an associated increase in oxygen is likely to have occurred during the deposition of the Bee Gorge Member. An increase in atmospheric oxygen would result in continental weathering of sulfide and other minerals, increasing the trace element content of the water column via erosion and avoiding excessive depletion of trace elements due to drawdown in seawater. Since some of these trace elements may also be limiting nutrients (such as Mo and Se) for the cyanobacteria, the degree of biological productivity may have further increased due to the increasing amount of trace elements introduced by oxygenation in a positive feedback loop. These periods of increased productivity and oxygen rise stopped prior to the onset of BIF deposition in the Hamersley Basin. This may be due to the ocean reaching an oxidation threshold, enabling the precipitation of hematite and magnetite BIF. The BIF deposition caused depletion of ocean nutrients such as phosphate, severely limiting the growth of cyanobacteria, and thus limiting further oxygen production.

  17. Reorientation and Allied Dynamics in Water and Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Laage, Damien; Stirnemann, Guillaume; Sterpone, Fabio; Rey, Rossend; Hynes, James T.

    2011-05-01

    The reorientation of a water molecule is important for a host of phenomena, ranging over—in an only partial listing—the key dynamic hydrogen-bond network restructuring of water itself, aqueous solution chemical reaction mechanisms and rates, ion transport in aqueous solution and membranes, protein folding, and enzymatic activity. This review focuses on water reorientation and related dynamics in pure water, and for aqueous solutes with hydrophobic, hydrophilic, and amphiphilic character, ranging from tetra-methylurea to halide ions and amino acids. Attention is given to the application of theory, simulation, and experiment in the probing of these dynamics, in usefully describing them, and in assessing the description. Special emphasis is placed on a novel sudden, large-amplitude jump mechanism for water reorientation, which contrasts with the commonly assumed Debye rotational diffusion mechanism, characterized by small-amplitude angular motion. Some open questions and directions for further research are also discussed.

  18. Monitoring of Aqueous Fullerene Dispersions by Thermal-Lens Spectrometry

    NASA Astrophysics Data System (ADS)

    Mikheev, I. V.; Volkov, D. S.; Proskurnin, M. A.; Korobov, M. V.

    2015-06-01

    Aqueous fullerene solutions (dispersions) are very promising materials of biomedicine and biotechnology. Of importance are the traceability of their production and characterization of their optical and colloidal properties. Thermal-lens spectrometry, as a method suitable for both optical and thermophysical studies, was used to elucidate the forms of non-modified fullerenes in their aqueous dispersions and to determine low concentrations of and fullerenes. It was shown that the residual amounts of toluene in aqueous fullerene dispersions made according to the solvent-exchange protocol could be detected by thermal lensing. As a result, the technique for the production of aqueous fullerene dispersions was improved compared to the existing data providing higher fullerene concentrations. The limits of detection of and fullerenes are approximately , which are 20-fold lower compared to conventional spectrophotometry. The distinction between aqueous fullerene dispersions in comparison with organic solutions of fullerenes caused by the formation of large clusters is shown by the comparison of transient and steady-state calibration curves for aqueous and organic fullerene solutions and model reference systems under various thermal-lens excitation conditions. The advantages of thermal lensing for such colloidal systems are discussed.

  19. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    NASA Technical Reports Server (NTRS)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  20. Aqueous photolysis of niclosamide

    USGS Publications Warehouse

    Graebing, P.W.; Chib, J.S.; Hubert, T.D.; Gingerich, W.H.

    2004-01-01

    The photodegradation of [14C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 A? 1.0 A?C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising 40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

  1. Aqueous chlorination of resorcinol

    USGS Publications Warehouse

    Heasley, V.L.; Burns, M.D.; Kemalyan, N.A.; Mckee, T.C.; Schroeter, H.; Teegarden, B.R.; Whitney, S.E.; Wershaw, R.L.

    1989-01-01

    An investigation of the aqueous chlorination (NaOCl) of resorcinol is reported. The following intermediates were detected in moderate to high yield at different pH values and varying percentages of chlorination: 2-chloro-, 4-chloro-, 2,4-dichloro-, 4,6-dichloro- and 2,4,6-trichlororesorcinol. Only trace amounts of the intermediates were detected when the chlorination was conducted in the presence of phosphate buffer. This result has significant implications since resorcinol in phosphate buffer has been used as a model compound in several recent studies on the formation of chlorinated hydrocarbons during chlorination of drinking water. Relative rates of chlorination were determined for resorcinol and several of the chlorinated resorcinols. Resorcinol was found to chlorinate only three times faster than 2,4,6-trichlororesorcinol. The structure 2,4,6-trichlororesorcinol was established as a monohydrate even after sublimation. A tetrachloro or pentachloro intermediate was not detected, suggesting that the ring-opening step of such an intermediate must be rapid. ?? 1989.

  2. Sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on the surface of porous graphitized carbon

    NASA Astrophysics Data System (ADS)

    Savchenkova, A. S.; Buryak, A. K.; Kurbatova, S. V.

    2015-09-01

    The sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on porous graphitized carbon was studied. The effect of the structure of analyte molecules and the eluent composition on the characteristics of retention under the conditions of RP HPLC was analyzed. The effect of pH of the eluent on the shift of equilibrium in aqueous acetonitrile solutions was investigated.

  3. ASSESSMENT OF LIQUID EMULSION MEMBRANE FOR CLEAN UP OF AQUEOUS WASTE EFFLUENTS FROM HAZARDOUS ELEMENTS

    SciTech Connect

    El-Reefy, Sohair A.; Selim, Y.T.; Hassan, M.A.; Aly, H.F.

    2003-02-27

    Four liquid emulsion membrane (LEM) systems are given to remove different hazardous elements such as uranium, thorium, cobalt, copper, lead, and cadmium from different aqueous waste effluents. The optimum conditions for use of these systems are deduced. The potentiality of LEM for removal of hazardous pollutants from aqueous waste solutions is given.

  4. Thermodynamics and mechanisms of glycine solvation in aqueous NaCl and KCl solutions at 298.15 K

    NASA Astrophysics Data System (ADS)

    Roy, S.; Hossain, A.; Mahali, K.; Dolui, B. K.

    2015-11-01

    In the present study the solubility of glycine in aqueous sodium chloride and potassium chloride solution was determined under different experimental conditions using `formol titrimetry' method. The thermodynamic parameters like standard transfer Gibbs energies and entropies have been evaluated at 298.15 K. Other important parameters like molar volume, densities, solvent diameter, etc., of the experimental solutions have also been determined in this study. The above mentioned parameters have been used to determine ? t,ch 0 ( i)i.e., chemical effects of the transfer Gibbs energies and T? t, ch 0 ( i)i.e., chemical effects of the transfer entropy. The solvation of glycine is influenced by different factors such as nature of the solute, interactions between solute and solvents, etc., which has been explained by different physical and analytical approach.

  5. Hydrodynamics of aqueous humor outflow

    E-print Network

    Overby, Darryl Ray, 1974-

    2002-01-01

    Primary open-angle glaucoma (POAG) is a leading cause of irreversible blindness resulting from elevated intraocular pressure caused by a pathologic increase in the resistance to aqueous humor outflow from the eye. Currently, ...

  6. CAPSULE REPORT: AQUEOUS MERCURY TREATMENT

    EPA Science Inventory

    This report describes established technologies and identifies evolving methods for treating aqueous mercury. The information provided encompasses full-, pilot- and bench-scale treatment results as presented in the technical literature. The report describes alternative technologi...

  7. Modelling the growth/no growth boundary of Zygosaccharomyces bailii in acidic conditions: a contribution to the alternative method to preserve foods without using chemical preservatives.

    PubMed

    Dang, T D T; Mertens, L; Vermeulen, A; Geeraerd, A H; Van Impe, J F; Debevere, J; Devlieghere, F

    2010-01-31

    The aim of the study was to develop mathematical models describing growth/no growth (G/NG) boundaries of the highly resistant food spoilage yeast-Zygosaccharomyces bailii-in different environmental conditions, taking acidified sauces as the target product. By applying these models, the stability of products with characteristics within the investigated pH, a(w) and acetic acid ranges can be evaluated. Besides, the well-defined no growth regions can be used in the development of guidelines regarding formulation of new shelf-stable foods without using chemical preservatives, which would facilitate the innovation of additive-free products. Experiments were performed at different temperatures and periods (22 degrees C for 45 and 60days, 30 degrees C for 45days) in 150 modified Sabouraud media characterized by high amount of sugars (glucose and fructose, 15% (w/v)), acetic acid (0.0-2.5% (v/v), 6 levels), pH (3.0-5.0, 5 levels) and a(w) (0.93-0.97, 5 levels). These time and temperature combinations were chosen as they are commonly applied for shelf-stable foods. The media were inoculated with ca. 4.5 log CFU/ml and yeast growth was monitored daily using optical density measurements. Every condition was examined in 20 replicates in order to yield accurate growth probabilities. Three separate ordinary logistic regression models were developed for different tested temperatures and incubation time. The total