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Sample records for acidic aqueous environments

  1. Dissolution of PZT 52/48 in aqueous sulfuric acid environments

    NASA Astrophysics Data System (ADS)

    Calebrese, Steven

    With the recent interest for PZT use as a self-powered nanonsensor in extreme environments, such as an oil well, it is important to ensure the stability of the material under these conditions. Oil wells are known for being extremely caustic, with high temperature, low pH and high pressures. It has been shown that in the presence of sulfuric acid PZT is subject to chemical attack. This study attempts to identify the effects that pH and temperature have on the rate of the reaction. Sulfuric acid was used as a proxy for the H2S environment found in oil wells. Exposure of bulk PZT and thin film specimens to H2S was studied. PZT 52/48 thin films were fabricated via the sol gel process. PZT was exposed to both single drops of aqueous sulfuric acid and submerged in a bath of solution. During bath exposure potential on the substrate surface of thin film samples was recorded using a voltmeter vs. and Ag/AgCl reference electrode. Thin Film samples were exposed to a single drop of 0.1 N and 1 N aqueous sulfuric acid solutions at temperatures between 25° C and 92° C. It was optically observed that a white filmed appeared on the surface as a reaction product. At both concentrations, increases in temperature lead to an increase in reaction rate for droplet exposed samples. These reactions were found to follow Arrhenius behavior. The 1 N solution activation energy of film appearance was found to be 69100 J, and for 0.1 N solution was found to be 48300 J. It was expected that an increase in concentration would lead to an increase in reaction rate as well. However for single droplet exposure it was found that lower concentrations resulted in increased reaction rate. This may be due to the difference in interfacial energy between the solution and PZT surface as a result of the concentration of sulfuric acid. The potential on the substrate during bath exposure was between -0.22 V and 0.1 V. As a ferroelectric, PZT is expected to spontaneously polarize and variations in potential

  2. MIPs in Aqueous Environments.

    PubMed

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

    2015-01-01

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

  3. Molecular Modeling of Ammonium, Calcium, Sulfur, and Sodium Lignosulphonates in Acid and Basic Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Salazar Valencia, P. J.; Bolívar Marinez, L. E.; Pérez Merchancano, S. T.

    2015-12-01

    Lignosulphonates (LS), also known as lignin sulfonates or sulfite lignin, are lignins in sulfonated forms, obtained from the "sulfite liquors," a residue of the wood pulp extraction process. Their main utility lies in its wide range of properties, they can be used as additives, dispersants, binders, fluxing, binder agents, etc. in fields ranging from food to fertilizer manufacture and even as agents in the preparation of ion exchange membranes. Since they can be manufactured relatively easy and quickly, and that its molecular size can be manipulated to obtain fragments of very low molecular weight, they are used as transport agents in the food industry, cosmetics, pharmaceutical and drug development, and as molecular elements for the treatment of health problems. In this paper, we study the electronic structural and optical characteristics of LS incorporating ammonium, sulfur, calcium, and sodium ions in acidic and basic aqueous media in order to gain a better understanding of their behavior and the very interesting properties exhibit. The studies were performed using the molecular modeling program HyperChem 5 using the semiempirical method PM3 of the NDO Family (neglect of differential overlap), to calculate the structural properties. We calculated the electronic and optical properties using the semiempirical method ZINDO / CI.

  4. Adsorption behavior of antimony(III) oxyanions on magnetite surface in aqueous organic acid environment

    NASA Astrophysics Data System (ADS)

    Mittal, Vinit K.; Bera, Santanu; Narasimhan, S. V.; Velmurugan, S.

    2013-02-01

    Antimony(III) adsorption is observed on magnetite (Fe3O4) surface under acidic and reducing condition through surface hydroxyl (SOH) groups bonding on Fe3O4 surface. Desorption of adsorbed Sb(III) is observed from Fe3O4 surface along with iron release in organic acid at 85 °C after 5 h of experiment. Tartaric acid (TA) shows minimum Sb(III) adsorption on Fe3O4 among the organic acid studied. The reason is TA having two sets of adjacent functional groups viz. Odbnd Csbnd OH and Csbnd OH which are responsible for the formation of five-membered bidendate chelate with Sb(III). Other oxyanions, cations or complexing agents along with TA influences the Sb(III) adsorption on Fe3O4. The surface of magnetite is modified by the addition of fatty acids viz. Lauric acid, benzoic acid to bind the Ssbnd OH groups present on the surface. This results in delaying the process of adsorption without changing the quantity of saturation adsorption of Sb(III) on Fe3O4 surface.

  5. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    SciTech Connect

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; Crocker, Mark; Lewis, Sr., Samuel A.; Lance, Michael J.; Meyer, III, Harry M.; More, Karren L.

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

  6. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    DOE PAGESBeta

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; Crocker, Mark; Lewis, Sr., Samuel A.; Lance, Michael J.; Meyer, III, Harry M.; More, Karren L.

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating themore » possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.« less

  7. Ancient aqueous environments at Endeavour crater, Mars

    USGS Publications Warehouse

    Arvidson, R. E.; Squyres, S. W.; Bell, J.F., III; Catalano, J.G.; Clark, B. C.; Crumpler, L.S.; de Souza, P.A., Jr.; Fairén, A.G.; Farrand, W. H.; Fox, V.K.; Gellert, Ralf; Ghosh, A.; Golombeck, M.P.; Grotzinger, J.P.; Guinness, E.A.; Herkenhoff, Kenneth E.; Jolliff, B.L.; Knoll, A.H.; Li, R.; McLennan, S.M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, Johnnie N.; Morris, R.V.; Murchie, S.L.; Parker, T.J.; Paulsen, G.; Rice, J.W.; Ruff, S.W.; Smith, M.D.; Wolff, M.J.

    2014-01-01

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe+3-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  8. Ancient aqueous environments at Endeavour crater, Mars.

    PubMed

    Arvidson, R E; Squyres, S W; Bell, J F; Catalano, J G; Clark, B C; Crumpler, L S; de Souza, P A; Fairén, A G; Farrand, W H; Fox, V K; Gellert, R; Ghosh, A; Golombek, M P; Grotzinger, J P; Guinness, E A; Herkenhoff, K E; Jolliff, B L; Knoll, A H; Li, R; McLennan, S M; Ming, D W; Mittlefehldt, D W; Moore, J M; Morris, R V; Murchie, S L; Parker, T J; Paulsen, G; Rice, J W; Ruff, S W; Smith, M D; Wolff, M J

    2014-01-24

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe(+3)-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum. PMID:24458648

  9. Heat-initiated prebiotic formation of peptides from glycine/aspartic acid and glycine/valine in aqueous environment and clay suspension

    NASA Astrophysics Data System (ADS)

    Pant, Chandra Kala; Lata, Hem; Pathak, Hari Datt; Mehata, Mohan Singh

    2009-04-01

    The effect of heat on the reaction system of glycine/aspartic acid and glycine/valine in the aqueous environment as well as in montmorillonite clay suspension with or without divalent cations (Ca2+, Mg2+ and Ni2+) has been investigated at 85°C±5°C for varying periods under prebiotic drying and wetting conditions. The resulting products were analysed and characterized by chromatographic and spectroscopic methods. Peptide formation appears to depend on the duration of heat effect, nature of reactant amino acids and, to some extent, on montmorillonite clay incorporated with divalent cations. In the glycine/aspartic acid system, oligomerization of glycine was limited up to trimer level (Gly)3 along with the formation of glycyl-aspartic acid, while linear and cyclic peptides of aspartic acid were not formed, whereas the glycine/valine system preferentially elongated homo-oligopeptide of glycine up to pentamer level (Gly)5 along with formation of hetero-peptides (Gly-Val and Val-Gly). These studies are relevant in the context of the prebiotic origin of proteins and the role of clay and metal ions in condensation and oligomerization of amino acids. The length of the bio-oligomer chain depends upon the reaction conditions. However, condensation into even a small length seems significant, as the same process would have taken millions of years in the primitive era of the Earth, leading to the first proteins.

  10. Fluorescent Ag nanoclusters prepared in aqueous poly(acrylic acid-co-maleic acid) solutions: a spectroscopic study of their excited state dynamics, size and local environment.

    PubMed

    Dandapat, Manika; Mandal, Debabrata

    2016-01-28

    Stable, fluorescent Ag nanoclusters were prepared in aqueous solutions of Na(+) salt of the carboxylate-rich polymer poly(acrylic acid-co-maleic acid) under brief spells of UV irradiation. The nanoclusters were nearly spherical, with diameters within 1.90 ± 0.50 nm, but displayed a prominent red edge excitation shift (REES) of fluorescence upon exciting within the visible absorption band, indicating heterogeneity of energy level distributions. Spectroscopic studies revealed that irrespective of whether the nanoclusters are excited in their UV or visible absorption bands, their fluorescence always ensues from the same manifold of emissive states, with a broad range of fluorescence lifetimes from ∼150 fs to 1 ns. PMID:26700465

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

    PubMed Central

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

    2014-01-01

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

  12. 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.

  13. Aqueous Photochemistry of Glyoxylic Acid.

    PubMed

    Eugene, Alexis J; Xia, Sha-Sha; Guzman, Marcelo I

    2016-06-01

    Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosols (SOA) from gas phase precursors is relatively well understood, studying aqueous chemical reactions contributing to the total SOA budget is the current focus of major attention. Field measurements have revealed that mono-, di-, and oxo-carboxylic acids are abundant species present in SOA and atmospheric waters. This work explores the fate of one of these 2-oxocarboxylic acids, glyoxylic acid, which can photogenerate reactive species under solar irradiation. Additionally, the dark thermal aging of photoproducts is studied by UV-visible and fluorescence spectroscopies to reveal that the optical properties are altered by the glyoxal produced. The optical properties display periodicity in the time domain of the UV-visible spectrum of chromophores with absorption enhancement (thermochromism) or loss (photobleaching) during nighttime and daytime cycles, respectively. During irradiation, excited state glyoxylic acid can undergo α-cleavage or participate in hydrogen abstractions. The use of (13)C nuclear magnetic resonance spectroscopy (NMR) analysis shows that glyoxal is an important intermediate produced during direct photolysis. Glyoxal quickly reaches a quasi-steady state as confirmed by UHPLC-MS analysis of its corresponding (E) and (Z) 2,4-dinitrophenylhydrazones. The homolytic cleavage of glyoxylic acid is proposed as a fundamental step for the production of glyoxal. Both carbon oxides, CO2(g) and CO(g) evolving to the gas-phase, are quantified by FTIR spectroscopy. Finally, formic acid, oxalic acid, and tartaric acid photoproducts are identified by ion chromatography (IC) with conductivity and electrospray (ESI) mass spectrometry (MS) detection and (1)H NMR spectroscopy. A reaction mechanism is proposed based on all experimental observations. PMID:27192089

  14. Unusual mercury isotopic compositions in aqueous environment

    NASA Astrophysics Data System (ADS)

    Chen, J.; Hintelmann, H.; Zheng, W.; Feng, X.; Cai, H.; Wang, Z.; Yuan, S.

    2014-12-01

    Preliminary studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in natural samples. Laboratory experiments showed that photochemical reduction of inorganic mercury (iHg) and methylmercury (MMHg) and liquid-vapour evaporation could produce MIF of odd Hg isotopes. This was thought to cause the MIF actually observed in aquatic organisms. Although isotopic measurements of Hg in aqueous environment would give direct evidence, little data was reported for surface water samples. Recent work reported, unexpectedly, positive MIF of odd Hg isotopes in both precipitation and ambient air, in contrast with the prediction of laboratory experiments and measurements of Hg accumulated in lichens . Intriguingly, MIF of even-mass Hg isotope (200Hg) was also recently determined in the atmosphere. In contrast with the now mainstream observation of odd Hg isotope anomaly that has several theoretical explanations, the hitherto mysterious even Hg isotope anomalies were neither reported in laboratory experiments, nor predicted by isotope fractionation mechanisms, highlighting the importance of further study on Hg isotopes in variable systems. Our measurements of lichens and lake water samples from different countries show for the first time significant Δ200Hg in surface terrestrial reservoirs, realizing a direct connection of even Hg isotope anomaly in the terrestrial reservoirs to the atmospheric deposition, and fulfilling the gap of Δ200Hg between the atmosphere and the terrestrial receptors. The specific odd Hg isotope compositions determined in lake waters also support the atmosphere contribution, and may be directly linked to the high Δ199Hg values largely determined and manifested on the top of aqueous food web. Our data show that the watershed Hg input is another contributing source, rather than the in-lake processes, to explain the lacustrine Hg isotope anomalies. Interestingly, lake sediments are isotopically

  15. Conductance Studies of Aqueous Succinic Acid

    NASA Astrophysics Data System (ADS)

    Apelblat, Alexander; Barthel, Josef

    1992-03-01

    Conductance measurements of aqueous solutions of succinic acid and of di-sodium succinate were performed from 278.15 to 308.15 K and the limiting conductances λ0 (1/2 Succ2- ) are reported. The Waiden product is independent of temperature: λ0(1/2 Succ2-)*η(T) = 0.503 ± 0.001. The salt conductances closely obey the Onsager limiting law. The evaluation of the equilibrium constants for the primary and secondary steps of dissociation, K1 and K2, and the limiting conductances of the hydrosuccinate ion, λ0(HSucc-), are discussed using the Quint and Viallard conductance equation

  16. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments. PMID:23258765

  17. RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

    DOEpatents

    Ader, M.

    1963-11-19

    A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

  18. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  19. PROCESS FOR RECOVERING URANIUM FROM AQUEOUS PHOSPHORIC ACID LIQUORS

    DOEpatents

    Schmitt, J.M.

    1962-09-01

    A liquid-liquid extraction method is given for recovering uranium values from aqueous solutions. An acidic aqueous solution containing uranium values is contacted with an organic phase comprising an organic diluent and the reaction product of phosphorous pentoxide and a substantially pure dialkylphosphoric acid. The uranium values are transferred to the organic phase even from aqueous solutions containing a high concentration of strong uranium complexing agents such as phosphate ions. (AEC)

  20. Aqueous diffusion in repository and backfill environments

    SciTech Connect

    Conca, J.L.; Apted, M.; Arthur, R.

    1993-12-31

    Aqueous diffusion coefficients have been experimentally determined in a variety of porous/fractured geologic and engineered media. For performance assessment applications, the purely diffusive flux must be separated from retardation effects. The simple diffusion coefficient, D, does not include any transient chemical effects, e.g., sorption, which lower the diffusion coefficient for some finite time period until equilibrium is reached. D is primarily a function of volumetric water content, {theta}, and not material characteristics. At high water contents, D gradually declines as water content decreases, from 10{sup -5} cm{sup 2}/sec at {theta} {approximately}0.5%. Although surface diffusion has a strong experimental basis in the transport of gases along metal surfaces experimental evidence for aqueous geologic/backfill/engineered systems strongly indicates that surface diffusion is not important, even in bentonite, because of the extremely poor connectivity among electric double-layers and the extremely low diffusivities and high {partial_derivative}C/{partial_derivative}x at small area/point contacts which more than negate the increased flux along intragrain surfaces.

  1. Photophysics of (CdSe)ZnS Colloidal Quantum Dots in an Aqueous Environment Stabilized with Amino Acids and Genetically-Modified Proteins

    SciTech Connect

    Ai, X.; Xu, Q.; Jones, M.; Song, Q.; Ding, S.-Y.; Ellingson, R. J.; Himmel, M.; Rumbles, G.

    2007-01-01

    Using a combination of two amino acids, histidine and N-acetyl-cysteine, to replace the original organic capping groups of (CdSe)ZnS quantum dots, water-soluble and highly luminescent (CdSe)ZnS quantum dots have been successfully prepared at pH 8. Characterization by steady-state and time-resolved photoluminescence spectroscopy, and transient absorption spectroscopy, demonstrate that the electronic properties of these quantum dots exceed those of the original as-synthesized samples dissolved in a more-conventional organic solvent. Furthermore, these amino acid-stabilized quantum dots have been assembled onto a cellulose substrate via cellulose binding proteins that specifically bind to cellulose and was genetically engineered to harbor dual hexahistidine tags at the N- and C-termini to confer binding with the zinc(II) on the quantum dot surface. The spectroscopic measurements show that the protein-bound quantum dots continue to retain their desirable electronic properties when bound on the substrate. Meanwhile, the specific and very selective binding properties of the proteins have remained effective. (1)Select optimal greenhouse gas (GHG) and petroleum reduction strategies for each fleet location, (2)Meet or exceed Federal fleet GHG and petroleum reduction requirements outlined in the Guidance, (3)Acquire vehicles to support these strategies while minimizing fleet size and vehicle miles traveled (VMT), (4)Refine strategies based on agency performance.

  2. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  3. Exploiting the interactions of aromatic units for folding and assembly in aqueous environments.

    PubMed

    Ikkanda, B A; Iverson, B L

    2016-06-14

    A variety of non-covalent interactions (including hydrogen bonding, ionic interactions, metal coordination and desolvation/solvation) have been utilized to organize oligomers into well-defined structures. Herein is described a survey of aromatic foldamers that capitalize on electrostatic complementarity of substituted aromatic units to drive folding and assembly in aqueous environments. A brief description of recent advances in the understanding of aromatic interactions is provided, followed by examples of foldamers that exploit interactions between aromatic units to drive their assembly in predictable fashion. The history of our aromatic foldamers is traced from the first structure designed to fold into a pleated structure in an aqueous environment to a heteroduplex system more related to nucleic acids. Taken together, the results demonstrate that electrostatic complementarity of aromatic units provides a versatile framework for driving predictable folding and assembly in aqueous environments. PMID:27080050

  4. Techniques for sensing methanol concentration in aqueous environments

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

    2001-01-01

    An analyte concentration sensor that is capable of fast and reliable sensing of analyte concentration in aqueous environments with high concentrations of the analyte. Preferably, the present invention is a methanol concentration sensor device coupled to a fuel metering control system for use in a liquid direct-feed fuel cell.

  5. Sonophotocatalytic mineralization of Norflurazon in aqueous environment.

    PubMed

    Sathishkumar, Panneerselvam; Mangalaraja, Ramalinga Viswanathan; Rozas, Oscar; Vergara, Carola; Mansilla, Héctor D; Gracia-Pinilla, M A; Anandan, Sambandam

    2016-03-01

    Norflurazon (4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)phenyl]pyridazin-3(2H)-one; C12H9ClF3N3O) is an excellent weed controlling agent being practiced in the agricultural lands. The excessive addition or the undissolved Norflurazon (maximum solubility 28 mg/L at 25 °C) enters into the aquatic environment and causes the adverse effects associated with its high concentration. To avoid the perilous effects, visible light assisted photocatalysis set-up coupled with the 42 kHz ultrasound producing bath type sonicator is used to completely mineralize the Norflurazon. TiO2, ZnO and gold loaded zinc oxide nanocatalysts were utilized to study the mineralization of Norflurazon. Au-ZnO shows the greater efficiency for the sonophotocatalytic removal of Norflurazon among the various nanocatalysts employed to study the mineralization. The order of Norflurazon mineralization was sonophotocatalysis > sonocatalysis > photocatalysis. The additive effect was achieved for the sonophotocatalytic degradation. The high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometric (LCMS) analyses were employed to identify the various intermediates produced during the mineralization. The identification of four pseudo molecular ions and various intermediates using the LCMS analysis evidently suggests the sonophotocatalytic degradation was preceded in various decay pathways. A suitable mechanism has been proposed for the sonophotocatalytic mineralization of Norflurazon. PMID:26735720

  6. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    USGS Publications Warehouse

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  7. 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...

  8. 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.

  9. Polymerization of beta-amino acids in aqueous solution

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

  10. Using isotope dilution mass spectrometry to determine aqueous trichloroacetic acid

    SciTech Connect

    Norwood, D.L.; Christman, R.F.; Johnson, J.D.; Hass, J.R.

    1986-01-01

    The development, verification, and application of a method based on isotope-dilution gas chromatography-mass spectrometry to determine aqueous trichloroacetic acid (TCAA) at the micrograms per litre level are described. The simultaneous determination of aqueous chloroform is also demonstrated. Trichloroacetic acid is shown to be a significant by-product of the chlorination of raw waters in the laboratory and to constitute a large fraction of the total organic halide (TOX) formed. Analysis of finished-water samples indicated that TCAA, like trihalomethanes is ubiquitous. Positive correlations exist between the levels of TCAA in laboratory-chlorinated raw waters and in finished waters and measured TOX.

  11. Effects of organic acids, amino acids and ethanol on the radio-degradation of patulin in an aqueous model system

    NASA Astrophysics Data System (ADS)

    Yun, Hyejeong; Lim, Sangyong; Jo, Cheorun; Chung, Jinwoo; Kim, Soohyun; Kwon, Joong-Ho; Kim, Dongho

    2008-06-01

    The effects of organic acids, amino acids, and ethanol on the radio-degradation of patulin by gamma irradiation in an aqueous model system were investigated. The patulin, dissolved in distilled water at a concentration of 50 ppm, was practically degraded by the gamma irradiation at the dose of 1.0 kGy, while 33% of the patulin remained in apple juice. In the aqueous model system, the radio-degradation of patulin was partially inhibited by the addition of organic acids, amino acids, and ethanol. The proportions of remaining patulin after irradiation with the dose of 1.0 kGy in the 1% solution of malic acid, citric acid, lactic acid, acetic acid, ascorbic acid, and ethanol were 31.4%, 2.3%, 31.2%, 6.1%, 50.8%, and 12.5%, respectively. During 30 days of storage, the remaining patulin was reduced gradually in the solution of ascorbic acid and malic acid compared to being stable in other samples. The amino acids, serine, threonine, and histidine, inhibited the radio-degradation of patulin. In conclusion, it was suggested that 1 kGy of gamma irradiation (recommended radiation doses for radicidation and/or quarantine in fruits) is effective for the reduction of patulin, but the nutritional elements should be considered because the radio-degradation effects are environment dependent.

  12. Esterified sago waste for engine oil removal in aqueous environment.

    PubMed

    Ngaini, Zainab; Noh, Farid; Wahi, Rafeah

    2014-01-01

    Agro-waste from the bark of Metroxylon sagu (sago) was studied as a low cost and effective oil sorbent in dry and aqueous environments. Sorption study was conducted using untreated sago bark (SB) and esterified sago bark (ESB) in used engine oil. Characterization study showed that esterification has successfully improved the hydrophobicity, buoyancy, surface roughness and oil sorption capacity of ESB. Sorption study revealed that water uptake of SB is higher (30 min static: 2.46 g/g, dynamic: 2.67 g/g) compared with ESB (30 min static: 0.18 g/g, dynamic: 0.14 g/g). ESB, however, showed higher oil sorption capacity in aqueous environment (30 min static: 2.30 g/g, dynamic: 2.14) compared with SB (30 min static: 0 g/g, dynamic: 0 g/g). ESB has shown great poTENTial as effective oil sorbent in aqueous environment due to its high oil sorption capacity, low water uptake and high buoyancy. PMID:25176478

  13. Raman spectra of amino acids and their aqueous solutions

    NASA Astrophysics Data System (ADS)

    Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

    2011-03-01

    Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

  14. Persistent Ion Pairing in Aqueous Hydrochloric Acid

    SciTech Connect

    Baer, Marcel D.; Fulton, John L.; Balasubramanian, Mahalingam; Schenter, Gregory K.; Mundy, Christopher J.

    2014-07-03

    For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of a chloride-Hyronium (Cl-H3O+) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counter ions do not behave merely as spectators. Through the use of modern extended X-ray absorption fine structure (EXAFS) measurements in conjunction with state-of-the-art density functional theory (DFT) simulations, we are able to obtain an unprecedented view into the molecular structure of medium to high concentrated electrolytes. Here we report that the Cl-H3O+ contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in micro-solvated hydrochloric acid clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to think about the activity of the proton that impacts our picture of the pH scale. Funding for CJM, GKS, and JLF was provided by DOE Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences. Funding for MDB was provided throught the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. MB was funded through Argonne National Laboratory.

  15. Amino-acid contamination of aqueous hydrochloric acid.

    NASA Technical Reports Server (NTRS)

    Wolman, Y.; Miller, S. L.

    1971-01-01

    Considerable amino-acid contamination in commercially available analytical grade hydrochloric acid (37% HCl) was found. One bottle contained 8,300 nmol of amino-acids per liter. A bottle from another supplier contained 6,700 nmol per liter. The contaminants were mostly protein amino-acids and several unknowns. Data on the volatility of the amino-acids during HCl distillation were also obtained.

  16. Conductance Studies on Aqueous Citric Acid

    NASA Astrophysics Data System (ADS)

    Apelblat, Alexander; Barthel, Josef

    1991-02-01

    Conductance measurements of citric acid and neutral citrates (tri-lithium citrate, tri-sodium citrate and tri-potassium citrate) were performed in water at 278.15 to 308.15 K. The equilibrium constants for the primary and secondary steps of dissociation, Kx and K2, and the limiting conductances, λ0(H2Cit-), λ°(1/2 HCit2-), and λ0(1/3 Cit3-) are reported as a function of temperature. They are obtained by application of the Quint and Viallard conductance equation. The enthalpies of dissociation are estimated.

  17. γ-Irradiation of malic acid in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Negron-Mendoza, Alicia; Graff, Rebecca L.; Ponnamperuma, Cyril

    1980-12-01

    The γ-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the non-volatile products. Thin layer chromotography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the γ-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  18. Carbon nanotube scanning probe for imaging in aqueous environment

    NASA Technical Reports Server (NTRS)

    Stevens, Ramsey M.; Nguyen, Cattien V.; Meyyappan, M.

    2004-01-01

    Carbon nanotubes (CNTs) used as a probe for scanning probe microscopy has become one of the many potential usages of CNTs that is finding real applications in scientific research and industrial communities. It has been proposed that the unique mechanical buckling properties of the CNT would lessen the imaging force exerted on the sample and, thus, make CNT scanning probes ideal for imaging soft materials, including biological samples in liquid environments. The hydrophobic nature of the CNT graphitic sidewall is clearly chemically incompatible with the aqueous solution requirements in some biological imaging applications. In this paper, we present electron micrograph results demonstrating the instability of CNT scanning probes when submerged in aqueous solution. Moreover, we also introduce a novel approach to resolve this chemical incompatibility problem. By coating the CNT probe with ethylenediamine, thus rendering the CNT probe less hydrophobic, we demonstrate the liquid imaging capability of treated CNT probes. Experimental data for imaging in aqueous solutions are presented, which include an ultrathin Ir film and DNA molecules on a mica surface.

  19. 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

  20. Solubility of chlorine in aqueous hydrochloric acid solutions.

    PubMed

    Alkan, Mahir; Oktay, Münir; Kocakerim, M Muhtar; Copur, Mehmet

    2005-03-17

    The solubility of chlorine in aqueous hydrochloric acid solutions was studied. The effects of HCl concentration and temperature on the solubility were evaluated, and the thermodynamic parameters of the dissolution were calculated. It was found that the solubility isotherms had a minimum at about 0.5M HCl concentration at all the temperatures studied and that solubility decreased with the increase of temperature at all the HCl concentration range investigated. PMID:15752843

  1. Response of Plasma-Polymerized Hexamethyldisiloxane Films to Aqueous Environments.

    PubMed

    Blanchard, Noemi E; Naik, Vikrant V; Geue, Thomas; Kahle, Olaf; Hegemann, Dirk; Heuberger, Manfred

    2015-12-01

    Thin plasma polymer films were deposited in hexamethyldisiloxane (HMDSO) and HMDSO/O2 low-pressure discharges and their chemical structures analyzed using infrared (IR) spectroscopy and neutron reflectometry (NR). The (plasma-polymerized) ppHMDSO film exhibits hydrophobic, poly(dimethylsiloxane)-like properties, while the retention of carbon groups is reduced by O2 addition, yielding a more inorganic, hydrophilic ppSiOx film. Both films show a minor (vertical) density gradient perpendicular to the substrate, where the exposed film surface seems to be more oxidized, indicating oxidative aging reactions upon contact with air. The hydration and water uptake abilities of the films in aqueous environments were investigated in humid environments using ellipsometry, NR in D2O, and multiple transmission-reflection IR measurements after equilibration of the films in water. PMID:26451512

  2. Multiple-acid equilibria in adsorption of carboxylic acids from dilute aqueous solution

    SciTech Connect

    Husson, S.M.; King, C.J.

    1999-02-01

    Equilibria were measured for adsorption of carboxylic acids from aqueous, binary-acid mixtures of lactic and succinic acids and acetic and formic acids onto basic polymeric sorbents. The experimentally determined adsorption isotherms compared well with model predictions, confirming that simple extensions from adsorption of individual acids apply. Fixed-bed studies were carried out that establish the efficacy of chromatographic fractionation of lactic and succinic acids using basic polymeric sorbents. Finally, sequential thermal and solvent regeneration of lactic and acetic acid-laden sorbents was investigated as a method to fractionate among coadsorbed volatile and nonvolatile acids. Essentially complete removal of the acetic acid from the acid-laden sorbent was achieved by vaporization under the conditions used; a small amount of loss of lactic acid (about 11%) was observed.

  3. Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

  4. Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

  5. Release of nitrous acid and nitrogen dioxide from nitrate photolysis in acidic aqueous solutions.

    PubMed

    Scharko, Nicole K; Berke, Andrew E; Raff, Jonathan D

    2014-10-21

    Nitrate (NO3(-)) is an abundant component of aerosols, boundary layer surface films, and surface water. Photolysis of NO3(-) leads to NO2 and HONO, both of which play important roles in tropospheric ozone and OH production. Field and laboratory studies suggest that NO3¯ photochemistry is a more important source of HONO than once thought, although a mechanistic understanding of the variables controlling this process is lacking. We present results of cavity-enhanced absorption spectroscopy measurements of NO2 and HONO emitted during photodegradation of aqueous NO3(-) under acidic conditions. Nitrous acid is formed in higher quantities at pH 2-4 than expected based on consideration of primary photochemical channels alone. Both experimental and modeled results indicate that the additional HONO is not due to enhanced NO3(-) absorption cross sections or effective quantum yields, but rather to secondary reactions of NO2 in solution. We find that NO2 is more efficiently hydrolyzed in solution when it is generated in situ during NO3(-) photolysis than for the heterogeneous system where mass transfer of gaseous NO2 into bulk solution is prohibitively slow. The presence of nonchromophoric OH scavengers that are naturally present in the environment increases HONO production 4-fold, and therefore play an important role in enhancing daytime HONO formation from NO3(-) photochemistry. PMID:25271384

  6. Dephosphorization of Steelmaking Slag by Leaching with Acidic Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qiao, Yong; Diao, Jiang; Liu, Xuan; Li, Xiaosa; Zhang, Tao; Xie, Bing

    2015-12-01

    In the present paper, dephosphorization of steelmaking slag by leaching with acidic aqueous solution composed of citric acid, sodium hydroxide, hydrochloric acid and ion-exchanged water was investigated. The buffer solution of C6H8O7-NaOH-HCl system prevented changes in the pH values. Kinetic parameters including leaching temperature, slag particle size and pH values of the solution were optimized. The results showed that temperature has no obvious effect on the dissolution ratio of phosphorus. However, it has a significant effect on the dissolution ratio of iron. The dephosphorization rate increases with the decrease of slag particle size and the pH value of the solution. Over 90% of the phosphorus can be dissolved in the solution while the corresponding leaching ratio of iron was only 30% below the optimal condition. Leaching kinetics of dephosphorization follow the unreacted shrinking core model with a rate controlled step by the solid diffusion layer, the corresponding apparent activation energy being 1.233 kJ mol-1. A semiempirical kinetic equation was established. After leaching, most of the nC2S-C3P solid solution in the steelmaking slag was selectively dissolved in the aqueous solution and the iron content in the solid residue was correspondingly enriched.

  7. Fermentation of aqueous plant seed extracts by lactic acid bacteria

    SciTech Connect

    Schafner, D.W.; Beuchat, R.L.

    1986-05-01

    The effects of lactic acid bacterial fermentation on chemical and physical changes in aqueous extracts of cowpea (Vigna unguiculata), peanut (Arachis hypogea), soybean (Glycine max), and sorghum (Sorghum vulgare) were studied. The bacteria investigated were Lactobacillus helveticus, L. delbrueckii, L. casei, L. bulgaricus, L. acidophilus, and Streptococcus thermophilus. Organisms were inoculated individually into all of the seed extracts; L. bulgaricus and S. thermophilus were also evaluated together as inocula for fermenting the legume extracts. During fermentation, bacterial population and changes in titratable acidity, pH, viscosity, and color were measured over a 72 h period at 37 degrees C. Maximum bacterial populations, titratable acidity, pH, and viscosity varied depending upon the type of extract and bacterial strain. The maximum population of each organism was influenced by fermentable carbohydrates, which, in turn, influenced acid production and change in pH. Change in viscosity was correlated with the amount of protein and titratable acidity of products. Color was affected by pasteurization treatment and fermentation as well as the source of extract. In the extracts inoculated simultaneously with L. bulgaricus and S. thermophilus, a synergistic effect resulted in increased bacterial populations, titratable acidity, and viscosity, and decreased pH in all the legume extracts when compared to the extracts fermented with either of these organisms individually. Fermented extracts offer potential as substitutes for cultured dairy products. 24 references.

  8. Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

    PubMed Central

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

  9. Polymerization of Pu(IV) in aqueous nitric acid solutions

    SciTech Connect

    Toth, L.M.; Friedman, H.A.; Osborne, M.M.

    1980-10-01

    The polymerization of Pu(IV) in aqueous nitric acid solutions has been studied spectrophotometrically both to establish the influence of large UO{sub 2}(NO{sub 3}){sub 2} concentrations on the polymerization rates and, more generally, to review the influence of the major parameters on the polymer reaction. Typically, experiments have been performed at 50{sup 0}C and with 0.05 M Pu in nitric acid solutions that vary in acidity from 0.07 to 0.4 M. An induction period usually precedes the polymer growth stage during which time nucleation of primary hydrolysis products occurs. Uranyl nitrate retards the polymerization reaction by approximately 35% in spite of the counteracting influence of the nitrate ions associated with this solute. The rate of polymer formation, expressed as d(percent polymer)/dt, has been shown to depend on the total plutonium concentration in reactions where the Pu(IV) concentration remained constant; and it is therefore suggested that the polymer reaction rate is not first order with respect to the concentration of plutonium as was previously thought. It has been shown further that accurate acid determinations on stock reagents are essential in order to obtain reliable polymerization experiments. Satisfactory procedures for these analyses did not exist, so appropriate modifications to the iodate precipitation methods were developed. The most ideal plutonium reagent material has been shown to be crystalline Pu(IV) nitrate because it can be added directly to acid solutions without the occurrence of unintentional hydrolysis reactions.

  10. A mild, near-surface aqueous environment on Noachian Mars preserved in ALH84001

    NASA Astrophysics Data System (ADS)

    Halevy, I.; Fischer, W. W.; Eiler, J. M.

    2011-12-01

    Despite widespread evidence for liquid water at the surface of Mars during parts of the Noachian epoch, the temperature of early aqueous environments has been impossible to establish, raising questions of whether Mars' surface was ever warmer than today. This has hindered insight into aqueous alteration processes, which, on the basis of orbital spectroscopy, appear to have been prevalent on Noachian Mars. It is important to understand such processes, as they link the observed secondary mineral assemblages to interactions between primary igneous silicates and the surface environment (atmosphere-hydrosphere). We have addressed this problem by determining the precipitation temperatures of secondary carbonate minerals preserved in the oldest known sample of Mars' crust-the meteorite Allan Hills 84001 (ALH84001). Using carbonate 'clumped' isotope thermometry we have found that the carbonates in ALH84001, which are 3.9-4.0 billion years old, formed at a temperature of ~18±4°C. With temperature known, we used the carbon and oxygen isotopic composition of the carbonates, as constrained by both our measurements and previous acid digestion and ion microprobe studies, to develop a model for their formation process and environment. The observed isotopic variation is best explained by carbonate precipitation out of a gradually evaporating, shallow subsurface aqueous solution (e.g. a regolith aquifer) at near-constant temperatures. Furthermore, on the basis of the isotopic composition of the earliest precipitated carbonates in ALH84001, the volatiles from which they formed (H2O and CO2) came not from depth, but from the early Martian surface. The occurrence of carbonates in other SNC meteorites and as a minor component of Martian dust implies that environments analogous to the one we studied may have been important in generating some of the observed secondary mineral assemblages by interaction between Mars' igneous crust and its atmosphere-hydrosphere.

  11. Amino acid synthesis in Europa's subsurface environment

    NASA Astrophysics Data System (ADS)

    Abbas, Sam H.; Schulze-Makuch, Dirk

    2008-10-01

    It has been suggested that Europa's subsurface environment may provide a haven for prebiotic evolution and the development of exotic biotic systems. The detection of hydrogen peroxide, sulfuric acid, water, hydrates and related species on the surface, coupled with observed mobility of icebergs, suggests the presence of a substantial subsurface liquid reservoir that actively exchanges materials with the surface environment. The atmospheric, surface and subsurface environments are described with their known chemistry. Three synthetic schemes using hydrogen peroxide, sulfuric acid and hydrocyanic acid leading to the production of larger biologically important molecules such as amino acids are described. Metabolic pathways based on properties of the subsurface ocean environment are detailed. Tidal heating, osmotic gradients, chemical cycling, as well as hydrothermal vents, provide energy and materials that may support a course of prebiotic evolution leading to the development or sustenance of simple biotic systems. Putative organisms may employ metabolic pathways based on chemical oxidation reduction cycles occurring in the putative subsurface ocean environment.

  12. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    Nanoscience is an emerging field that can provide potential routes towards addressing critical issues such as clean and sustainable energy, environmental remediation and human health. Specifically, porous nanomaterials, such as zeolites and mesoporous silica, are found in a wide range of applications including catalysis, drug delivery, imaging, environmental protection, and sensing. The characterization of the physical and chemical properties of nanocrystalline materials is essential to the realization of these innovative applications. The great advantage of porous nanocrystals is their increased external surface area that can control their biological, chemical and catalytic activities. Specific functional groups synthesized on the surface of nanoparticles are able to absorb heavy metals from the solution or target disease cells, such as cancer cells. In these studies, three main issues related to functionalized nanomaterials will be addressed through the application of nuclear magnetic resonance (NMR) techniques including: 1) surface composition and structure of functionalized nanocrystalline particles; 2) chemical properties of the guest molecules on the surface of nanomaterials, and 3) adsorption and reactivity of surface bound functional groups. Nuclear magnetic resonance (NMR) is one of the major spectroscopic techniques available for the characterization of molecular structure and conformational dynamics with atomic level detail. This thesis deals with the application of 1H solution state NMR to porous nanomaterial in an aqueous environment. Understanding the aqueous phase behavior of functionalized nanomaterials is a key factor in the design and development of safe nanomaterials because their interactions with living systems are always mediated through the aqueous phase. This is often due to a lack of fundamental knowledge in interfacial chemical and physical phenomena that occur on the surface of nanoparticles. The use of solution NMR spectroscopy results

  13. Robust magnetic/polymer hybrid nanoparticles designed for crude oil entrapment and recovery in aqueous environments.

    PubMed

    Pavía-Sanders, Adriana; Zhang, Shiyi; Flores, Jeniree A; Sanders, Jonathan E; Raymond, Jeffery E; Wooley, Karen L

    2013-09-24

    Well-defined, magnetic shell cross-linked knedel-like nanoparticles (MSCKs) with hydrodynamic diameters ca. 70 nm were constructed through the co-assembly of amphiphilic block copolymers of PAA20-b-PS280 and oleic acid-stabilized magnetic iron oxide nanoparticles using tetrahydrofuran, N,N-dimethylformamide, and water, ultimately transitioning to a fully aqueous system. These hybrid nanomaterials were designed for application as sequestering agents for hydrocarbons present in crude oil, based upon their combination of amphiphilic organic domains, for aqueous solution dispersibility and capture of hydrophobic guest molecules, with inorganic core particles for magnetic responsivity. The employment of these MSCKs in a contaminated aqueous environment resulted in the successful removal of the hydrophobic contaminants at a ratio of 10 mg of oil per 1 mg of MSCK. Once loaded, the crude oil-sorbed nanoparticles were easily isolated via the introduction of an external magnetic field. The recovery and reusability of these MSCKs were also investigated. These results suggest that deployment of hybrid nanocomposites, such as these, could aid in environmental remediation efforts, including at oil spill sites, in particular, following the bulk recovery phase. PMID:23987122

  14. Sunlight-initiated Chemistry of Aqueous Pyruvic Acid: Building Complexity in the Origin of Life

    NASA Astrophysics Data System (ADS)

    Griffith, Elizabeth C.; Shoemaker, Richard K.; Vaida, Veronica

    2013-10-01

    Coupling chemical reactions to an energy source is a necessary step in the origin of life. Here, we utilize UV photons provided by a simulated sun to activate aqueous pyruvic acid and subsequently prompt chemical reactions mimicking some of the functions of modern metabolism. Pyruvic acid is interesting in a prebiotic context due to its prevalence in modern metabolism and its abiotic availability on early Earth. Here, pyruvic acid (CH3COCOOH, a C3 molecule) photochemically reacts to produce more complex molecules containing four or more carbon atoms. Acetoin (CH3CHOHCOCH3), a C4 molecule and a modern bacterial metabolite, is produced in this chemistry as well as lactic acid (CH3CHOHCOOH), a molecule which, when coupled with other abiotic chemical reaction pathways, can provide a regeneration pathway for pyruvic acid. This chemistry is discussed in the context of plausible environments on early Earth such as near the ocean surface and atmospheric aerosol particles. These environments allow for combination and exchange of reactants and products of other reaction environments (such as shallow hydrothermal vents). The result could be a contribution to the steady increase in chemical complexity requisite in the origin of life.

  15. Conformation of poly(γ-glutamic acid) in aqueous solution.

    PubMed

    Muroga, Yoshio; Nakaya, Asami; Inoue, Atsuki; Itoh, Daiki; Abiru, Masaya; Wada, Kaori; Takada, Masako; Ikake, Hiroki; Shimizu, Shigeru

    2016-04-01

    Local conformation and overall conformation of poly(γ-DL-glutamic acid) (PγDLGA) and poly(γ-L-glutamic acid) (PγLGA) in aqueous solution was studied as a function of degree of ionization ε by (1) H-NMR, circular dichroism, and potentiometric titration. It was clarified that their local conformation is represented by random coil over an entire ε range and their overall conformation is represented by expanded random-coil in a range of ε > ε(*) , where ε(*) is about 0.3, 0.35, 0.45, and 0.5 for added-salt concentration of 0.02M, 0.05M, 0.1M, and 0.2M, respectively. In a range of ε < ε(*) , however, ε dependence of their overall conformation is significantly differentiated from each other. PγDLGA tends to aggregate intramolecularly and/or intermolecularly with decreasing ε, but PγLGA still behaves as expanded random-coil. It is speculated that spatial arrangement of adjacent carboxyl groups along the backbone chain essentially affects the overall conformation of PγGA in acidic media. PMID:26574908

  16. (Acidic deposition and the environment)

    SciTech Connect

    Garten, C.T.; Lindberg, S.E.; Van Miegroet, H.

    1990-10-24

    The travelers presented several papers at the Fourth International Conference on Acidic Deposition. These covered the following topics: atmospheric chemistry and deposition of airborne nitrogen compounds, soil solution chemistry in high-elevation spruce forests, and forest throughfall measurements for estimating total sulfur deposition to ecosystems. In addition, S. E. Lindberg was invited to organize and chair a conference session on Throughfall and Stemflow Experiments, and to present an invited lecture on Atmospheric Deposition and Canopy Interactions of Metals and Nitrogen in Forest Ecosystems: The Influence of Global Change'' at the 110th Anniversary Celebration of the Free University of Amsterdam.

  17. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid.

    PubMed

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-28

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (E(p), 1.10 ≤ E(p) ≤ 1.50 V), polarization time (t(p), 10(0) ≤ t(p) ≤ 10(4) s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (d(ox)). Because X1 > d(ox) for the entire range of E(p), t(p), and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt(δ+)-O(δ-) surface dipole (μ(PtO)), and the potential drop (V(ox)) and electric field (E(ox)) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide. PMID:25362330

  18. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  19. INTERACTION OF AQUEOUS SOLUTIONS OF CHLORINE WITH MALIC ACID, TARTARIC ACID, AND VARIOUS FRUIT JUICES, A SOURCE OF MUTAGENS

    EPA Science Inventory

    The interactions of aqueous solutions of chlorine with some fruit acids (citric acid, DL-malic acid, and L-tartaric acid) at different pH values were studied. iethyl ether extraction followed by GC/MS analysis indicated that a number of mutagens (certain chlorinated propanones an...

  20. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

    DOE PAGESBeta

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S. Michael; et al

    2015-02-10

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights intomore » the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.« less

  1. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

    SciTech Connect

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S. Michael; Lokitz, Bradley S.; Minko, Sergiy; Hinrichs, Karsten

    2015-02-10

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights into the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.

  2. Pineal hormone melatonin: solubilization studies in model aqueous gastrointestinal environments.

    PubMed

    Vlachou, Marilena; Eikosipentaki, Aphrodite; Xenogiorgis, Vassilios

    2006-07-01

    In view of the variable oral absorption, short biological half-life and extensive first pass metabolism of the pineal hormone melatonin, an investigation of its solubilization profile in modified aqueous media is described. Four readily available surfactants were examined with respect to their ability to enhance the solubility of melatonin under simulated physiological conditions. The most effective surfactant was found to be the sodium salt of dioctyl sulfosuccinate (DSS), which augmented the aqueous solubility of the hormone by 23%. This is attributed to a favourable stereoelectronic interaction between DSS and the nucleus of melatonin, which seems to be independent of the pH of the dissolution medium. A noteworthy synergistic effect in the aqueous solubilization of the hormone occurs when a 1:2 DSS-sodium dodecyl sulphate mixture is used. PMID:16848727

  3. Optical properties of chitosan in aqueous solution of L- and D-ascorbic acids

    NASA Astrophysics Data System (ADS)

    Malinkina, Olga N.; Shipovskaya, Anna B.; Kazmicheva, Olga F.

    2016-04-01

    The optical properties of aqueous chitosan solutions in L- and D-ascorbic acids were studied by optical rotatory dispersion and spectrophotometry. The specific optical rotation [α] of all chitosan solutions tested was positive, in contrast to aqueous solutions of the ascorbic acid enantiomers, which exhibit an inverse relationship of [α] values. Significant differences in the absolute values of [α] of the chitosan solutions at polymer-acid ratios exceeding the equimolar one were found.

  4. Acid-base properties of aqueous illite surfaces

    SciTech Connect

    Du, Q.; Sun, Z.; Forsling, W.; Tang, H.

    1997-03-01

    In this paper, the acid-base properties of illite/water suspensions are examined using the constant capacitance surface complexation model. On the basis of results of potentiometric titrations and solubility experiments, the authors conclude that the proton reactions in the supernatants of illite suspensions can be successfully represented by proton reactions of Al(H{sub 2}O){sub 6}{sup 3+} and Si(OH){sub 4} in water solutions. For illustrating the acidic characteristics of aqueous illite surfaces, two surface protonation models are proposed: (1) one site-one pK{sub a} model, {triple_bond}SOH {r_reversible} {triple_bond}SO{sup {minus}} + H{sup +}, pK{sub a}{sup int} = 4.12-4.23; (2) two sites-two pK{sub a}s model, {triple_bond}S{sub 1}OH {r_reversible} {triple_bond}S{sup 1}O{sup {minus}} + H{sup +}, pK{sub a{sub I}} = 4.17-4.44, and {triple_bond}S{sub II}OH {r_reversible} {triple_bond}S{sub II}O{sup {minus}} + H{sup +}, pK{sub a{sub II}}{sup int} = 6.35-7.74. Evaluation of these two models indicates that both of them can give good descriptions of the experimental data of systems with different illite concentrations and ionic strengths and that the one site-one pK{sub a} model can be considered as a simplification of the two sites-two pK{sub a}s model. Since both models assume only deprotonation reactions at the illite surfaces, they suggest that the surface behavior of the illite is similar to that of amorphous SiO{sub 2}. Model assumptions, experimental procedures, and evaluative criteria are detailed in the paper.

  5. Selective plasmon-driven catalysis for para-nitroaniline in aqueous environments

    NASA Astrophysics Data System (ADS)

    Cui, Lin; Wang, Peijie; Li, Yuanzuo; Sun, Mengtao

    2016-02-01

    The plasmon-driven oxidation of amine (-NH2) groups and the reduction of nitro (-NO2) groups on a nanostructured metal surface in an aqueous environment have been reported experimentally and theoretically. The question of which process occurs first in the aqueous environment is an interesting question in the field of plasmon-related photochemistry. Para-nitroaniline (PNA), with both nitro (-NO2) and amine (-NH2) groups, is the best candidate for studying the priority of the plasmon-driven oxidation and the reduction reactions in an aqueous environment. Using surface-enhanced Raman scattering (SERS) spectroscopy, our experimental results and theoretical simulations reveal that PNA is selectively catalyzed to 4,4‧-diaminoazobenzene (DAAB) through the plasmon-assisted dimerization of the nitro (-NO2) group into an azo group in an aqueous environment. This indicates that the plasmon-driven reduction of the nitro (-NO2) group clearly occurs before the oxidation of the amine (-NH2) group in an aqueous environment. The plasmon-driven reduction of PNA to DAAB is a selective surface catalytic reduced reaction in aqueous environment.

  6. Effects of aqueous environment on long-term durability of phosphate-bonded ceramic waste forms

    SciTech Connect

    Singh, D.; Wagh, A.S.; Jeong, S.Y.

    1996-03-01

    Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests.

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

    NASA Astrophysics Data System (ADS)

    Pristinski, Denis

    We present an investigation of charge-dependent physical properties of water-soluble synthetic polymers and polymer-based layered structures, using optical detection methods in a visible range. We apply in situ nanoscale optical techniques to study response of polymer systems to changes in pH, polymer concentration, and concentration and type of counterions. This work describes three optical techniques and custom built instrumental setups for nanoscale polymer characterization in aqueous environment. Phase-modulated ellipsometry was applied to determine the refraction coefficient and the thickness of a hydrogel-like polymer layer on a substrate. The present study describes the sensitivity of the phase modulated ellipsometry to errors of measurement and determines conditions for decoupling film thickness and refraction index. It is shown that, for a certain range of film thickness, both the thickness and the refractive index can be determined from a single measurement with high precision. This optimal range of the film thickness is calculated for organic thin films, and the analysis is tested on crosslinked poly(methacrylic acid) polymer films in air and in water. Fluorescent correlation spectroscopy was used to investigate diffusion of a synthetic polyelectrolyte in aqueous solutions. Translational diffusion of Alexa-labeled poly(methacrylic acid) chains was studied in very dilute, 10-4 mg/ml, solutions as a function of polymer charge density and counterion concentration. The results illustrate the utility of the technique for studying hydrodynamic sizes of polyelectrolyte coils in response to variation in solution pH or concentration of salt and polyelectrolytes. We apply surface-enhanced Raman scattering (SERS) for studying of enhancement capabilities of individual silver nanoparticles attached to glass and silicon substrates. Nanoparticles were electrostatically bound to a self-assembled polyallylamine hydrochloride (PAH) monolayer, which was deposited on

  8. Activation of Carbonyl-Containing Molecules with Solid Lewis Acids in Aqueous Media

    SciTech Connect

    Román-Leshkov, Yuriy; Davis, Mark E.

    2011-09-28

    Current interest in reacting carbonyl-containing molecules in aqueous media is primarily due to the growing emphasis on conversion of biomass to fuels and chemicals. Recently, solid Lewis acids have been shown to perform catalytic reactions with carbonyl-containing molecules such as sugars in aqueous media. Here, catalysis mediated by Lewis acids is briefly discussed, Lewis acid solids that perform catalysis in aqueous media are then described, and the review is concluded with a few comments on the outlook for the future.

  9. New crystallization of fatty acids from aqueous ethanol solution combined with liquid-liquid extraction

    SciTech Connect

    Maeda, Kouji; Nomura, Yoshihisa; Tai, Kimihiko; Ueno, Yoshitaka; Fukui, Keisuke; Hirota, Syouji

    1999-06-01

    A new separation process of saturated fatty acids (lauric acid-myristic acid) using crystallization from an aqueous ethanol solution has been examined. There were two vessels in this separation process: an extraction vessel and a crystallization vessel. The fatty acids in the aqueous phase were first extracted from their organic phase (melt) in the extraction vessel. The fatty acids in the aqueous phase were continuously introduced to the crystallization vessel, and then the fatty acids were crystallized there. The crystals of the fatty acids were collected continuously above the aqueous phase in the crystallization vessel. In this process, the yield and the purity of the crystals over time were measured, and it was found that the purity of lauric acid increased unsteadily up to 0.98 mole fraction of lauric acid with an increase in the yield of the low yield range. The mole fraction of ethanol in the aqueous phase could be significant to control the relationship between the yield and the purity of the crystals. Three different mole fractions of lauric acid in the organic phase were used to be separated in this process. Moreover, the authors have considered the effective separations of this process, and the maximum yield and purity of the crystals have been estimated by a simple mass balance.

  10. Multiple Glass Transitions and Freezing Events of Aqueous Citric Acid

    PubMed Central

    2014-01-01

    Calorimetric and optical cryo-microscope measurements of 10–64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid–glass transitions upon cooling and from one to six liquid–glass and reverse glass–liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role. PMID:25482069

  11. Thermodynamics of the complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mudarisova, R. Kh.; Badykova, L. A.

    2016-03-01

    The thermodynamics of complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions is studied by means spectroscopy. The standard thermodynamic characteristics (Δ H°; Δ G°; Δ S°) of complexation are calculated.

  12. Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Michelsen, Rebecca R.; Ashbourn, Samatha F. M.; Rammer, Thomas A.; Golden, David M.

    2005-01-01

    Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

  13. Behaviors of acrylamide/itaconic acid hydrogels in uptake of uranyl ions from aqueous solutions

    SciTech Connect

    Karadag, E.; Saraydin, D.; Gueven, O.

    1995-12-01

    In this study, adsorptions of uranyl ions from two different aqueous uranyl solutions by acrylamide-itaconic acid hydrogels were investigated by a spectroscopic method. The hydrogels were prepared by irradiating with {gamma}-radiation. In the experiment of uranyl ions adsorption, Type II adsorption was found. One gram of acrylamide-itaconic acid hydrogels sorbed 178-219 mg uranyl ions from the solutions of uranyl acetate, 42-76 mg uranyl ions from the aqueous solutions of uranyl nitrate, while acrylamide hydrogel did not sorb any uranyl ion. For the hydrogel containing 40 mg of itaconic acid and irradiated to 3.73 kGy, swelling of the hydrogels was observed in water (1660%), in the aqueous solution of uranyl acetate (730%), and in the aqueous solution of uranyl nitrate (580%). Diffusions of water onto hydrogels were a non-Fickian type of diffusion, whereas diffusions of uranyl ions were a Fickian type of diffusion.

  14. Alteration of amino acids and related compounds in space environments

    NASA Astrophysics Data System (ADS)

    Kobayashi, K.; Tsuboi, T.; Kaneko, T.; Takano, Y.; Hashimoto, H.; Haruyama, J.; Yamashita, M.

    Organic compounds have been found in carbonaceous chondrites and in comets, which were possible materials for the first life on the Earth. It is suggested that these organics were originally formed in ice mantles of interstellar dusts (ISD) in molecular cloud. A number of studies were done to simulate reactions in ISD: Formation of amino acid precursors was reported when simulated interstellar media was irradiated with protons [1] or UV [2]. Extraterrestrial amino acids or their precursors in interstellar space, comets or meteorites were exposed to cosmic rays and UV before they were delivered to planets. Here we investigated stability of amino acids and related compounds in interstellar, lunar and planetary environments. Target compounds are (i) free amino acids, (ii) human serum albumin (HSA) and (iii) "possible interstellar complex organics (PICO)", which were formed from a mixture of carbon monoxide, ammonia and water by proton irradiation. Aqueous solutions of the target compounds were irradiated with gamma rays at room temperature, and they were acid-hydrolyzed before amino acid analysis. Recovery ratio of amino acids in HSA and PICO was much more than that of free amino acids. Samples mixed with basalt powder were more stable than those without the regolith. When the targets were irradiated after freeze-dried, their decomposition was not observed up to 30 kGy dosage. The present results show that extraterrestrial amino acids are quite stable if they are present as complex precursors in mineral matrix. Organic compounds in ISD are exposed not only to cosmic rays but also UV photons. It would be of interest to test stability of organic compounds in actual space environments: The exposure facility of International Space Station would be the place where the target molecules can be irradiated with cosmic rays and solar UV (including extreme UV) at the same time. [1] Kobayashi et al., Adv. Space Res., 16, 21 (1995), Kasamatsu et al., Bull. Chem. Soc. Jpn., 70

  15. Aqueous chlorination of mefenamic acid: kinetics, transformation by-products and ecotoxicity assessment.

    PubMed

    Adira Wan Khalit, Wan Nor; Tay, Kheng Soo

    2016-05-18

    Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination. PMID:27062128

  16. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases.

    PubMed

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases. PMID:24952470

  17. Method of inhibiting crosslinking of aqueous xanthan gums in the presence of ferric acid ions

    SciTech Connect

    Crowe, C.W.

    1982-03-02

    The cross linking of aqueous xanthan gums in the presence of ferric ions is inhibited or prevented by adding a soluble alkanoic and/or alkenoic acid having at least 4 carbon atoms and bearing at least 2 hydroxyl groups per molecule, and/or a soluble salt of ..gamma..-lactone. This combination of ingredients forms gelled acid compositions which are useful in acidizing treatments of wells. The gelled acid compositions are viscous fluids which have increased stability against shear and thermal degradation and other properties which result in retarded reaction rates and reduced fluid leak-off during acidizing treatments of subterranean formations surrounding well bores. The aqueous gelled acids have the further advantage of inhibiting or preventing the formation of insoluble compounds, such as ferric hydroxide, during such acidizing treatments. 13 claims.

  18. ACID GASES IN CO2-RICH SUBSURFACE GEOLOGIC ENVIRONMENTS

    SciTech Connect

    Chialvo, Ariel A; Vlcek, Lukas; Cole, David

    2013-01-01

    The analysis of species behavior involving dilute fluid environments has been crucial for the advance of modern solvation thermodynamics through molecular-based formalisms to guide the development of macroscopic regression tools in the description of fluid behavior and correlation of experimental data (Chialvo 2013). Dilute fluid environments involving geologic formations are of great theoretical and practical relevance regardless of the thermodynamic state conditions. The most challenging systems are those involving highly compressible and reactive confined environments, i.e., where small perturbations of pressure and/or temperature can trigger considerable density changes. This in turn can alter significantly the species solvation, their preferential solvation, and consequently, their reactivity with one another and with the surrounding mineral surfaces whose outcome is the modification of the substrate porosity and permeability, and ultimately, the integrity of the mineral substrates. Considering that changes in porosity and permeability resulting from dissolution and precipitation phenomena in confined environments are at the core of the aqueous CO2-mineral interactions, and that caprock integrity (e.g., sealing capacity) depends on these key parameters, it is imperative to gain fundamental understanding of the mineral-fluid interfacial phenomena and fluid-fluid equilibria under mineral confinement at subsurface conditions. In order to undertand the potential effects of acid gases as contaminants of supercritical CO2 streams, in the next section we will discuss the thermodynamic behavior of CO2 fluid systems by addressing two crucial issues in the context of carbon capture, utilization and sequestration (CCUS) technologies: (i) Why should we consider (acid gas) CO2 impurities? and (ii) Why are CO2 fluid - mineral interactions of paramount relevance?

  19. Rosmarinic acid content in antidiabetic aqueous extract of Ocimum canum Sims grown in Ghana

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rosmarinic acid (RA) is an important polyphenol that is found in a variety of herbs including Ocimum canum sims (locally called eme or akokobesa in Ghana). Aqueous extracts from the leaves of O.canum are used as an antidiabetic herbal medicine in Ghana. Interestingly, rosmarinic acid content and p...

  20. KINETIC ASPECTS OF CATION-ENHANCED AGGREGATION IN AQUEOUS HUMIC ACIDS. (R822832)

    EPA Science Inventory

    The cation-enhanced formation of hydrophobic domains in aqueous humic acids has been shown to be a slow process, consistent with the evolution and disintegration of humic acid configurations over periods lasting from days to weeks. After the addition of a magnesium salt to a humi...

  1. ADIPIC ACID DEGRADATION MECHANISM IN AQUEOUS FGD (FLUE GAS DESULFURIZATION) SYSTEMS

    EPA Science Inventory

    The report gives results of a field and laboratory study of the adipic acid degradation mechanism in aqueous flue gas desulfurization (FGD) systems. (Adding adipic acid to limestone-based, SO2 wet scrubbers increases SO2 removal and limestone utilization. However, as much as 80% ...

  2. Coulometric titration of acids in non-aqueous solvents.

    PubMed

    Fritz, J S; Gainer, F E

    1968-09-01

    Coulometric titrations of mineral acids, sulphonic acids, carboxylic acids, enols, imides and phenols have been carried out in t-butanol or in acetone with electrically generated tetrabutylammonium hydroxide. Either a potentiometric titration or a visual indicator end-point may be used. The amount of acid titrated ranges from 10 to 60 muequiv, and the precision and accuracy of the method are excellent. PMID:18960387

  3. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment.

    PubMed

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S Michael; Lokitz, Bradley S; Minko, Sergiy; Hinrichs, Karsten

    2015-06-17

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes containing poly(N-isopropylacrylamide) and poly(acrylic acid) with high potential for biosensing and biomedical applications are studied by in situ infrared-spectroscopic ellipsometry (IRSE). IRSE is a highly sensitive nondestructive technique that allows protein adsorption on polymer brushes to be investigated in an aqueous environment as external stimuli, such as temperature and pH, are varied. These changes are relevant to conditions for regulation of protein adsorption and desorption for biotechnology, biocatalysis, and bioanalytical applications. Here brushes are used as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. The important finding of this work is that IRSE in the in situ experiments in protein solutions can distinguish between contributions of polymer brushes and proteins. The vibrational bands of the polymers provide insights into the hydration state of the brushes, whereas the protein-specific amide bands are related to changes of the protein secondary structure. PMID:25668395

  4. Arsenic(V) biosorption by charred orange peel in aqueous environments.

    PubMed

    Abid, Muhammad; Niazi, Nabeel Khan; Bibi, Irshad; Farooqi, Abida; Ok, Yong Sik; Kunhikrishnan, Anitha; Ali, Fawad; Ali, Shafaqat; Igalavithana, Avanthi Deshani; Arshad, Muhammad

    2016-05-01

    Biosorption efficiency of natural orange peel (NOP) and charred orange peel (COP) was examined for the immobilization of arsenate (As(V)) in aqueous environments using batch sorption experiments. Sorption experiments were carried out as a function of pH, time, initial As(V) concentration and biosorbent dose, using NOP and COP (pretreated with sulfuric acid). Arsenate sorption was found to be maximum at pH 6.5, with higher As(V) removal percentage (98%) by COP than NOP (68%) at 4 g L(-1) optimum biosorbent dose. Sorption isotherm data exhibited a higher As(V) sorption (60.9 mg g(-1)) for COP than NOP (32.7 mg g(-1)). Langmuir model provided the best fit to describe As(V) sorption. Fourier transform infrared spectroscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy analyses revealed that the -OH, -COOH, and -N-H surface functional groups were involved in As(V) biosorption and the meso- to micro-porous structure of COP sequestered significantly (2-times) higher As(V) than NOP, respectively. Arsenate desorption from COP was found to be lower (10%) than NOP (26%) up to the third regeneration cycle. The results highlight that this method has a great potential to produce unique 'charred' materials from the widely available biowastes, with enhanced As(V) sorption properties. PMID:26552612

  5. Improvement in Aqueous Solubility of Retinoic Acid Receptor (RAR) Agonists by Bending the Molecular Structure.

    PubMed

    Hiramatsu, Michiaki; Ichikawa, Yuki; Tomoshige, Shusuke; Makishima, Makoto; Muranaka, Atsuya; Uchiyama, Masanobu; Yamaguchi, Takao; Hashimoto, Yuichi; Ishikawa, Minoru

    2016-08-01

    Aqueous solubility is a key requirement for many functional molecules, e. g., drug candidates. Decrease of the partition coefficient (log P) by chemical modification, i.e., introduction of hydrophilic group(s) into molecules, is a classical strategy for improving aqueous solubility. We have been investigating alternative strategies for improving the aqueous solubility of pharmaceutical compounds by disrupting intermolecular interactions. Here, we show that introducing a bend into the molecular structure of retinoic acid receptor (RAR) agonists by changing the substitution pattern from para to meta or ortho dramatically enhances aqueous solubility by up to 890-fold. We found that meta analogs exhibit similar hydrophobicity to the parent para compound, and have lower melting points, supporting the idea that the increase of aqueous solubility was due to decreased intermolecular interactions in the solid state as a result of the structural changes. PMID:27378357

  6. Heteroaggregation of engineered nanoparticles and kaolin clays in aqueous environments.

    PubMed

    Wang, Hongtao; Dong, Ya-nan; Zhu, Miao; Li, Xiang; Keller, Arturo A; Wang, Tao; Li, Fengting

    2015-09-01

    The increasing and wide use of nanoparticles (NPs), including TiO2 and Ag NPs, have raised concerns due to their potential toxicity and environmental impacts. Kaolin is a very common mineral in aquatic systems, and there is a very high probability that nanoparticles (NPs) will interact with these clay minerals. We studied the effect of kaolin particles on the aggregation of NPs under different conditions, including the role of pH, ionic strength (IS), and humic acid (HA). We show that kaolin reduces the energy barrier and the Critical Coagulation Concentration (CCC) at pH 4. At pH 8, even though the energy barrier of the system without kaolin increases, kaolin promotes NP aggregation via heteroaggregation. When IS is equal to or greater than the CCC, on the one hand HA promotes aggregation of TiO2 NPs, but on the other hand HA decreases the rate of Ag NP aggregation because the existence of a surface coating may limit the adsorption of HA on these Ag NPs. In addition, the presence of HA increases the energy barrier and the CCC of the binary system (kaolin + NPs). Thus, the complex interactions of clay, NPs, IS, pH, and HA concentration determine the colloidal stability of the NPs. We find that kaolin is a potential coagulant for removal of NPs that behave like Ag and TiO2. PMID:26001279

  7. [Kinetics of distribution of specific contaminants in an aqueous environment].

    PubMed

    Bogacka, T

    1993-01-01

    The study was carried out for establishing the distribution of benzo(a)pyrene, fluoroanthene, methylene chloride, chloroform and carbon tetrachloride under model conditions, simulating the environment of river water moderately contaminated and distilled water. The experiments were carried out for safe concentrations and concentrations 2-5 times greater at two temperatures: about 20 degrees C and 4 degrees C, and after adaptation of microorganisms to the presence of the analysed substances. In the light of the obtained results the kinetic parameters were established of the degradation process: rate constant and degradation half-times. The process developed in accordance with the kinetic equation of 1st order and depended on the model, group of determined compounds, initial concentration, temperature and microflora adaptation to the presence of the studied substances. Of the studied contaminants the degradation of polycyclic aromatic hydrocarbons-benzo(a)pyrene and fluoroanthene, progressed at the highest rate. The higher rate of degradation in river water than in distilled water suggests that microorganisms present in natural waters participated in the degradation od the determined compounds. This process was slowed down by temperature fall to about 4 degrees C. When the microflora had been adapted to the presence of chlorinated methane derivatives the process of degradation was as rule slower than in the situation of their direct addition to the experimental model adaptation was shown to have no effect on the kinetics of polycyclic hydrocarbon degradation. PMID:8016544

  8. Mid-Infrared Sensing of Organic Pollutants in Aqueous Environments

    PubMed Central

    Pejcic, Bobby; Myers, Matthew; Ross, Andrew

    2009-01-01

    The development of chemical sensors for monitoring the levels of organic pollutants in the aquatic environment has received a great deal of attention in recent decades. In particular, the mid-infrared (MIR) sensor based on attenuated total reflectance (ATR) is a promising analytical tool that has been used to detect a variety of hydrocarbon compounds (i.e., aromatics, alkyl halides, phenols, etc.) dissolved in water. It has been shown that under certain conditions the MIR-ATR sensor is capable of achieving detection limits in the 10–100 ppb concentration range. Since the infrared spectral features of every single organic molecule are unique, the sensor is highly selective, making it possible to distinguish between many different analytes simultaneously. This review paper discusses some of the parameters (i.e., membrane type, film thickness, conditioning) that dictate MIR-ATR sensor response. The performance of various chemoselective membranes which are used in the fabrication of the sensor will be evaluated. Some of the challenges associated with long-term environmental monitoring are also discussed. PMID:22454582

  9. Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution.

    PubMed

    Cui, Lei; Chen, He; Liu, Chao; Li, Chaozhong

    2016-05-01

    Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 as the catalyst, the reactions of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in satisfactory yields under mild conditions. This site-specific allylation method is applicable to all primary, secondary, and tertiary alkyl acids and exhibits wide functional group compatibility. PMID:27065060

  10. Phosphorylation of Glyceric Acid in Aqueous Solution Using Trimetaphosphate

    NASA Technical Reports Server (NTRS)

    Kolb, Vera; Orgel, Leslie E.

    1996-01-01

    The phosphorylation of glyceric acid is an interesting prebiotic reaction because it converts a simple, potentially prebiotic organic molecule into phosphate derivatives that are central to carbohydrate metabolism. We find that 0.05 M glyceric acid in the presence of 0.5 M trimetaphosphate in alkaline solution gives a mixture of 2- and 3-phosphoglyceric acids in combined yields of up to 40%.

  11. Diglycolamic acid modified silica gel for the separation of hazardous trivalent metal ions from aqueous solution.

    PubMed

    Suneesh, A S; Syamala, K V; Venkatesan, K A; Antony, M P; Vasudeva Rao, P R

    2015-01-15

    The surface of the silica gel was modified with diglycolamic acid moieties and the product (Si-DGAH) was characterized by elemental analysis, TG-DTA, (1)H and (29)Si NMR and scanning electron microscopy (SEM). The adsorption behavior of hazardous americium (III) and europium (III) in Si-DGAH was studied from aqueous nitric acid medium to examine the feasibility using the modified silica for the separation of Am(III) and Eu(III) from aqueous wastes. In this context, the effect of various parameters such as the duration of equilibration, and concentrations of europium, nitric acid, sodium nitrate and diethylenetriaminepentaacetic acid (DTPA) in aqueous phase, on the distribution coefficient (K(d)) of Am(III) and Eu(III) was investigated. The distribution coefficient of ∼10(3) mL/g (>99.9% extraction) was obtained for both Am(III) and Eu(III) at pH 3, and the K(d) values decreased with increase in the concentration of nitric acid. Rapid kinetics of extraction in the initial stages of equilibration, followed by the establishment of equilibrium occurred within 30 min. The extraction data were fitted into Langmuir adsorption model and the apparent europium extraction capacity was determined. Europium loading capacity of the sorbent was determined at various feed pH by column method. The study indicated the possibility of using diglycolamic acid-modified silica for the separation of Eu(III) and Am(III) from aqueous wastes. PMID:25454425

  12. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  13. The Earliest Aqueous, Habitable(?) Environments on Mars: A View from Orbit

    NASA Astrophysics Data System (ADS)

    Ehlmann, Bethany

    2012-07-01

    The emerging picture of Mars' first billion years includes diverse environments involving liquid water and chemical alteration. Clay, carbonate, chloride, and sulfate minerals have all been detected and mapped from orbit in coherent geologic units. When near-infrared spectroscopic detections of minerals from the orbiting CRISM imaging spectrometer are coupled with high-resolution images of morphology provided by orbiting cameras, distinctive aqueous, potentially habitable, environments can be identified, preserved in the geologic record. I will give a global overview of the most recent findings, delve into the details of transitions recorded in a few key stratigraphic sections, and discuss the hypothesis that the most widespread and long-lived aqueous environments on early Mars were in the subsurface.

  14. PELS (Planetary Environmental Liquid Simulator): a new type of simulation facility to study extraterrestrial aqueous environments.

    PubMed

    Martin, Derek; Cockell, Charles S

    2015-02-01

    Investigations of other planetary bodies, including Mars and icy moons such as Enceladus and Europa, show that they may have hosted aqueous environments in the past and may do so even today. Therefore, a major challenge in astrobiology is to build facilities that will allow us to study the geochemistry and habitability of these extraterrestrial environments. Here, we describe a simulation facility (PELS: Planetary Environmental Liquid Simulator) with the capability for liquid input and output that allows for the study of such environments. The facility, containing six separate sample vessels, allows for statistical replication of samples. Control of pressure, gas composition, UV irradiation conditions, and temperature allows for the precise replication of aqueous conditions, including subzero brines under martian atmospheric conditions. A sample acquisition system allows for the collection of both liquid and solid samples from within the chamber without breaking the atmospheric conditions, enabling detailed studies of the geochemical evolution and habitability of past and present extraterrestrial environments. The facility we describe represents a new frontier in planetary simulation-continuous flow-through simulation of extraterrestrial aqueous environments. PMID:25651097

  15. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  16. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  17. Multi-walled carbon nanotubes in aqueous phytic acid for enhancing biosensor

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoyu; Miao, Yun; Ye, Pingping; Wen, Ying; Yang, Haifeng

    2014-04-01

    The poor dispersion of carbon based nanomaterials without strong acid pretreatment in aqueous solution is a fundamental problem, limiting its applications in biology-related fields. A good dispersion of multi-walled carbon nanotubes (MWCNTs) in water was realized by 50 wt.% phytic acid (PA) solution. As an application case, the PA-MWCNTs dispersion in aqueous solution was used for the immobilization of horseradish peroxidase (HRP) and its direct electrochemistry was realized. The constructed biosensor has a sound limit of detection, wide linear range, and high affinity for hydrogen peroxide (H2O2) as well as being free from interference of co-existing electro-active species.

  18. Dissolution state of cellulose in aqueous systems. 2. Acidic solvents.

    PubMed

    Alves, Luis; Medronho, Bruno; Antunes, Filipe E; Topgaard, Daniel; Lindman, Björn

    2016-10-20

    Cellulose is insoluble in water but can be dissolved in strong acidic or alkaline conditions. How well dissolved cellulose is in solution and how it organizes are key questions often neglected in literature. The typical low pH required for dissolving cellulose in acidic solvents limits the use of typical characterization techniques. In this respect, Polarization Transfer Solid State NMR (PT ssNMR) emerges as a reliable alternative. In this work, combining PT ssNMR, microscopic techniques and X-ray diffraction, a set of different acidic systems (phosphoric acid/water, sulfuric acid/glycerol and zinc chloride/water) is investigated. The studied solvent systems are capable to efficiently dissolve cellulose, although degradation occurs to some extent. PT ssNMR is capable to identify the liquid and solid fractions of cellulose, the degradation products and it is also sensitive to gelation. The materials regenerated from the acidic dopes were found to be highly sensitive to the solvent system and to the presence of amphiphilic additives in solution. PMID:27474617

  19. Histological effects of aqueous acids and gaseous hydrogen chloride on bean leaves

    SciTech Connect

    Swiecki, T.J.; Endress, A.G.; Taylor, O.C.

    1982-01-01

    Primary leaves of Phaseoulus vulgaris L. (pinto bean), 9 or 12 days from sowing, were exposed to aqueous acids, chloride salts, or hydrogen chloride gas. Leaves were examined for the presence and severity of resultant visible injury and samples for light and scanning electron microscopy. Exposure to 0.06 N HCl, HNO/sub 3/, H/sub 2/SO/sub 4/ or 14.5-19.0 mg m/sup -3/ gaseous HCl for 20 min evoked similar foliar injury including glazing and necrosis of the laminas. This injury appeared to result initially from plasmolysis and collapse of the epidermis and subsequently of the underlying mesophyll. Cellular injury was accompanied by various cytoplasmic alterations. Microscopic symptoms observed in leaves exposed to gaseous HCl or aqueous acids included vesicles and particulates within the larger vacuoles. Similar symptoms were present in leaves exposed to polyethylene glycol 6000. Differential effects included formation of necrotic pits and preferential injury to paravascular tissues in leaves treated with aqueous acids and crystalline chloroplast inclusions in gaseous HCl-treated and water-stressed leaves. The visible and microscopic appearances of leaves exposed to aqueous acids or gaseous HCl were compared and related to injury stemming from acid precipitation and a possible mechanism of action for gaseous HCl phytotoxicity.

  20. Acid gas absorption in aqueous solutions of mixed amines

    SciTech Connect

    Rinker, E.B.; Ashour, S.S.; Sandall, O.C.

    1996-12-31

    A mass transfer model has been developed to describe the rate of absorption (or desorption) of H{sub 2}S and CO{sub 2} in aqueous blends of a tertiary and a secondary or a primary amine. The model is based on penetration theory, and all significant chemical reactions are incorporated in the model. The reactions are taken to be reversible, with reactions involving only a proton transfer considered to be at equilibrium. The particular amines studied in this research were methyldiethanolamine (MDEA), a tertiary amine, and diethanolamine (DEA), a secondary amine. Key physicochemical data needed in the model, such as diffusion coefficients, kinetic rate constants, and gas solubilities, were measured. Experimental absorption rates of CO{sub 2} and H{sub 2}S were measured in a model gas-liquid contacting device and were compared with model predictions. Experiments were carried out for single amine solutions (both MDEA and DEA) and for amine blends.

  1. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    PubMed

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end. PMID:26077317

  2. Acid gas treating by aqueous alkanolamines. Annual report, January-December 1994

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Ashour, S.

    1994-12-01

    The objective of this work is to investigate the simulateneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed this year the authors have measured the density, viscosity and surface tension of pure MDEA and DEA over a range in temperatures. The diffusivity of N2O was measured in aqueous blends of MDEA and DEA at 50 wt% total amine for various ratios of DEA to MDEA over the temperature range 20 to 80 deg. C. A theoretically-based model has been developed for the correlation of the physical solubility of N2O in aqueous amine solutions. A penetration theory type model which was developed to describe acid gas absorption in aqueous amine solutions was used to carry out a sensitivity analysis for the various parameters affecting the rate of absorption of CO2 in MDEA solutions.

  3. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

    2016-09-01

    Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

  4. STABILITY OF MFI ZEOLITE-FILLED PDMS MEMBRANES DURING PERVAPORATIVE ETHANOL RECOVERY FROM AQUEOUS MIXTURES CONTAINING ACETIC ACID

    EPA Science Inventory

    Pervaporation is a potential process for recovering bioethanol produced from biomass fermentation. Fermentation broths contain ethanol, water, and a variety of other compounds, often including carboxylic acids. The effects of acetic acid on long-term pervaporation of aqueous et...

  5. Comparison of XAD macroporous resins for the concentration of fulvic acid from aqueous solution

    USGS Publications Warehouse

    Aiken, G.R.

    1979-01-01

    Five macroreticular, nonlonlc AmberlHe XAD resins were evaluated for concentration and Isolation of fulvlc acid from aqueous solution. The capacity of each resin for fulvlc acid was measured by both batch and column techniques. Elution efficiencies were determined by desorptlon with 0.1 N NaOH. Highest recoveries were obtained with the acrylic ester resins which proved to be most efficient for both adsorption and elution of fulvlc acid. Compared to the acrylic ester resins, usefulness of the styrene dvlnybenzene resins to remove fulvlc acid is limited because of slow diffusion-controlled adsorption and formation of charge-transfer complexes, which hinders elution. ?? 1979 American Chemical Society.

  6. Transmission X-ray microscopy reveals the clay aggregate discrete structure in aqueous environment.

    PubMed

    Zbik, Marek S; Frost, Ray L; Song, Yen-Fang; Chen, Yi-Ming; Chen, Jian-Hua

    2008-03-15

    The utilization of new transmission X-ray microscopy (TXM) using the synchrotron photon source enable for the first time the study in three dimensions microsize clay particles in aggregates in their natural aqueous environment. This technique makes possible remarkable accurate images of nanosize mineral interparticle structure which forms a new nanocomposite. The Birdwood kaolinite/LDH aggregates observed in the TXM are much more compact than observed before in pure Birdwood kaolinite suspension and similar to aggregates formed after treatment by positively charged surfactant. Kaolinite/LDH aggregates in water reveal complex structure of larger kaolinite platelets connected together by gelled nanoparticles which are most probably LDH colloidal plates. Comparisons of the transmission electron microscope (TEM) and TXM techniques show similarities in particle morphology. The ability to study particles and aggregates in their natural aqueous environment and in 3-dimensions make this technique superior to the TEM technique. PMID:18187142

  7. Spectroelectrochemical photoluminescence of titanium dioxide nanosheets and nanoparticles in aqueous and nonaqueous environments

    NASA Astrophysics Data System (ADS)

    Rex, Riley E.; Knorr, Fritz J.; McHale, Jeanne L.

    2014-09-01

    Spectroelectrochemical photoluminescence (SEPL) is used to investigate surface electron and hole traps on anatase nanoparticles, anatase nanosheets and rutile nanowires in aqueous and nonaqueous environments. In aqueous environment there is an overvoltage for occupying surface electron traps in rutile and anatase samples. For anatase, this overvoltage is larger on (101) nanoparticles than on (001) nanosheets. The electrochemical energy levels of electron traps determined by SEPL in acetonitrile are consistent with emitted photon energies as determined by the photoluminescence spectrum. Our results show how the contacting solvent and particle morphology can influence the redox potential of surface electron traps and thus guide further research on improving the performance of nano- TiO2 in applications such as dye-sensitized solar cells and solar water splitting.

  8. Spectral identification of hydrated sulfates on Mars and comparison with acidic environments on Earth

    NASA Astrophysics Data System (ADS)

    Bishop, Janice L.; Darby Dyar, M.; Lane, Melissa D.; Banfield, Jillian F.

    2004-10-01

    We interpret recent spectral data of Mars collected by the Mars Exploration Rovers to contain substantial evidence of sulfate minerals and aqueous processes. We present visible/near-infrared (VNIR), mid-IR and Mössbauer spectra of several iron sulfate minerals and two acid mine drainage (AMD) samples collected from the Iron Mountain site and compare these combined data with the recent spectra of Mars. We suggest that the sulfates on Mars are produced via aqueous oxidation of sulfides known to be present on Mars from Martian meteorites. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to AMD environments on Earth. Because microorganisms are typically involved in the oxidation of sulfides to sulfates in terrestrial AMD sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals is likely to lead to aqueous processes and chemical weathering. Our results imply that sulfate minerals formed in Martian soils via chemical weathering, perhaps over very long time periods, and that sulfate minerals precipitated following aqueous oxidation of sulfides to form the outcrop rocks at Meridiani Planum.

  9. Hydrogen-Deuterium Exchange of Meteoritic Dicarboxylic Acids During Aqueous Extraction

    NASA Technical Reports Server (NTRS)

    Fuller, M.; Huang, Y.

    2002-01-01

    This study examines the extent of hydrogen-deuterium exchange on dicarboxylic acids during aqueous extraction. Deuterium enrichment was observed to be a function of diacid structure as well as delta-D. Additional information is contained in the original extended abstract.

  10. POLYSTYRENE SULFONIC ACID CATALYZED GREENER SYNTHESIS OF HYDRAZONES IN AQUEOUS MEDIUM USING MICROWAVES

    EPA Science Inventory

    An environmentally benign aqueous protocol for the synthesis of cyclic, bi-cyclic, and heterocyclic hydrazones using polystyrene sulfonic acid (PSSA) as a catalyst has been developed; the simple reaction proceeds efficiently in water in the absence of any organic solvent under mi...

  11. Rosmarinic acid content in antidiabetic aqueous extract from ocimum canum sims in Ghana

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rosmarinic acid (RA) is an important polyphenol that is found in a variety of herbs including Ocimum canum sims (locally called eme or akokobesa in Ghana). Aqueous extracts from the leaves of O. canum are used as an antidiabetic herbal medicine in Ghana. Analytical TLC was used to examine the compos...

  12. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  13. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  14. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  15. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  16. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  17. SOLVENT EXTRACTION PROCESS FOR SEPARATING URANIUM AND PLUTONIUM FROM AQUEOUS ACIDIC SOLUTIONS OF NEUTRON IRRADIATED URANIUM

    DOEpatents

    Bruce, F.R.

    1962-07-24

    A solvent extraction process was developed for separating actinide elements including plutonium and uranium from fission products. By this method the ion content of the acidic aqueous solution is adjusted so that it contains more equivalents of total metal ions than equivalents of nitrate ions. Under these conditions the extractability of fission products is greatly decreased. (AEC)

  18. THE ROLE OF SELECTED CATIONS IN THE FORMATION OF PSEUDOMICELLES IN AQUEOUS HUMIC ACID (R822832)

    EPA Science Inventory

    The fluorescence intensity enhancement of a pyrene probe in aqueous humic acid solutions was assessed in terms of added lanthanide and thorium cations. Among the trivalent ions it was found that size played a role, with the small Lu3+ ion producing the greatest increase in pyrene...

  19. Standard enthalpies of formation of α-aminobutyric acid and products of its dissociation in an aqueous solution

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.

    2016-08-01

    Heats of solution of crystalline α-aminobutyric acid in water and in aqueous solutions of potassium hydroxide at 298.15 K are measured by means of direct calorimetry. Standard enthalpies of formation of the amino acid and products of its dissociation in an aqueous solution are calculated.

  20. Curcumin-cysteine and curcumin-tryptophan conjugate as fluorescence turn on sensors for picric Acid in aqueous media.

    PubMed

    Gogoi, Bedanta; Sen Sarma, Neelotpal

    2015-06-01

    Rapid detection of picric acid in real sample is of outmost importance from the perspective of health, safety, and environment. In this study, a very simple and cost-effective detection of picric acid is accomplished by developing a couple of biobased conjugates curcumin-cysteine (CC) and curcumin-tryptophan (CT), which undergo efficient fluorescence turn on toward picric acid in aqueous media. Both the probes experience about 26.5-fold fluorescence enhancements at 70 nM concentration of the analyte. Here, the fluorescence turn on process is governed by the aggregation induced emission, which is induced from the electrostatic interaction between the conjugates with picric acid. The detection limit of CC and CT are about 13.51 and 13.54 nM of picric acid, respectively. Importantly, both the probes exhibit high selectivity and low interference of other analogues toward the detection of picric acid. In addition, the probes are highly photostable, show low response time and are practically applicable for sensing picric acid in real environmental samples, which is the ultimate goal of this work. PMID:25955402

  1. Salt and mesophase formation in aqueous suspensions of lauric acid.

    PubMed

    Smith, S W; Anderson, B D

    1993-10-01

    The solubility and solution behavior of lauric acid (LA) and its 1:1 acid soap (potassium hydrogen dilaurate) were investigated at 32 degrees C over a pH range of 2.5-8.5 and at varying KCl concentrations to examine the self-association of this long-chain carboxylic acid under these conditions. LA's solubility in water exhibited the classical pH dependence of a monocarboxylic acid with no evidence of self-association. In 0.1 M KCl between pH 6.3 and pH 7.3, filtered samples were turbid, suggesting the presence of high molecular weight aggregates (mesophase), which could be removed by ultrafiltration. The apparent LA solubility vs pH profile in ultrafiltered samples was consistent with a solid phase consisting of either the free acid (pH < 6.5) or potassium hydrogen dilaurate (pH > 6.5), again with no evidence of self-association to form low molecular weight species (dimers, etc.). Quasi-elastic light scattering (QLS) studies and mannitol trapping experiments indicated that vesicles were present in samples containing mesophase. The mesophase composition was characterized and a mass-action law for mesophase formation was developed to describe the apparent LA solubility versus pH in the mesophase region in terms of three parameters. The index of cooperativity, theta, indicated that the mesophase consists of approximately 25 molecules of LA with an acid:anion ratio, rho, of 1.7. The standard free energy of mesophase formation per mole of monomer was determined to be -6.3 kcal/mol. The aggregate size determined thermodynamically is several orders of magnitude less than that of the mesophase particle size determined by QLS measurements, suggesting that the LA monomer concentration in equilibrium with mesophase may be governed by a small unit domain of the vesicle. These observations may have a bearing on the thermodynamics of self-assembly of lipid bilayer membranes. PMID:8272419

  2. Emergency cooling experiments with aqueous boric acid solution in the REWET-II facility

    SciTech Connect

    Kervinen, T.; Tuunanen, J.

    1987-01-01

    Although boron is widely used as soluble neutron poison in nuclear reactors (boric acid in pressurized water reactors, sodium pentaborate in boiling water reactors), there is a lack of experimental data about aqueous boron solution behavior during loss-of-coolant accidents. The main aims of the REWET boric acid experiments were to study the behavior of aqueous boric acid solution during long-term cooling of a nuclear reactor and to find out the circumstances in which boric acid crystallization takes place. In the experiments, carried out in the facility of a 19-fuel-rod simulator bundle, boric acid crystallization caused the uncovering of the bundle, which always occurred on the water surface. However, crossflows and backflows in a reactor presumably make the concentrations uniform and thus retard crystallization. Therefore, experimental investigations of aqueous boric acid solution behavior will be carried out for the next 2 yr in a larger scale experimental facility. The new facility will be a simulator of the Loviisa VVER-440 reactor with a scaling factor of 1:349 for power and volumes and 1:1 for elevations. The facility will contain a full-scale rod bundle.

  3. IMMOBILIZATION OF AQUEOUS PYRENE BY DISSOLVED HUMIC ACID (R822832)

    EPA Science Inventory

    Abstract

    Pyrene is frequently used as a fluorescent probe in the study of solution environments. Purging with nitrogen is a common practice for the elimination of oxygen from solutions, but this procedure leads to the loss of pyrene through carry-over in the nitrogen s...

  4. Theoretical insights into the properties of amino acid ionic liquids in aqueous solution.

    PubMed

    Zhu, Xueying; Ai, Hongqi

    2016-07-01

    This report presents a systematic investigation of the interactions of water molecule(s) with a series of amino acid cations (Gly(+), Ala(+), Val(+), and Leu(+)), halogen anions (Cl(-), Br(-), BF4 (-), and PF6 (-)), and clusters (GlyCl) n (n = 1-5). The results reveal that H-bonds between amino acid ionic liquids (AAILs) and water molecules are crucial to the properties of aqueous solution of AAILs. The properties of AAIL in water solution depend on the alkyl chain of the amino acid cation, the size of the halogen anion, and the number of water molecules, which provides a certain theoretical basis for the design and application of new AAILs. A series of calculations for some different models showed that quadruple-GlyCl hydrate represents a basic unit for the Gly-water binary system, and can be employed as the simplest model for studying an AAIL-water cluster. On the basis of this model, the effects of water on the hygroscopicity, speed of solubility, viscosity, density, solution enthalpy, and polarity of the AAIL were also predicted. Most importantly, unlike traditional ILs, the novel GlyCl-type AAIL favors interaction of its cationic part, rather than its anionic part, with surrounding water molecules, thus amino acid cationic ILs expand the types of IL available, increasing the choice of ILs for different purposes. We hope that the application of this AAIL in many fields will lead to optimization of this class of compound and be of benefit to the environment. Graphical Abstract Quadruple-GlyCl hydrate represents the basic unit for a GlyCl-water binary system, which can be employed as the simplest model for studying an amino acid ionic liquid (AAIL)-water cluster. The effects of available water on some properties of AAIL are predicted. GlyCl-type AAIL is a novel IL, which prefers its cationic part over its anionic part for interaction with surrounding water molecules. The properties of AAIL in water solution can be adjusted by varying the ion used and the

  5. The effect of thermal treatment on the fracture properties of alloy X-750 in aqueous environments

    SciTech Connect

    Ballinger, R.; Elliott, C.S.; Hwang, I.S.; Prybylowski, J.

    1993-05-01

    Alloy X-750 is a high strength, age hardenable nickel-base alloy used in light water nuclear reactors. The excellent corrosion resistance and high temperature strength of alloy X-750 make it suitable for use in a variety of structure components in both pressurized water reactors and boiling water reactors. These applications involve exposure of highly stressed material to aqueous media. Operational stresses are subject to low frequency thermally induced fluctuations and high frequency flow induced fluctuations. In general, alloy X-750 has performed well in light water reactors. However, an economically significant number of components have failed unexpectedly due to localized forms of attack such as corrosion fatigue and stress corrosion cracking. Thermal processing history is known to play a significant role in the fracture properties of alloy X-750 in aqueous environments. While thermal treatments have been developed recently to improve performance, in many cases the reason for improved performance remains unclear. Therefore, identification of the mechanisms responsible for the degradation of fracture properties in aqueous environments is necessary. As a corollary it is necessary to achieve an understanding of how thermal treatment influences microstructure and, in turn, how microstructure influences fracture properties in aqueous environments. This report discusses five thermal treatments which were studied: (1) SA-1 hr at 1093{degree}C, (2) AH - 24 hr at 885{degree}C + 20 hr at 704{degree}C, (3) HTH - 1 hr at 1093{degree}C + 20 hr at 704{degree}C, (4) AHTH - 1 hr at 1093{degree}C + 24 hr at 885{degree}C + 20 hr at 704{degree}C, and (5) HOA - 1 hr at 1093{degree}C + 100 hrs at 760{degree}C. Microstructural characterization of these materials was accomplished through the use of optical microscopy, transmission electron microscopy,scanning transmission electron microscopy, energy dispersive x-ray spectroscopy, and x-ray diffractometry.

  6. Reduction of hexavalent chromium by ascorbic acid in aqueous solutions.

    PubMed

    Xu, Xiang-Rong; Li, Hua-Bin; Li, Xiao-Yan; Gu, Ji-Dong

    2004-11-01

    Hexavalent chromium is a priority pollutant in the USA and many other countries. Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Reduction of Cr(VI) by ascorbic acid (vitamin C) as a reductant was studied using potassium dichromate solution as the model pollutant. Effects of concentration of vitamin C, pH, temperature, irradiation and reaction time on the reduction of Cr(VI) were examined. Cr(VI) might be reduced by vitamin C not only in acidic conditions but also in weakly alkaline solutions. The reduction of Cr(VI) by vitamin C might occur not only under irradiation but also in the dark. Vitamin C is an important biological reductant in humans and animals, and not toxic. It is water-soluble and can easily permeate through various types of soils. The results indicate that vitamin C could be used in effective remediation of Cr(VI)-contaminated soils and groundwater in a wide range of pH, with or without sunlight. PMID:15488923

  7. Aminocarbonyloxymethyl ester prodrugs of flufenamic acid and diclofenac: suppressing the rearrangement pathway in aqueous media.

    PubMed

    Ribeiro, Lina; Silva, Nuno; Iley, Jim; Rautio, Jarkko; Järvinen, Tomi; Mota-Filipe, Hélder; Moreira, Rui; Mendes, Eduarda

    2007-01-01

    Aminocarbonyloxymethyl ester prodrugs are known to undergo rearrangement in aqueous solutions to form the corresponding N-acylamine side product via an O-->N intramolecular acyl transfer from the carbamate conjugate base. Novel aminocarbonyloxymethyl esters of diclofenac and flufenamic acid containing amino acid amide carriers were synthesized and evaluated as potential prodrugs displaying less ability to undergo rearrangement. These compounds were prepared in reasonable yield by a four-step synthetic method that uses the appropriate N-Boc-protected amino acid N-hydroxysuccinimide ester and secondary amine and chloromethyl chloroformate as key reactants. Their reactivity in pH 7.4 buffer and 80% human plasma at 37 degrees C was assessed by RP-HPLC. The aminocarbonyloxymethyl esters containing a secondary carbamate group derived from amino acids such as glycine or phenylalanine were hydrolyzed quantitatively to the parent drug both in non-enzymatic and enzymatic conditions, with no rearrangement product being detected. The oral bioavailability in rats was determined for selected diclofenac derivatives. These derivatives displayed a bioavailability of 25 to 68% relative to that of diclofenac, probably due to their poor aqueous solubility and lipophilicity. These results suggest that further optimization of aminocarbonyloxymethyl esters as potential prodrugs for non-steroidal anti-inflammatory drugs require the use of amino acid carriers with ionizable groups to improve aqueous solubility. PMID:17206608

  8. Regeneration of an aqueous solution from an acid gas absorption process by matrix stripping

    DOEpatents

    Rochelle, Gary T.; Oyenekan, Babatunde A.

    2011-03-08

    Carbon dioxide and other acid gases are removed from gaseous streams using aqueous absorption and stripping processes. By replacing the conventional stripper used to regenerate the aqueous solvent and capture the acid gas with a matrix stripping configuration, less energy is consumed. The matrix stripping configuration uses two or more reboiled strippers at different pressures. The rich feed from the absorption equipment is split among the strippers, and partially regenerated solvent from the highest pressure stripper flows to the middle of sequentially lower pressure strippers in a "matrix" pattern. By selecting certain parameters of the matrix stripping configuration such that the total energy required by the strippers to achieve a desired percentage of acid gas removal from the gaseous stream is minimized, further energy savings can be realized.

  9. Analysis of the amino acids of soy globulins by AOT reverse micelles and aqueous buffer.

    PubMed

    Zhao, Xiaoyan; Chen, Jun; Lu, Zhifang; Ling, Xiangqing; Deng, Peng; Zhu, Qingjun; Du, Fangling

    2011-10-01

    The 7S and 11S globulins from soybean proteins using reverse micelle and aqueous buffer extraction methods were characterized by using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) and scanning electron microscope (SEM), and their amino acid compositions were also evaluated. SDS-PAGE did not show electrophoretic differences between 7S and 11S globulin subunits with two extraction methods. SEM analysis showed that the AOT reverse micelle processing of 7S and 11S globulins induced a reduction of droplet size. Some individual amino acid contents of 7S and 11S globulins using two extraction methods were different, some were similar. In all the samples, the glutamic acid, aspartic acid, and leucine were the dominant amino acids while the cystine and methionine were the first-limiting amino acids. The proportion of essential amino acids to the total amino acids (E/T) of the 7S globulin from aqueous buffer and reverse micelles was similar. While significant differences were obtained in the proportion of E/T of the 11S globulin. PMID:21647686

  10. Gamma-irradiation of malic acid in aqueous solutions. [prebiotic significance

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Graff, R. L.; Ponnamperuma, C.

    1980-01-01

    The gamma-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the nonvolatile products. Thin layer chromatography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the gamma-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

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

    PubMed Central

    2011-01-01

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

  12. Conversion of Aqueous Ammonia-Treated Corn Stover to Lactic Acid by Simultaneous Saccharification and Cofermentation

    NASA Astrophysics Data System (ADS)

    Zhu, Yongming; Lee, Y. Y.; Elander, Richard T.

    Treatment of corn stover with aqueous ammonia removes most of the structural lignin, whereas retaining the majority of the carbohydrates in the solids. After treatment, both the cellulose and hemicellulose in corn stover become highly susceptible to enzymatic digestion. In this study, corn stover treated by aqueous ammonia was investigated as the substrate for lactic acid production by simultaneous saccharification and cofermentation (SSCF). A commercial cellulase (Spezyme-CP) and Lactobacillus pentosus American Type Culture Collection (ATCC) 8041 (Spanish Type Culture Collection [CECT]-4023) were used for hydrolysis and fermentation, respectively. In batch SSCF operation, the carbohydrates in the treated corn stover were converted to lactic acid with high yields, the maximum lactic acid yield reaching 92% of the stoichiometric maximum based on total fermentable carbohydrates (glucose, xylose, and arabinose). A small amount of acetic acid was also produced from pentoses through the phosphoketolase pathway. Among the major process variables for batch SSCF, enzyme loading and the amount of yeast extract were found to be the key factors affecting lactic acid production. Further tests on nutrients indicated that corn steep liquor could be substituted for yeast extract as a nitrogen source to achieve the same lactic acid yield. Fed-batch operation of the SSCF was beneficial in raising the concentration of lactic acid to a maximum value of 75.0 g/L.

  13. A method for determining thermophysical properties of organic material in aqueous solutions: Succinic acid

    NASA Astrophysics Data System (ADS)

    Riipinen, I.; Svenningsson, B.; Bilde, M.; Gaman, A.; Lehtinen, K. E. J.; Kulmala, M.

    2006-12-01

    A method for determining evaporation rates and thermodynamic properties of aqueous solution droplets is introduced. The method combines evaporation rate measurements using modified TDMA technique with data evaluation using an accurate evaporation model. The first set of data has been collected and evaluated for succinic acid aqueous solution droplets. Evaporation rates of succinic acid solution droplets have been measured using a TDMA system at controlled relative humidity (65%) and temperature (298 K). A temperature-dependent expression for the saturation vapour pressure of pure liquid phase succinic acid at atmospheric temperatures has been derived by analysing the evaporation rate data with a numerical model. The obtained saturation vapour pressure of liquid phase succinic acid is ln( p) = 118.41 - 16204.8/ T - 12.452ln( T). The vapour pressure is in unit of Pascal and the temperature in Kelvin. A linear expression for the enthalpy of vaporization for liquid state succinic acid is also presented. According to the results presented in the following, a literature expression for the vapour pressure of liquid phase succinic acid defined for temperatures higher than 461 K [Yaws, C.L., 2003. Yaws' Handbook of Thermodynamic and Physical Properties of Chemical Compounds, Knovel] can be extrapolated to atmospheric temperatures with very good accuracy. The results also suggest that at 298 K the mass accommodation coefficient of succinic acid is unity or very close to unity.

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

    NASA Astrophysics Data System (ADS)

    Jaramillo, Paula; Coutinho, Kaline; Canuto, Sylvio

    2009-09-01

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

  15. Electrochemiluminescence of Tris(2,2'-bipyridyl)ruthenium(II) with Ascorbic Acid and Dehydroascorbic Acid in Aqueous and Non-aqueous Solutions.

    PubMed

    Takahashi, Fumiki; Hattori, Kaoru; Matsuoka, Masanori; Jin, Jiye

    2016-01-01

    The electrochemiluminescence (ECL) of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+)) is studied in non-aqueous media using dehydroascorbic acid (DHA) as coreactant to validate the evidence for the mechanism of the ascorbic acid (H2A)/Ru(bpy)3(2+) ECL system in an aqueous media. DHA is electrochemically reduced around -1.2 V vs. Ag/Ag(+) in pure acetonitrile to generate the ascorbyl radical anion (A(•-)), which is confirmed by in-situ UV-visible absorption measurements using a thin-layer spectroelectrochemical cell. The ECL of the DHA/Ru(bpy)3(2+) system in non-aqueous media is not observed in the potential range from 0 to +1.4 V in anodic potential sweep mode; however, distinct ECL is detected using double potential step electrolysis from -1.2 to +1.4 V vs. Ag/Ag(+). The ECL may be generated by a homogeneous charge-transfer process between A(•-) produced during the first pulse potential step (-1.2 V) and Ru(bpy)3(3+) generated during the second pulse potential step (+1.4 V). The calculated standard enthalpy (-ΔH°) for the charge-transfer reaction between A(•-) and Ru(bpy)3(3+) is 2.29 eV, which is larger than the lowest excited singlet state energy of Ru(bpy)3(2+) (*Ru(bpy)3(2+); 2.03 eV, 610 nm). It is determined that the generated intermediate A(•-) is crucial in the Ru(bpy)3(2+) ECL reaction. PMID:27063718

  16. 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 α-cellulose. PMID:23898802

  17. Crystallization and immersion freezing ability of oxalic and succinic acid in multicomponent aqueous organic aerosol particles

    NASA Astrophysics Data System (ADS)

    Wagner, Robert; Höhler, Kristina; Möhler, Ottmar; Saathoff, Harald; Schnaiter, Martin

    2015-04-01

    This study reports on heterogeneous ice nucleation efficiency of immersed oxalic and succinic acid crystals in the temperature range from 245 to 215 K, as investigated with expansion cooling experiments using suspended particles. In contrast to previous laboratory work with emulsified solution droplets where the precipitation of solid inclusions required a preceding freezing/evaporation cycle, we show that immersed solids readily form by homogeneous crystallization within aqueous solution droplets of multicomponent organic mixtures, which have noneutonic compositions with an excess of oxalic or succinic acid. Whereas succinic acid crystals did not act as heterogeneous ice nuclei, immersion freezing by oxalic acid dihydrate crystals led to a reduction of the ice saturation ratio at freezing onset by 0.066-0.072 compared to homogeneous freezing, which is by a factor of 2 higher than previously reported laboratory data. These observations emphasize the importance of oxalic acid in heterogeneous ice nucleation.

  18. Effective Removal of Tetracycline from Aqueous Solution by Organic Acid-Coated Magnetic Nanoparticles.

    PubMed

    Guo, Liang; Liang, Yuyan; Chen, Xuelan; Xu, Wei; Wu, Kesheng; Wei, Hua; Xiong, Yonghua

    2016-03-01

    Self-assembled iron oxide nanocomposites are good magnetic nano-adsorbents that can be prepared using simple methods. Four types of organic acid-functionalised (oleic acid, undecenoic acid, caprylic acid or hexanoic acid) magnetic nanoparticles (MNPs) were synthesised through a one-pot chemisorption method for the removal of tetracycline (TC) from aqueous solution. The undecenoic acid-coated MNPs (UA-MNPs) exhibited the highest adsorption efficiency and can be easily retrieved with a low-gradient magnetic separator (0.4 Tesla) at pH 5.0 aqueous solution. The TC adsorption process on the UA-MNPs followed the Langmuir isotherm and the maximum adsorption capacities increased from 86.96 mg g(-1) to 222.2 mg g(-1) with the increase in temperature from 288 K to 318 K. The kinetics of adsorption fits pseudo-second-order model perfectly with a rate constant, 5.946 g mg(-1) min(-1) at 298 K. The positive values of the enthalpy (AH) and the negative value of the free energy (AG) indicated an endothermic and spontaneous adsorption process of TC on the UA-MNPs. Moreover, the UA-MNPs possessed excellent ability to adsorb the other three major types of TC antibiotics, including chlortetracycline, oxytetracycline and doxycycline. PMID:27455621

  19. Stability of titania nanotube arrays in aqueous environment and the related factors

    PubMed Central

    Cao, Can; Yan, Jun; Zhang, Yumei; Zhao, Lingzhou

    2016-01-01

    Titania nanotube arrays (NTAs) on titanium (Ti) fabricated by electrochemical anodization have attracted tremendous interest for diverse applications, of which most perform in aqueous environment or related to interaction with water. The NTAs are widely studied however the related factor of stability of NTAs when applied in such environment has rarely been concerned. We report that the annealed anatase NTAs are stable but the non-annealed amorphous NTAs are unstable to undergo specific structural change accompanied with a process of amorphous TiO2 dissolution and anatase TiO2 recrystallization. Quite unexpectedly, the non-annealed NTAs still show good stability without structural change in the cell culture media, possibly due to the presence of inorganics that may interfere with the TiO2 dissolution/redeposition process. The pH value of the aqueous environment is not a determinant factor for the structural change for non-annealed NTAs or not, while the temperature and the existence of F− can accelerate the structural change process. F− may play a very important role in the change process. PMID:26960922

  20. Stability of titania nanotube arrays in aqueous environment and the related factors

    NASA Astrophysics Data System (ADS)

    Cao, Can; Yan, Jun; Zhang, Yumei; Zhao, Lingzhou

    2016-03-01

    Titania nanotube arrays (NTAs) on titanium (Ti) fabricated by electrochemical anodization have attracted tremendous interest for diverse applications, of which most perform in aqueous environment or related to interaction with water. The NTAs are widely studied however the related factor of stability of NTAs when applied in such environment has rarely been concerned. We report that the annealed anatase NTAs are stable but the non-annealed amorphous NTAs are unstable to undergo specific structural change accompanied with a process of amorphous TiO2 dissolution and anatase TiO2 recrystallization. Quite unexpectedly, the non-annealed NTAs still show good stability without structural change in the cell culture media, possibly due to the presence of inorganics that may interfere with the TiO2 dissolution/redeposition process. The pH value of the aqueous environment is not a determinant factor for the structural change for non-annealed NTAs or not, while the temperature and the existence of F‑ can accelerate the structural change process. F‑ may play a very important role in the change process.

  1. Heavy metals removal from aqueous environments by electrocoagulation process- a systematic review.

    PubMed

    Bazrafshan, Edris; Mohammadi, Leili; Ansari-Moghaddam, Alireza; Mahvi, Amir Hossein

    2015-01-01

    Heavy metals pollution has become a more serious environmental problem in the last several decades as a result releasing toxic materials into the environment. Various techniques such as physical, chemical, biological, advanced oxidation and electrochemical processes were used for the treatment of domestic, industrial and agricultural effluents. The commonly used conventional biological treatments processes are not only time consuming but also need large operational area. Accordingly, it seems that these methods are not cost-effective for effluent containing toxic elements. Advanced oxidation techniques result in high treatment cost and are generally used to obtain high purity grade water. The chemical coagulation technique is slow and generates large amount of sludge. Electrocoagulation is an electrochemical technique with many applications. This process has recently attracted attention as a potential technique for treating industrial wastewater due to its versatility and environmental compatibility. This process has been applied for the treatment of many kinds of wastewater such as landfill leachate, restaurant, carwash, slaughterhouse, textile, laundry, tannery, petroleum refinery wastewater and for removal of bacteria, arsenic, fluoride, pesticides and heavy metals from aqueous environments. The objective of the present manuscript is to review the potential of electrocoagulation process for the treatment of domestic, industrial and agricultural effluents, especially removal of heavy metals from aqueous environments. About 100 published studies (1977-2016) are reviewed in this paper. It is evident from the literature survey articles that electrocoagulation are the most frequently studied for the treatment of heavy metal wastewater. PMID:26512324

  2. Ion Pair in Extreme Aqueous Environments, Molecular-Based and Electric Conductance Approaches

    SciTech Connect

    Chialvo, Ariel A; Gruszkiewicz, Miroslaw {Mirek} S; Simonson, J Michael {Mike}; Palmer, Donald; Cole, David R

    2009-01-01

    We determine by molecular-based simulation the density profiles of the Na+!Cl! ion-pair association constant in steam environments along three supercritical isotherms to interrogate the behavior of ion speciation in dilute aqueous solutions at extreme conditions. Moreover, we describe a new ultra-sensitive flow-through electric conductance apparatus designed to bridge the gap between the currently lowest steam-density conditions at which we are experimentally able to attain electric conductance measurements and the theoretically-reachable zero-density limit. Finally, we highlight important modeling challenges encountered near the zero-density limit and discuss ways to overcome them.

  3. Sequence of morphological transitions in two-dimensional pattern growth from aqueous ascorbic Acid solutions.

    PubMed

    Paranjpe, A S

    2002-08-12

    A sequence of morphological transitions in two-dimensional dehydration patterns of aqueous solutions of ascorbic acid is observed with humidity as a control parameter. Change in morphology occurs due to humidity induced variation in the concentration of the metastable supersaturated solution phase formed after initial solvent evaporation. As percent humidity is varied from 40 to 80, patterns change from compact circular --> radial --> density modulated radial (a new morphology) --> density modulated circular --> density modulated dendritic (a new morphology) --> dense branching. PMID:12190528

  4. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  5. Air pollution, acid rain and the environment

    SciTech Connect

    Mellanby, K.

    1988-01-01

    This book reports on the Watt Committee's working group on acid rain, which was set up in 1981. The authors consider the relationship between natural and the man-made factors and the effects of possible remedial strategies. In the first phase of the study, the group looked at the fate of airborne pollution, vegetation and soils, freshwater and remedial strategy. In this report, which contains the results of a further phase of study, these topics are included and have been brought up to date. The scope of the report is extended to include buildings and non-living materials. Consideration is given to the problem of acid rain and air pollution worldwide. Emphasis is placed on the United Kingdom. The main conclusion is that more research is necessary on some aspects of acid rain and air pollution, but that some of the reports widespread damage caused by acid rain cannot be confirmed.

  6. Sulfate Mineral Formation from Acid-Weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2015-01-01

    Phyllosilicates on Mars are thought to have formed under neutral to alkaline conditions during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Gya). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Gya). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the geologic and aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era may have been weathered by the prevailing acidic conditions that characterize the Hesperian. Therefore, the purpose of this study is to characterize the alteration products resulting from acid-sulfate weathered phyllosilicates in laboratory experiments. This study focuses on two phyllosilicates commonly identified with sulfates on Mars: nontronite and saponite. We also compare our results to observations of phyllosilicates and sulfates on Mars to better understand the formation process of sulfates in close proximity to phyllosilicates on Mars and constrain the aqueous conditions of these regions on Mars.

  7. Insights Into the Aqueous History of Mars from Acid-Sulfate Weathered Phyllosilicates

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2016-01-01

    Phyllosilicates on Mars are thought to have formed during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Ga). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Ga). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era would have been weathered by the prevailing acidic conditions that define the Hesperian. Therefore, the purpose of this study is to characterize the alteration products of acid-sulfate weathered phyllosilicates in laboratory experiments, focusing on the Fe/Mg-smectites commonly identified on Mars. We also compare our results to observations of phyllosilicates and sulfates on Mars in regions such as Endeavour Crater and Mawrth Vallis to understand the formation process of sulfates and constrain the aqueous history of these regions.

  8. Compartmentalization of amino acids in surfactant aggregates - Partitioning between water and aqueous micellar sodium dodecanoate and between hexane and dodecylammonium propionate trapped water in hexane

    NASA Technical Reports Server (NTRS)

    Fendler, J. H.; Nome, F.; Nagyvary, J.

    1975-01-01

    The partitioning of amino acids (glycine, alanine, leucine, phenylalanine, histidine, aspartic acid, glutamic acid, lysine, isoleucine, threonine, serine, valine, proline, arginine) in aqueous and nonaqueous micellar systems was studied experimentally. Partitioning from neat hexane into dodecylammonium propionate trapped water in hexane was found to be dependent on both electrostatic and hydrophobic interactions, which implies that the interior of dodecylammonium propionate aggregates is negatively charged and is capable of hydrogen bonding in addition to providing a hydrophobic environment. Unitary free energies of transfer of amino acid side chains from hexane to water were determined and solubilities of amino acids in neat hexane substantiated the amino acid hydrophobicity scale. The relevance of the experiments to prebiotic chemistry was examined.

  9. Micellization properties of zwitterionic surfactants derived from nicotinic acid in aqueous solutions

    SciTech Connect

    Wiederkehr, N.A.; Kalyanasundaram, K.; Graetzel, M. ); Viscardi, G.; Savarino, P.; Barni, E. )

    1991-01-01

    Various properties of monomeric and micellar (aggregated) forms of a series of zwitterionic surfactants based on nicotinic acid (N-alkylnicotinic acids), R-NA (R = C{sub 8}, C{sub 10}, C{sub 12}, C{sub 14}, and C{sub 16}) have been determined in aqueous solution by utilization of a number of physical methods (visible light absorption, fluorescence probe analysis, surfactant tension measurements, and low-angle light scattering): protonation equilibria, extent of counterion adsorption, critical micellar temperature, critical micellar concentration, and micellar aggregation number.

  10. Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

    NASA Astrophysics Data System (ADS)

    Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

    2013-05-01

    The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

  11. Statistical Thermodynamic Model for Surface Tension of Aqueous Organic Acids with Consideration of Partial Dissociation.

    PubMed

    Boyer, Hallie C; Dutcher, Cari S

    2016-06-30

    With statistical mechanics, an isotherm-based surface tension model for single solute aqueous solutions was derived previously (Wexler et al. J. Phys. Chem. Lett. 2013) for the entire concentration range, from infinite dilution to pure liquid solute, as a function of solute activity. In recent work (Boyer et al. J. Phys. Chem. Lett. 2015), empirical model parameters were reduced through physicochemical interpretations of both electrolyte and organic solutes, enabling surface tension predictions for systems where there is little or no data. The prior binary model is extended in the current work for the first time to treat multicomponent systems to predict surface tensions of partially dissociating organic acids (acetic, butyric, citric, formic, glutaric, maleic, malic, malonic, oxalic, propionic, and succinic acids). These organic acids are especially applicable to the study of atmospheric aqueous aerosols, due to their abundance in the atmosphere. In the model developed here, surface tension depends explicitly on activities of both the neutral organic and deprotonated components of the acid. The relative concentrations of the nondissociated and dissociated mole fractions are found using known dissociation constants. Model parameters strongly depend on molecular size, number of functional groups, O:C ratio, and number of carbons. For all organic acids in this study, fully predictive modeling of surface tensions is demonstrated. PMID:27219322

  12. The Solubility of Xenon in Simple Organic Solvents and in Aqueous Amino Acid Solutions.

    NASA Astrophysics Data System (ADS)

    Himm, Jeffrey Frank

    We have measured the Ostwald solubility (L) of ('133)Xe in a variety of liquids, including normal alkanes, normal alkanols, and aqueous solutions of amino acids, NaCl, and sucrose. For the alkanes and alkanols, measurements were made in the temperature range from 10-50(DEGREES)C. Values of L were found to decrease with increasing temperature, and also with increasing chain length, for both series of solvents. Thermodynamic properties of solution (enthalpy and entropy of solution) are calculated using both mole fraction and number density scales. Results are interpreted using Uhlig's model of the solvation process. Measurements of L in aqueous amino acid solutions were made at 25(DEGREES)C. Concentrations of amino acids in solution varied from near saturation for each of the amino acids studied to pure water. In all solutions, except those with NaCl, L decreases linearly with increasing solution molarity. Hydration numbers (H), the mean number of water molecules associated with each solute molecule, were determined for each amino acid, for NaCl, and for sucrose. Values of H obtained ranged from near zero (arginine, H = 0.2 (+OR-) 0.5) to about 16 (NaCl, H = 16.25 (+OR-) 0.3).

  13. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  14. Radiolysis of aqueous solutions of acetic acid in the presence of Na-montmorillonite

    NASA Technical Reports Server (NTRS)

    Navarro-Gonzalez, R.; Negron-Mendoza, A.; Ramos, S.; Ponnamperuma, C.

    1990-01-01

    The gamma-irradiation of 0.8 mol dm-3 aqueous, oxygen-free acetic acid solutions was investigated in the presence or absence of Na-montmorillonite. H2, CH4, CO, CO2, and several polycarboxylic acids were formed in all systems. The primary characteristics observed in the latter system were: (1) Higher yield of the decomposition of acetic acid; (2) Lower yield of the formation of polycarboxylic acids; (3) No effect on the formation of methane; (4) Higher yield of the formation of carbon dioxide; and (5) The reduction of Fe3+ in the octahedral sites of Na-montmorillonite. A possible reaction scheme was proposed to account for the observed changes. The results are important in understanding heterogeneous processes in radiation catalysis and might be significant to prebiotic chemistry.

  15. Theoretical and computational studies of the interactions between small nanoparticles and with aqueous environments

    NASA Astrophysics Data System (ADS)

    Villarreal, Oscar D.

    Interactions between nanoparticles (metallic, biological or a hybrid mix of the two) in aqueous solutions can have multiple biological applications. In some of them their tendency towards aggregation can be desirable (e.g. self-assembly), while in others it may impact negatively on their reliability (e.g. drug delivery). A realistic model of these systems contains about a million or more degrees of freedom, but their study has become feasible with today's high performance computing. In particular, nanoparticles of a few nanometers in size interacting at sub-nanometer distances have become a novel area of research. The standard mean-field model of colloid science, the Derjaguin-Landau-Verwey-Overbeak (DLVO) theory, and even the extended version (XDLVO) have encountered multiple challenges when attempting to understand the interactions of small nanoparticles in the short range, since assumptions of continuous effects no longer apply. Because the region of the interaction is in the angstrom scale, the effects of atomic finite sizes and unique entropic interactions cannot be described through simple analytical formulae corresponding to generalized interaction potentials. In this work, all-atom molecular dynamics simulations have been performed on small nanoparticles in order to provide a theoretical background for their interactions with various liquid environments as well as with each other. Such interactions have been quantified and visualized as the processes occur. Potentials of mean force have been computed as functions of the separation distances in order to obtain the binding affinities. The atomistic details of how a nanoparticle interacts with its aqueous environments and with another nanoparticle have been understood for various ligands and aqueous solutions.

  16. Subcritical crack growth in glasses under cyclic loads: Effect of hydrodynamic pressure in aqueous environments

    SciTech Connect

    Yi, K.S.; Dill, S.J.; Dauskardt, R.H.

    1997-07-01

    The effect of hydrodynamic pressure developed in the wake of a crack growing in a brittle material under cyclic loads in an aqueous environment is considered. The pressure acts in opposition to the movement of the crack faces, thus shielding the crack up from the applied loads. A general hydrodynamic fluid pressure relation based on a one-dimensional Reynolds equation, which applicable to a crack with an arbitrary crack opening profile, is developed. The model is modified to account for side flow through the thickness of the sample and cavitation near the crack tip. Both effects significantly modify the hydrodynamic pressure distribution. Finally, the resulting hydrodynamic pressure relations are combined with a fracture mechanics model to account for the change in the near-tip stress intensity. Resulting predictions of the cyclic crack-growth rate are found to be in good agreement with measured values for a borosilicate glass tested at various frequencies in a water environment.

  17. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    NASA Astrophysics Data System (ADS)

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-01

    In this paper, we obtain the energy band positions of amorphous carbon (a-C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H2/H2O and O2/H2O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp2 sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  18. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    SciTech Connect

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-21

    In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H{sub 2}/H{sub 2}O and O{sub 2}/H{sub 2}O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp{sup 2} sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  19. Photo-transformation of pharmaceutically active compounds in the aqueous environment: a review.

    PubMed

    Yan, Shuwen; Song, Weihua

    2014-04-01

    In the past few years, the fate and transportation of pharmaceutically active compounds (PhACs) in aqueous environments have raised significant concerns among the public, scientists and regulatory groups. Photodegradation is an important removal process in surface waters. This review summarizes the last 10 years (2003-2013) of studies on the solar or solar-simulated photodegradation of PhACs in aqueous environments. The PhACs covered include: beta-blockers, antibiotics, non-steroidal anti-inflammatory drugs (NSAIDs), histamine H₂-receptor antagonists, lipid regulators, carbamazepine, steroid hormones, and X-ray contrast media compounds. Kinetic studies, degradation mechanisms and toxicity removal are the three major topics involved in this review. The quantum yield for the direct photolysis of PhACs and the bimolecular reaction rate constants of PhACs with reactive oxygen species (ROS), such as the ˙OH radical and singlet oxygen, are also summarized. This information is not only important to predict the PhAC photodegradation fate, but also is very useful for advanced treatment technologies, such as ozone or advanced oxidation processes. PMID:24608883

  20. [Studies on carbonization of saccharides by using aqueous solution of various acids].

    PubMed

    Zhang, Xin; He, An-Qi; Kang, Ting-Guo; Xia, Jin-Ming; Weng, Shi-Fu; Xu, Yi-Zhuang; Wu, Jin-Guang

    2014-09-01

    The authors tried to establish an approach to use acids to convert biomass into a fuel with higher carbon content and lower oxygen content in a zero-energy-consumption fashion. Considering that biomass is composed of monosaccharide, we used aqueous solutions of variation acids including hydrochloric acid, sulfuric acid and perchloric acid to treat 2-deoxy-ribose and fructose at ambient temperature and pressure. Black substances were produced after a period of time when 2-deoxy-ribose and fructose were mixed with aqueous solutions containing 8 mol · L(-1) acids. The black substance was collected and characterized by using elemental analysis, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Elemental analysis results indicate that the contents of carbon increases significantly in the black substances in comparison with 2-deoxy-ribose and fructose. Moreover, XPS results indicate that the content of oxygen in the black substance undergoes a significant decrease compared with pure 2-deoxy-ribose and fructose. In the XPS spectra, the is peaks of 2-deoxy-ribose, strong sub peak at 286. 05 eV, which is assigned to carbon linked to oxygen directly, dominate in the C is peak envelop. After treatment by HClO4, the peak decreased dramatically. This result also supports the conclusion that the content of oxygen in mono-saccharide is significantly reduced after treatment by acids. In the FTIR spectra of the black substances, strong peaks can be observed around 1 600 cm(-1), indicating that C==C bond is formed in the product. The above results suggest that treatments with acids may be developed as a new zero-energy-consumption approach to convert biomass in a new fuel with improved energy output efficiency. PMID:25532323

  1. INFLUENCE OF AQUEOUS ALUMINUM AND ORGANIC ACIDS ON MEASUREMENT OF ACID NEUTRALIZING CAPACITY IN SURFACE WATERS

    EPA Science Inventory

    Acid neutralizing capacity (ANC) is used to quantify the acid-base status of surface waters. Acidic waters have bean defined as having ANC values less than zero, and acidification is often quantified by decreases in ANC. Measured and calculated values of ANC generally agree, exce...

  2. Interaction of Atmospheric-Pressure Air Microplasmas with Amino Acids as Fundamental Processes in Aqueous Solution

    PubMed Central

    Zhou, Renwu; Zhou, Rusen; Zhuang, Jinxing; Zong, Zichao; Zhang, Xianhui; Liu, Dongping; Bazaka, Kateryna; Ostrikov, Kostya

    2016-01-01

    Plasma medicine is a relatively new field that investigates potential applications of cold atmospheric-pressure plasmas in bioengineering, such as for bacterial inactivation and degradation of organic molecules in water. In order to enunciate mechanisms of bacterial inactivation at molecular or atomic levels, we investigated the interaction of atmospheric-pressure air microplasmas with amino acids in aqueous solution by using high-resolution mass spectrometry (HRMS). Results show that the oxidation effect of plasma-induced species on the side chains of the amino acids can be categorized into four types, namely hydroxylation, nitration, dehydrogenation and dimerization. In addition, relative activities of amino acids resulting from plasma treatment come in descending order as follows: sulfur-containing carbon-chain amino acids > aromatic amino acids > five-membered ring amino acids > basic carbon-chain amino acids. Since amino acids are building blocks of proteins vital to the growth and reproduction of bacteria, these results provide an insight into the mechanism of bacterial inactivation by plasma. PMID:27183129

  3. Interaction of Atmospheric-Pressure Air Microplasmas with Amino Acids as Fundamental Processes in Aqueous Solution.

    PubMed

    Zhou, Renwu; Zhou, Rusen; Zhuang, Jinxing; Zong, Zichao; Zhang, Xianhui; Liu, Dongping; Bazaka, Kateryna; Ostrikov, Kostya

    2016-01-01

    Plasma medicine is a relatively new field that investigates potential applications of cold atmospheric-pressure plasmas in bioengineering, such as for bacterial inactivation and degradation of organic molecules in water. In order to enunciate mechanisms of bacterial inactivation at molecular or atomic levels, we investigated the interaction of atmospheric-pressure air microplasmas with amino acids in aqueous solution by using high-resolution mass spectrometry (HRMS). Results show that the oxidation effect of plasma-induced species on the side chains of the amino acids can be categorized into four types, namely hydroxylation, nitration, dehydrogenation and dimerization. In addition, relative activities of amino acids resulting from plasma treatment come in descending order as follows: sulfur-containing carbon-chain amino acids > aromatic amino acids > five-membered ring amino acids > basic carbon-chain amino acids. Since amino acids are building blocks of proteins vital to the growth and reproduction of bacteria, these results provide an insight into the mechanism of bacterial inactivation by plasma. PMID:27183129

  4. Radiation-induced degradation of cyclohexanebutyric acid in aqueous solutions by gamma ray irradiation

    NASA Astrophysics Data System (ADS)

    Jia, Wenbao; He, Yanquan; Ling, Yongsheng; Hei, Daqian; Shan, Qing; Zhang, Yan; Li, Jiatong

    2015-04-01

    The radiation-induced degradation of cyclohexanebutyric acid under gamma ray irradiation was investigated. Degradation experiments were performed with 100 mL sealed Pyrex glass vessels loaded with 80 mL of cyclohexanebutyric acid solutions at various initial concentrations of 10, 20, and 40 mg L-1. The absorbed doses were controlled at 0, 0.65, 1.95, 3.25, 6.5, 9.75, and 13 kGy. The results showed that gamma ray irradiation could effectively degrade cyclohexanebutyric acid in aqueous solutions. The removal rate of cyclohexanebutyric acid increased significantly with the increase of absorbed dose and the decrease of its initial concentration. At the same time, the removal of chemical oxygen demand (COD) was as effective as that of cyclohexanebutyric acid. The kinetic studies showed that the degradation of cyclohexanebutyric acid followed pseudo first-order reaction. Above all, the proposed mechanism obtained when NaNO2, NaNO3 and tert-butanol were added showed that the •OH radical played a major role in the gamma degradation process of cyclohexanebutyric acid, while •H and eaq- played a minor role in the gamma degradation process. The degradation products were identified by Fourier transform infrared spectroscopy (FTIR) and gas chromatography/mass spectrometry (GC/MS) during cyclohexanebutyric acid degradation.

  5. Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

    SciTech Connect

    de Almeida, Valmor F; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

    2010-01-01

    Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

  6. The infrared optical constants of sulfuric acid at 250 K. [spectral reflectance measurement of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Williams, D.

    1976-01-01

    Results are presented for measurements of the IR spectral reflectance at near-normal incidence of aqueous solutions of sulfuric acid with acid concentrations of 75% and 95.6% by weight. Kramers-Kronig analyses of the reflectance data are employed to obtain values of the optical constants n(nu) and k(nu) in the spectral range from 400 to 6000 cm to the -1 power. The optical constants of these solutions at 250 K and 300 K are compared. It is found that in spectral regions remote from strong absorption bands, the values of the n(nu) indices obtained at 250 K agree with the values given by Lorentz-Lorenz correction of the same indices at 300 K. All absorption bands observed at 300 K are found to be present at 250 K with slight shifts in frequency and with significant differences in the k(nu) indices at the band maxima. Based on these results, it is concluded that the clouds of Venus probably consist of droplets of aqueous solutions of sulfuric acid with acid concentrations of about 75% by weight.

  7. Sorption of basic and acid dyes from aqueous solutions onto oxihumolite.

    PubMed

    Janos, Pavel; Sedivý, Pavel; Rýznarová, Milena; Grötschelová, Sylvie

    2005-05-01

    Naturally occurring kind of weathered and oxidised young brown coal called oxihumolite was used for an adsorptive removal of basic (Methylene Blue, Malachite Green) as well as acid (Egacid Orange, Midlon Black) dyes from waters. It was shown that both kinds of dyes can be sorbed onto oxihumolite. The maximum sorption capacities determined from the parameters of Langmuir isotherms ranged from 0.070 mmol g-1 (for Midlon Black) to 0.278 mmol g-1 (for Malachite Green) and did not differ significantly for basic and acid dyes. The dye sorption (except of Midlon Black) increased in the presence of inorganic salt. Non-ionic surfactants, and surfactants bearing the same charge as the dye exhibited only a minor effect on the dye sorption, whereas oppositely charged surfactants enhanced the dye sorption to a certain extent. The pH value of the aqueous phase exhibited rather pronounced effect on the sorption of acid dyes causing a suppression of the sorption with increasing pH. The sorption of basic dyes, on the other hand, remained almost unchanged in the examined pH range. Oxihumolite is recommended for the treatment of acid wastewaters because of its limited stability in alkaline aqueous solutions. PMID:15811417

  8. Zeolite-type metal organic frameworks immobilized Eu³⁺ for cation sensing in aqueous environment.

    PubMed

    Liu, Chang; Yan, Bing

    2015-12-01

    A novel luminescent lanthanide metal organic framework (Ln-MOF) is synthesized by in situ encapsulating Eu(3+) ions to partial replace the transition-metal clusters in the channels of CPM-17-Zn nanocrystals. The Eu(3+) functionalized zeolite-type MOF hybrid system shows excellent luminescence property and photo-stability in aqueous environment for the sensitization and protection from the host framework. Subsequently, as a highly selective and sensitive sensor, its nanocrystals can be used to detect Cd(2+) in aqueous solution. In addition, the possible sensing mechanism based on ion exchange is discussed in detail. This work is one of the few cases for detecting Cd(2+) in aqueous solution based on a zeolite-type MOF. The good fluorescence stability, low detection limit and broad linear range in aqueous environment make this probe to be expected to have potential application in intracellular sensing and imaging of Cd(2+) potentially. PMID:26298079

  9. The Formation and Aggregation of Iron Oxyhydroxide Nanoparticles in the Aqueous Environment

    NASA Astrophysics Data System (ADS)

    Legg, Benjamin Adam

    This dissertation consists of four studies, which seek explain how iron oxyhydroxide nanoparticles nucleate and develop new structures via aggregation, within the aqueous environment. The aim of the first study is to determine the structure of ferrihydrite nanoparticle aggregates in aqua. This is achieved using complimentary cryo-TEM and SAXS methodologies. Ferrihydrite nanoparticles are known to form complex aggregate structures. Interpretation of SAXS data is difficult due to suspension polydispersity. Cryo-ET is used to obtain three-dimensional images of the nanoparticle suspensions. A variety of aggregate structures are observed, with branched networks of linear chains of particles being prevalent in most suspensions. The tomographic structural models are processed to determine aggregate fractal dimensions, using an autocorrelation function based approach. These results are combined with SAXS data to obtain a more comprehensive understanding of the suspension complexity. The networks of linear chains are shown to possess low fractal dimensions, between 1.0 and 1.4; significantly lower than would be expected from traditional models for aggregation. This has important consequences for the aggregate's physical behavior, and allows very large aggregates to exist in stable colloidal suspension without flocculation. The second study addresses how the ferrihydrite aggregate structure responds to changes in the ionic strength of the suspension, and how low-dimensional aggregate structures may influence nanoparticle transport through subsurface environments. Introducing ferrihydrite particle aggregates into solutions of 2 mM to 50 mM NaNO3 is shown to induce aggregate collapse, with more salt leading to the formation of denser aggregate structures and eventual flocculation. Complementary experiments show that millimolar quantities of NaNO3 induce a fundamental change in nanoparticle transport through a saturated quartz sand column. In deionized water, where low fractal

  10. Yeast fermentation of carboxylic acids obtained from pyrolytic aqueous phases for lipid production.

    PubMed

    Lian, Jieni; Garcia-Perez, Manuel; Coates, Ralph; Wu, Hongwei; Chen, Shulin

    2012-08-01

    The presence of very reactive C1-C4 molecules adversely affects the quality bio-oils produced from the pyrolysis of lignocellulosic materials. In this paper a scheme to produce lipids with Cryptococcus curvatus from the carboxylic acids in the pyrolytic aqueous phase collected in fractional condensers is proposed. The capacities of three oleaginous yeasts C. curvatus, Rhodotorula glutinis, Lipomyces starkeyi to ferment acetate, formate, hydroxylacat-aldehyde, phenol and acetol were investigated. While acetate could be a good carbon source for lipid production, formate provides additional energy and contributes to yeast growth and lipid production as auxiliary energy resource. Acetol could slightly support yeast growth, but it inhibits lipid accumulation. Hydroxyacetaldehyde and phenols showed high yeast growth and lipid accumulation inhibition. A pyrolytic aqueous phase with 20 g/L acetate was fermented with C. curvatus, after neutralization and detoxification to produce 6.9 g/L dry biomass and 2.2 g/L lipid. PMID:22705522

  11. Changing interfaces: Photoluminescent ZnO nanoparticle powders in different aqueous environments

    NASA Astrophysics Data System (ADS)

    Kocsis, Krisztina; Niedermaier, Matthias; Bernardi, Johannes; Berger, Thomas; Diwald, Oliver

    2016-10-01

    We transformed vapor phase grown ZnO nanoparticle powders into aqueous ZnO nanoparticle dispersions and studied the impact of associated microstructure and interface property changes on their spectroscopic properties. With photoluminescence (PL) spectroscopy, we probed oxygen interstitials Oi2 - in the near surface region and tracked their specific PL emission response at hvEM = 2.1 eV during the controlled conversion of the solid-vacuum into the solid-liquid interface. While oxygen adsorption via the gas phase does affect the intensity of the PL emission bands, the O2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hvEM = 3.2 eV gains relative intensity with regard to the PL emission features in the visible light region. Searching for potential PL indicators that are specific to early stages of particle dissolution, we addressed for aqueous ZnO nanoparticle dispersions the effect of formic acid adsorption. In the absence of related spectroscopic features, we were able to consistently track ZnO nanoparticle dissolution and the concomitant formation of solvated Zinc formate species by means of PL and FT-IR spectroscopy, dynamic light scattering, and zeta potential measurements. For a more consistent and robust assessment of nanoparticle properties in different continuous phases, we discuss characterization challenges and potential pitfalls that arise upon replacing the solid-gas with the solid-liquid interface.

  12. Experimental Shock Chemistry of Aqueous Amino Acid Solutions and the Cometary Delivery of Prebiotic Compounds

    NASA Astrophysics Data System (ADS)

    Blank, Jennifer G.; Miller, Gregory H.; Ahrens, Michael J.; Winans, Randall E.

    2001-02-01

    A series of shock experiments were conducted to assess the feasibility of the delivery of organic compounds to the Earth via cometary impacts. Aqueous solutions containing near-saturation levels of amino acids (lysine, norvaline, aminobutyric acid, proline, and phenylalanine) were sealed inside stainless steel capsules and shocked by ballistic impact with a steel projectile plate accelerated along a 12-m-long gun barrel to velocities of 0.5-1.9 km sec^-1. Pressure-temperature-time histories of the shocked fluids were calculated using 1D hydrodynamical simulations. Maximum conditions experienced by the solutions lasted 0.85-2.7 μs and ranged from 5.1-21 GPa and 412-870 K. Recovered sample capsules were milled open and liquid was extracted. Samples were analyzed using high performance liquid chromatography (HPLC) and mass spectrometry (MS). In all experiments, a large fraction of the amino acids survived. We observed differences in kinetic behavior and the degree of survivability among the amino acids. Aminobutyric acid appeared to be the least reactive, and phenylalanine appeared to be the most reactive of the amino acids. The impact process resulted in the formation of peptide bonds; new compounds included amino acid dimers and cyclic diketopiperazines. In our experiments, and in certain naturally occurring impacts, pressure has a greater influence than temperature in determining reaction pathways. Our results support the hypothesis that significant concentrations of organic material could survive a natural impact process.

  13. Experimental shock chemistry of aqueous amino acid solutions and the cometary delivery of prebiotic compounds.

    PubMed

    Blank, J G; Miller, G H; Ahrens, M J; Winans, R E

    2001-01-01

    A series of shock experiments were conducted to assess the feasibility of the delivery of organic compounds to the Earth via cometary impacts. Aqueous solutions containing near-saturation levels of amino acids (lysine, norvaline, aminobutyric acid, proline, and phenylalanine) were sealed inside stainless steel capsules and shocked by ballistic impact with a steel projectile plate accelerated along a 12-m-long gun barrel to velocities of 0.5-1.9 km sec-1. Pressure-temperature-time histories of the shocked fluids were calculated using 1D hydrodynamical simulations. Maximum conditions experienced by the solutions lasted 0.85-2.7 microseconds and ranged from 5.1-21 GPa and 412-870 K. Recovered sample capsules were milled open and liquid was extracted. Samples were analyzed using high performance liquid chromatography (HPLC) and mass spectrometry (MS). In all experiments, a large fraction of the amino acids survived. We observed differences in kinetic behavior and the degree of survivability among the amino acids. Aminobutyric acid appeared to be the least reactive, and phenylalanine appeared to be the most reactive of the amino acids. The impact process resulted in the formation of peptide bonds; new compounds included amino acid dimers and cyclic diketopiperazines. In our experiments, and in certain naturally occurring impacts, pressure has a greater influence than temperature in determining reaction pathways. Our results support the hypothesis that significant concentrations of organic material could survive a natural impact process. PMID:11296518

  14. Thermosensitivity of bile acid-based oligo(ethylene glycol) stars in aqueous solutions.

    PubMed

    Strandman, Satu; Le Dévédec, Frantz; Zhu, X X

    2011-08-01

    Amphiphilic star-shaped oligo(ethylene glycol)s with a hydrophobic bile acid core and varying number of hydrophilic arms have been made. Their thermal behavior in aqueous solutions depends on the number rather than the length of the arms. The two-armed lithocholate derivative showed the strongest tendency for association and exhibited the lowest cloud point (79 °C) of the oligomers made, as well as another phase separation at a lower temperature (31 °C). The "double thermosensitivity" arising both from the salt-dependent LCST of the oligo(ethylene glycol) segments and the temperature-responsive self-assembly of amphiphilic bile acid derivative provides an interesting path in the design of bile acid-based smart materials. PMID:21661073

  15. Solid supported in situ derivatization extraction of acidic degradation products of nerve agents from aqueous samples.

    PubMed

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

    2014-09-12

    This study deals with the solid supported in situ derivatization extraction of acidic degradation products of nerve agents present in aqueous samples. Target analytes were alkyl alkylphosphonic acids and alkylphosphonic acids, which are important environmental signatures of nerve agents. The method involved tert-butyldimethylchlorosilane mediated in situ silylation of analytes on commercially available diatomaceous solid phase extraction cartridges. Various parameters such as derivatizing reagent, its concentration, reaction time, temperature and eluting solvent were optimized. Recoveries of the analytes were determined by GC-MS which ranged from 60% to 86%. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes were achieved down to 78 and 213ngmL(-1) respectively, in selected ion monitoring mode. The successful applicability of method was also demonstrated on samples of biological origin such as plasma and to the samples received in 34th official proficiency test conducted by the Organization for Prohibition the of Chemical Weapons. PMID:25103280

  16. Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

  17. Corrosion studies in fuel element reprocessing environments containing nitric acid

    SciTech Connect

    Beavers, J A; White, R R; Berry, W E; Griess, J C

    1982-04-01

    Nitric acid is universally used in aqueous fuel element reprocessing plants; however, in the processing scheme being developed by the Consolidated Fuel Reprocessing Program, some of the equipment will be exposed to nitric acid under conditions not previously encountered in fuel element reprocessing plants. A previous report presented corrosion data obtained in hyperazeotropic nitric acid and in concentrated magnesium nitrate solutions used in its preparation. The results presented in this report are concerned with the following: (1) corrosion of titanium in nitric acid; (2) corrosion of nickel-base alloys in a nitric acid-hydrofluoric acid solution; (3) the formation of Cr(VI), which enhances corrosion, in nitric acid solutions; and (4) corrosion of mechanical pipe connectors in nitric acid. The results show that the corrosion rate of titanium increased with the refreshment rate of boiling nitric acid, but the effect diminished rapidly as the temperature decreased. The addition of iodic acid inhibited attack. Also, up to 200 ppM of fluoride in 70% HNO/sub 3/ had no major effect on the corrosion of either titanium or tantalum. In boiling 8 M HNO/sub 3/-0.05 M HF, Inconel 671 was more resistant than Inconel 690, but both alloys experienced end-grain attack. In the case of Inconel 671, heat treatment was very important; annealed and quenched material was much more resistant than furnace-cooled material.The rate of oxidation of Cr(III) to Cr(VI) increased significantly as the nitric acid concentration increased, and certain forms of ruthenium in the solution seemed to accelerate the rate of formation. Mechanical connectors of T-304L stainless steel experienced end-grain attack on the exposed pipe ends, and seal rings of both stainless steel and a titanium alloy (6% Al-4% V) underwent heavy attack in boiling 8 M HNO/sub 3/.

  18. Fabrication of ZnO:Mn nanoparticles with organic shell in a highly alkaline aqueous environment

    NASA Astrophysics Data System (ADS)

    Chawla, Santa; Sharda; Jayanthi, K.

    2011-01-01

    Synthesis of undoped and Mn doped ZnO nanoparticles by an inclusive co precipitation method and in situ capping with heteromultifunctional organic stabilizer mercaptosuccinic acid (MSA) in a core shell structure, in highly alkaline aqueous matrix have been accomplished. Near room temperature synthesis resulted in high quality monophasic wurtzite hexagonal structure of rod shaped nanoparticles of bare ZnO:Mn with no signature of dopant as separate phase. MSA capping resulted in nanoball like formation. Thermo gravimetric analysis (TGA) and FTIR confirmed MSA capping. ZnO: Mn particles emit in orange and red when excited by UV and blue light. Surface modification makes the nanoparticles hydrophilic with active organic surface easy for bioconjugation with any ligand and can have applications in drug delivery or as nanoscale fluorescent probe in a biological system.

  19. Studies on the adsorption of americium on alumina from aqueous nitric acid-oxalic acid solutions

    SciTech Connect

    Subba Rao, M.; Gaikwad, A.M.; Rao, V.K.; Natarajan, P.R.

    1985-01-01

    This paper reports a study on the adsorption of Am(III) on alumina from oxalic acid-nitric acid solutions. Distribution coefficients for Am(III) on alumina at different oxalic acid-nitric acid concentrations have been determined and optimum conditions for loading and elution of Am from alumina columns have been established. Separation of Am from Pu and the effects of other ions, such as U(VI) and Fe(III), have also been studied. Am and Pu recoveries better than 99.5% were obtained. 3 references, 2 figures, 5 tables.

  20. Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens.

    PubMed

    Drabowicz, Józef; Jordan, Frank; Kudzin, Marcin H; Kudzin, Zbigniew H; Stevens, Christian V; Urbaniak, Paweł

    2016-02-01

    The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by (31)P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine. PMID:26631424

  1. Vine-shoot waste aqueous extract applied as foliar fertilizer to grapevines: Effect on amino acids and fermentative volatile content.

    PubMed

    Sánchez-Gómez, R; Garde-Cerdán, T; Zalacain, A; Garcia, R; Cabrita, M J; Salinas, M R

    2016-04-15

    The aim of this work was to study the influence of foliar applications of different wood aqueous extracts on the amino acid content of musts and wines from Airén variety; and to study their relationship with the volatile compounds formed during alcoholic fermentation. For this purpose, the foliar treatments proposed were a vine-shoot aqueous extract applied in one and two times, and an oak extract which was only applied once. Results obtained show the potential of Airén vine-shoot waste aqueous extracts to be used as foliar fertilizer, enhancing the wine amino acid content especially when they were applied once. Similar results were observed with the aqueous oak extract. Regarding wine fermentative volatile compounds, there is a close relationship between musts and their wines amino acid content allowing us to discuss about the role of proline during the alcoholic fermentation and the generation of certain volatiles. PMID:26616933

  2. ''Pulling'' Nanoparticles into Water: Phase Transfer of Oleic Acid Stabilized Monodisperse Nanoparticles into Aqueous Solutions of alpha-Cyclodextrin

    SciTech Connect

    Wang, Y.; Wong, J.F.; Teng, X.; Lin, X.Z.; Yang, H.

    2003-10-18

    (B204)This paper describes a general method to drastically improve the disparity of oleic acid stabilized nanoparticles in aqueous solutions. We use oleic acid stabilized monodisperse nanoparticles of iron oxides and silver as model systems, and have modified the surface properties of these nanoparticles through the formation of an inclusion complex between surface-bound surfactant molecules and alpha-cyclodextrin (alpha-CD). After the modification, the nanoparticles of both iron oxide and Ag can transfer from hydrophobic solvents, such as hexane, to alpha-CD aqueous phase. The efficiency of the phase transfer to the aqueous solutions depend son the initial alpha-CD concentration. The alpha-CD/oleic acid complex stabilized nanoparticles can be stable for long periods of time in aqueous phase under ambient atmospheric conditions. Transmission electron microscopy (TME), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, and colorimetric methods have been used in the characterization of these nanoparticles.

  3. Isolation and separation of transplutonium elements from other actinides on ion exchange resins from aqueous and aqueous ethanol solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1987-11-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on an anion exchange resin and a cation exchange resin in aqueous and aqueous alcohol solutions of sulfuric acid was investigated as a function of the concentration of various components of the solution. It was found that the presence of alcohol in sulfuric acid solutions leads to an increase in the distribution coefficients both on cation exchange resins and on anion exchange resins. The possibility of using ion exchange resins for the concentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements that form strong complexes with sulfate ions in a wide range of sulfuric acid concentrations was demonstrated.

  4. Sulfate Mineral Formation from Acid-weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Astrophysics Data System (ADS)

    Craig, Patricia; Ming, Douglas; Rampe, Elizabeth

    2014-11-01

    Phyllosilicates on Mars are common in Noachian terrains whereas sulfates are found in the younger Hesperian terrains and suggest alteration under more acidic conditions. Phyllosilicates that formed during the Noachian era would have been exposed to the prevailing acidic conditions during the Hesperian. The purpose of this project is to characterize the effects of acid-weathering on phyllosilicates to better understand the aqueous history of Mars. Nontronite, montmorillonite, and saponite were exposed to H2SO4 solutions at water-rock (WR) ratios of 50 and 25.X-ray diffraction (XRD) patterns of all three acid-treated minerals showed progressive collapse of the phyllosilicate basal spacing with increasing acid concentration. Bassanite formed as an intermediate phase in weathered nontronite and montmorillonite from extracted interlayer Ca. The octahedral cation determined which sulfate formed at high acid concentration: rhomboclase from nontronite, alunogen from montmorillonite, hexahydrite and kieserite from saponite. Gypsum and anhydrite also formed as intermediate phases in nontronite treated at WR=25, showing a change in sulfate hydration state with changing acid concentration (i.e. water activity). Scanning electron microscopy analyses detected phases not identified by XRD. Al-sulfate was found in nontronite weathered at WR=25 and Ca-sulfate in weathered saponite. Near-infrared reflectance spectra of the weathered samples showed decreasing intensity of the hydration/hydroxylation bands and a change or disappearance of metal-OH bands indicating dehydration and dissociation of the interlayers and octahedral layers, respectively, with increased acid weathering.Sulfate mineral formation from acid-weathered phyllosilicates may explain the presence of phyllosilicates and sulfates in close proximity to each other on Mars, such as in Gale Crater. The CheMin XRD instrument on Curiosity may find evidence for acid-weathered phyllosilicates in Mt. Sharp by comparing the 001

  5. Aqueous extracts of Mozambican plants as alternative and environmentally safe acid-base indicators.

    PubMed

    Macuvele, Domingos Lusitaneo Pier; Sithole, Gerre Zebedias Samo; Cesca, Karina; Macuvele, Suzana Lília Pinare; Matsinhe, Jonas Valente

    2016-06-01

    Indicators are substances that change color as the pH of the medium. Many of these substances are dyes of synthetic origin. The mulala plant (Euclea natalensis), which roots are commonly used by rural communities for their oral hygiene, and roseira (Hibiscus rosa-sinensis), an ornamental plant, are abundant in Mozambique. Currently, synthetic acid-base indicators are most commonly used but have environmental implications and, on the other hand, are expensive products, so the demand for natural indicators started. This study investigated the applicability of aqueous extracts of H. rosa-sinensis and E. natalensis as acid-base indicators. Ground on this work, the extracts can be used as acid-base indicators. On the basis of the absorption spectroscopy in both the UV-Vis region and previous studies, it was possible to preliminarily pinpoint anthocyanins and naphthoquinones as responsible for the shifting of colors depending on the pH range of aqueous extracts of H. rosa-sinensis and E. natalensis. These natural indicators are easily accessible, inexpensive, easy to extract, environmentally safe, and locally available. PMID:26936478

  6. Inhibition of gastric acid secretion by the aqueous extract and purified extracts of Stachytarpheta cayennensis.

    PubMed

    Vela, S M; Souccar, C; Lima-Landman, M T; Lapa, A J

    1997-02-01

    Stachytarpheta cayennensis Schauer (Verbenaceae) is used in folk medicine to treat gastric and intestinal disturbances. The freeze-dried aqueous extract of the whole plant tested to rodents up to the dose of 2 g kg-1, p.o., did not produce signs of toxicity. The extract (0.5-2 g kg-1, p.o.) increased the intestinal motility and protected mice against ulcers induced by restraintin-cold, ethanol or indomethacin. Injected into the duodenal lumen the extract inhibited the basal acid secretion as well as that induced by histamine and bethanecol in pylorus-ligated mice. Partition of the aqueous extract in organic solvents yielded semipurified fractions whose antiacid activity guided further chemical purification. All the fractions were chromatographically characterized, the main substances in the active extract being flavonoids and amines; some substances were revealed only under UV light. The most purified active fraction obtained presented a specific activity 5-10 times higher than that detected in the original extract. Data from pharmacological studies indicate that the antiulcer activity of S. cayennensis is related to a specific inhibition of gastric acid secretion. Cholinergic and histaminergic stimulation of acid secretion were similarly reduced by the extracts suggesting inhibition of common steps in both pathways, possibly at the level of histamine release/H2 receptor interaction, or at the proton pump. Whatever the mechanisms involved, the present data confirm the plant effectiveness as antiacid/antiulcer and laxative. PMID:9063095

  7. Thermodynamics of aqueous sodium sulfate from the temperatures 273 K to 373 K and mixtures of aqueous sodium sulfate and sulfuric acid at 298. 15 K

    SciTech Connect

    Hovey, J.K.; Pitzer, K.S. ); Rard, J.A. )

    1991-07-01

    New isopiestic vapor-pressure measurements on the aqueous system {l brace}(1{minus}y)H{sub 2}SO{sub 4}+yNA{sub 2}SO{sub 4}{r brace} along with earlier experimental investigations that span the range from y=0 to y=1 and infinitely dilute to supersaturated molalities have been analyzed in terms of the Pitzer ion-interaction model. Refined ion-interaction parameters for aqueous sodium sulfate valid over the temperature range 273 K to 373 K have been calculated and used for analyzing results for mixtures containing sulfuric acid and sodium sulfate at 298.15 K. Analysis of experimental results for these aqueous mixtures required explicit consideration of the dissociation reaction of bisulfate ion. Previous treatments of aqueous sulfuric acid and subsequently the bisulfate dissociation equilibrium valid in the range 273 K to 343 K were employed as a first approximation in representing the mixed solutions. Two sets of Pitzer ion-interaction parameters are presented for (sodium sulfate + sulfuric acid). The validity of the first set is limited in ionic strength and molality to saturated solutions of pure aqueous sodium sulfate (4 mol{center dot}kg{sup {minus}1}). The second set of parameters corresponds to a slightly less precise representation but is valid over the entire range of experimental results considered. Both sets of parameters provide a more complete description of pure sulfuric acid solutions because of the removal of various redundancies of ion-interaction parameters. The specific ion-interaction terms used and the overall fitting procedure are described as well as selected examples of relevant thermodynamic calculations in the mixed system Na{sub 2}SO{sub 4}-H{sub 2}SO{sub 4}-H{sub 2}O. 33 refs., 6 figs., 5 tabs.

  8. Thermodynamics of aqueous sodium sulfate from the temperatures 273 K to 373 K and mixtures of aqueous sodium sulfate and sulfuric acid at 298.15 K

    SciTech Connect

    Hovey, J.K.; Pitzer, K.S.; Rard, J.A.

    1991-07-01

    New isopiestic vapor-pressure measurements on the aqueous system {l_brace}(1{minus}y)H{sub 2}SO{sub 4}+yNA{sub 2}SO{sub 4}{r_brace} along with earlier experimental investigations that span the range from y=0 to y=1 and infinitely dilute to supersaturated molalities have been analyzed in terms of the Pitzer ion-interaction model. Refined ion-interaction parameters for aqueous sodium sulfate valid over the temperature range 273 K to 373 K have been calculated and used for analyzing results for mixtures containing sulfuric acid and sodium sulfate at 298.15 K. Analysis of experimental results for these aqueous mixtures required explicit consideration of the dissociation reaction of bisulfate ion. Previous treatments of aqueous sulfuric acid and subsequently the bisulfate dissociation equilibrium valid in the range 273 K to 343 K were employed as a first approximation in representing the mixed solutions. Two sets of Pitzer ion-interaction parameters are presented for (sodium sulfate + sulfuric acid). The validity of the first set is limited in ionic strength and molality to saturated solutions of pure aqueous sodium sulfate (4 mol{center_dot}kg{sup {minus}1}). The second set of parameters corresponds to a slightly less precise representation but is valid over the entire range of experimental results considered. Both sets of parameters provide a more complete description of pure sulfuric acid solutions because of the removal of various redundancies of ion-interaction parameters. The specific ion-interaction terms used and the overall fitting procedure are described as well as selected examples of relevant thermodynamic calculations in the mixed system Na{sub 2}SO{sub 4}-H{sub 2}SO{sub 4}-H{sub 2}O. 33 refs., 6 figs., 5 tabs.

  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. 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

  11. Stress Corrosion Cracking Behavior of Alloy 22 in Multi-Ionic Aqueous Environments

    SciTech Connect

    K.J. King; J.C. Estill; R.B. Rebak

    2002-07-15

    The US Department of Energy is characterizing a potential repository site for nuclear waste in Yucca Mountain (NV). In its current design, the nuclear waste containers consist of a double metallic layer. The external layer would be made of NO6022 or Alloy 22 (Ni-22Cr-13Mo-3W-3Fe). Since over their lifetime, the containers may be exposed to multi-ionic aqueous environments, a potential degradation mode of the outer layer could be environmentally assisted cracking (EAC) or stress corrosion cracking (SCC). In general, Alloy 22 is extremely resistant to SCC, especially in concentrated chloride solutions. Current results obtained through slow strain rate testing (SSRT) shows that Alloy 22 may suffer SCC in simulated concentrated water (SCW) at applied potentials approximately 400 mV more anodic than the corrosion potential (E{sub rr}).

  12. Optimization of liquid scintillation measurements applied to smears and aqueous samples collected in industrial environments

    NASA Astrophysics Data System (ADS)

    Chapon, Arnaud; Pigrée, Gilbert; Putmans, Valérie; Rogel, Gwendal

    Search for low-energy β contaminations in industrial environments requires using Liquid Scintillation Counting. This indirect measurement method supposes a fine control from sampling to measurement itself. Thus, in this paper, we focus on the definition of a measurement method, as generic as possible, for both smears and aqueous samples' characterization. That includes choice of consumables, sampling methods, optimization of counting parameters and definition of energy windows, using the maximization of a Figure of Merit. Detection limits are then calculated considering these optimized parameters. For this purpose, we used PerkinElmer Tri-Carb counters. Nevertheless, except those relative to some parameters specific to PerkinElmer, most of the results presented here can be extended to other counters.

  13. Synthesis of antimicrobial silver nanoparticles through a photomediated reaction in an aqueous environment

    PubMed Central

    Banasiuk, Rafał; Frackowiak, Joanna E; Krychowiak, Marta; Matuszewska, Marta; Kawiak, Anna; Ziabka, Magdalena; Lendzion-Bielun, Zofia; Narajczyk, Magdalena; Krolicka, Aleksandra

    2016-01-01

    A fast, economical, and reproducible method for nanoparticle synthesis has been developed in our laboratory. The reaction is performed in an aqueous environment and utilizes light emitted by commercially available 1 W light-emitting diodes (λ =420 nm) as the catalyst. This method does not require nanoparticle seeds or toxic chemicals. The irradiation process is carried out for a period of up to 10 minutes, significantly reducing the time required for synthesis as well as environmental impact. By modulating various reaction parameters silver nanoparticles were obtained, which were predominantly either spherical or cubic. The produced nanoparticles demonstrated strong antimicrobial activity toward the examined bacterial strains. Additionally, testing the effect of silver nanoparticles on the human keratinocyte cell line and human peripheral blood mononuclear cells revealed that their cytotoxicity may be limited by modulating the employed concentrations of nanoparticles. PMID:26855570

  14. The dissolution of calcite in aqueous acid: The influence of humic species

    SciTech Connect

    Compton, R.G.; Sanders, G.H.W. )

    1993-07-01

    The kinetics of proton-induced calcite dissolution in aqueous solution in the presence of humic acids and their sodium salts are reported. In equilibrated acid solutions (pH <4) there is no inhibition by humic material and dissolution proceeds at a rate simply determined by the solution pH. Contrastingly the sodium salts of humic acids were found to have a significant inhibitory effect on the acid catalyzed dissolution. This was quantified using a novel channel flow cell experiment which employed two electrodes, the upstream of which was used to inject protons into a neutral solution, which also contained sodium salts of humic acid, via electrolytic oxidation of dissolved hydroquinone. The two electrodes were located immediately upstream and downstream of a calcite crystal so that the proton injection served to dissolve the calcite in the (inhibiting) presence of humic salts unequilibrated with the solution pH. The amount of H[sup +] which survived passage to the downstream detector'' electrode was used to quantify the rate of dissolution and hence the inhibitory effects of the humic acid. The latter were found to operate in a manner not inconsistent with Langmuirian adsorption.

  15. Adsorption of naphthalene from aqueous solution onto fatty acid modified walnut shells.

    PubMed

    Zhu, Mijia; Yao, Jun; Dong, Lifu; Sun, Jingjing

    2016-02-01

    The removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous solution is challenging to environmental technologists. Agricultural waste is apparently the most attractive materials in removing PAHs because of its abundance, renewability, and economic advantage. The adsorption of PAHs (e.g., naphthalene) onto walnut shell (WNS) and its fatty acid (e.g., capric acid, lauric acid, palmitic acid, and oleic acid)-modified equivalent were investigated in this work to develop low-cost biosorbents for hydrophobic organic compounds. Compared with other modified sorbents, oleic acid graftted walnut shell (OWNS) showed the maximum partition coefficient (4330 ± 8.8 L kg(-1)) because of its lowest polarity and highest aromaticity. The adsorption capacity (7210 μg g(-1)) of OWNS at the temperature of 298 K was observed for an initial naphthalene concentration of 25 mg L(-1) with contact time of 40 h, sorbent dosage of 1 g L(-1), and in neutral condition. Furthermore, the regeneration capability of OWNS implied that it was a promising biosorbent for naphthalene removal. PMID:26517393

  16. Stability of rare-earth complexes with acetylacetone and methaccrylic acid in aqueous solution

    SciTech Connect

    Panyushkin, V.T.; Akhrimenko, N.V.

    1995-09-01

    The stability constants for lanthanide (Ln) complexes with methacrylic acid (HL) (log{beta}{sub LnL}{sup Ln}), acetylacetone (HAA) (log{beta}{sub Ln(AA){sub 3}}{sup Ln}), and mixed-ligand complexes (log{beta}{sub LnL(AA){sub 2}}{sup Ln}), [Ln(III)=La, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Yb, Lu] in aqueous solution are determined by potentiometric titration at 25{degrees}C and {mu}=0.1 (KCl). A nonmonotonous change in the stability constants with an increase in the atomic number number of the rare-earth metal is found to occur.

  17. Acridine-based complex as amino acid anion fluorescent sensor in aqueous solution

    NASA Astrophysics Data System (ADS)

    Dai, Yanpeng; Xu, Kuoxi; Li, Qian; Wang, Chaoyu; Liu, Xiaoyan; Wang, Peng

    2016-03-01

    Novel acridine-based fluorescence sensors containing alaninol ligands, L1 and D1, were designed and synthesized. The structure of the compound was characterized by IR, 1H NMR, 13C NMR, MS spectra. L1 and D1 possess efficient Cu2 + cation ON-OFF selective signaling behavior based on ligand-to-metal binding mechanism at physiological pH condition. Additionally, the L1-Cu(II) and D1-Cu(II) complexes could further serve as reversible OFF-ON signaling sensing ensemble to allow ratiometric response to amino acid anion in aqueous solution.

  18. Readily available phosphate from minerals in early aqueous environments on Mars

    NASA Astrophysics Data System (ADS)

    Adcock, C. T.; Hausrath, E. M.; Forster, P. M.

    2013-10-01

    If the chemistry essential to life was present in water-containing environments on Mars, the processes that led to life on Earth may have also occurred on the red planet. Phosphate is one of the chemical nutrients thought to be essential for life and is also considered critical to reactions that may have led to life on Earth. However, low prebiotic availability of phosphate may have been a complicating factor in terrestrial abiogenesis, suggesting that a similar hurdle may have confronted the development of life on Mars. Phosphate available for biological reactions can be introduced into aqueous environments through dissolution of primary phosphate minerals during water-rock interactions, but little is known about the dissolution of the dominant phosphate minerals found in martian meteorites and presumably on Mars. Here we present dissolution rates, phosphate release rates and solubilities of phosphate minerals found in martian rocks as determined from laboratory measurements. Our experimental findings predict phosphate release rates during water-rock interactions on Mars that are as much as 45 times higher than on Earth and phosphate concentrations of early wet martian environments more than twice those of Earth. We suggest that available phosphate may have mitigated one of the hurdles to abiogenesis on Mars.

  19. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  20. The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

    NASA Astrophysics Data System (ADS)

    Rouvière, A.; Ammann, M.

    2010-12-01

    The reactive uptake of ozone to deliquesced potassium iodide aerosol particles coated with linear saturated fatty acids (C9, C12, C15, C18 and C20) was studied. The experiments were performed in an aerosol flow tube at 293 K and atmospheric pressure. The uptake coefficient on pure deliquesced KI aerosol was γ = (1.10±0.20)×10-2 at 72-75% relative humidity. In presence of organic coatings, the uptake coefficient decreased significantly for long straight chain surfactants (≥C15), while it was only slightly reduced for the short ones (C9, C12). We linked the kinetic results to the monolayer properties of the surfactants, and specifically to the expected phase state of the monolayer formed (liquid expanded or liquid condensed state). The results showed a decrease of the uptake coefficient by 30% for C12, 85% for C15 and 50% for C18 in presence of a monolayer of a fatty acid at the equilibrium spreading pressure at the air/water interface. The variation among C12, C15 and C18 follows the density of the monolayer at equilibrium spreading pressure, which is highest for the C15 fatty acid. We also investigated the effect of organic films to mixed deliquesced aerosol composed of a variable mixture of KI and NaCl, which allowed determining the resistance exerted to O3 at the aqueous surface by the two longer chained surfactants pentadecanoic acid (C15) and stearic acid (C18). For these, the probability that a molecule hitting the surface is actually transferred to the aqueous phase underneath was βC15=6.8×10-4 and βC18 = 3.3×10-4, respectively. Finally, the effect of two-component coatings, consisting of a mixture of long and short chained surfactants, was studied qualitatively.

  1. Optical characterization of ultrasmall, hydrogen-terminated and carboxyl-functionalized silicon nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Eckhoff, Dean Alan

    The primary theme of this dissertation is to characterize the optical and chemical properties of ultrasmall (˜1 nm) silicon nanoparticles (Si-np) in aqueous environments, focusing on their potential for use as luminescent markers in biophysical and biological applications. Two systems are presented in detail: hydrogen-terminated Si-np prepared through electrochemical dispersion of a crystalline Si wafer and carboxyl-functionalized Si-np prepared via thermal hydrosilylation of surface Si-H bonds with an o-ester 1-alkene. Chemical and physical characterizations are done using nuclear magnetic resonance, size exclusion chromatography, and infrared spectroscopy. Optical characterization is done via absorption and steady-state photoluminescence (PL) and using capillary electrophoresis coupled with laser-induced fluorescence detection. The behavior of the hydrogen-terminated Si-np is studied over time as-prepared in isopropanol and during treatments with water, NaOH, HCl, and H2O 2. The PL spectra show three distinct, near-Gaussian states with a FWHM ˜0.45 eV and their respective emissions in the UV-B (˜305 nm), UV-A (˜340 nm), and 'hard-blue' (˜400 nm) regions of the spectrum. The 'hard-blue' emission is shown to have a simple pH dependence with a pKa ˜3, demonstrating the possibility of using Si-np as environmental probes. These results offer some promise for tailoring the PL properties of ultrasmall Si-np through control of their surface chemistry. In the second part, three central elements establish that the carboxyl-functionalized Si-np have excellent potential for use as a luminescent marker in aqueous systems. First, they are shown to be ultrasmall, with a diameter of ˜1 nm, comparable to that of common organic fluorophores. Second, they are shown to have narrow PL in the near-UV with a nearly-symmetric lineshape and a FWHM as small as 30 nm. Third, it is shown that standard chemical means can be used to functionalize the Si-np with carboxyl groups, giving

  2. Microstructural dependence of aqueous-environment-assisted crack growth and hydrogen uptake in AA 7050

    NASA Astrophysics Data System (ADS)

    Young, Lisa Marie

    This goal of this research was to explain the effects of heat treatment, Cu content, and electrode potential (EApp) on short-transverse aqueous environment assisted cracking (EAC) in a precipitation hardened Al-Zn-Mg-(Cu) alloy. Substantial intergranular EAC susceptibility was observed in several underaged (UA) and peak aged (PA) tempers of AA 7050, where increasing E App produced a slow crack growth rate (da/dt) incubation and transition to fast da/dt. Above the transition potential, da/dt was dramatically increased by further increases in EApp. In contrast the overaged (OA) condition was highly EAC resistant, exhibiting transgranular da/dt ≤2 x 10-8 mm/sec or ≈ 10,000 times slower than PA. Crack growth rates in the low Cu alloy were several orders of magnitude higher than those exhibited by the high Cu material at similar EApp and were only slightly reduced on overaging. Thermal desorption spectroscopy (TDS) results showed enhanced hydrogen uptake in fast-cracking EAC regions compared to as-received hydrogen concentrations. Hydrogen analyses were complicated by the dependence of H-production and uptake on wake exposure time and a pH gradient in the occluded crack environment. Trends between applied anodic potential, crack wake H concentration (normalized by the wake exposure time), and aqueous da/dt were observed. Nuclear reaction analysis revealed unexpectedly high near-surface H concentrations ( ≈ 2000 wppm). The H-concentration profiles indicate that the observed da/dt can be rate-limited by bulk H-diffusion into the crack tip process zone, where EAC is promoted by a hydrogen embrittlement mechanism. The transition potential to fast da/dt increased in the anodic direction with increased isothermal aging time. Additionally, the presence of large Cu-containing second phase particles (S-phase) on high angle grain boundaries partially negated the beneficial effect of overaging on EAC in the Cu-containing alloy, an effect not observed in humid air cracking

  3. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    SciTech Connect

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  4. 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.

  5. Formation of isomers of anionic hemiesters of sugars and carbonic acid in aqueous medium.

    PubMed

    Dos Santos, Vagner B; Vidal, Denis T R; Francisco, Kelliton J M; Ducati, Lucas C; do Lago, Claudimir L

    2016-06-16

    Hemiesters of carbonic acid can be freely formed in aqueous media containing HCO3(-)/CO2 and mono- or poly-hydroxy compounds. Herein, (13)C NMR spectroscopy was used to identify isomers formed in aqueous solutions of glycerol (a prototype compound) and seven carbohydrates, as well as to estimate the equilibrium constant of formation (Keq). Although both isomers are formed, glycerol 1-carbonate corresponds to 90% of the product. While fructose and ribose form an indistinct mixture of isomers, the anomers of d-glucopyranose 6-carbonate correspond to 74% of the eight isomers of glucose carbonate that were detected. The values of Keq for the disaccharides sucrose (4.3) and maltose (4.2) are about twice the values for the monosaccharides glucose (2.0) and fructose (2.3). Ribose (Keq = 0.89)-the only sugar without a significant concentration of a species containing a -CH2OH group in an aqueous solution-resulted in the smallest Keq. On the basis of the Keq value and the concentrations of HCO3(-) and glucose in blood, one can anticipate a concentration of 2-4 µmol L(-1) for glucose 6-carbonate, which corresponds to ca. of 10% of its phosphate counterpart (glucose 6-phosphate). PMID:27111726

  6. Engineered metal based nanomaterials in aqueous environments: Interactions, transformations and implications

    NASA Astrophysics Data System (ADS)

    Mudunkotuwa, Imali Ama

    Nanoscience and nanotechnology offer potential routes towards addressing critical issues such as clean and sustainable energy, environmental protection and human health. Specifically, metal and metal oxide nanomaterials are found in a wide range of applications and therefore hold a greater potential of possible release into the environment or for the human to be exposed. Understanding the aqueous phase behavior of metal and metal oxide nanomaterials is a key factor in the safe design of these materials because their interactions with living systems are always mediated through the aqueous phase. Broadly the transformations in the aqueous phase can be classified as dissolution, aggregation and adsorption which are dependent and linked processes to one another. The complexity of these processes at the liquid-solid interface has therefore been one of the grand challenges that has persisted since the beginning of nanotechnology. Although classical models provide guidance for understanding dissolution and aggregation of nanoparticles in water, there are many uncertainties associated with the recent findings. This is often due to a lack of fundamental knowledge of the surface structure and surface energetics for very small particles. Therefore currently the environmental health and safety studies related to nanomaterials are more focused on understanding the surface chemistry that governs the overall processes in the liquid-solid interfacial region at the molecular level. The metal based nanomaterials focused on in this dissertation include TiO2, ZnO, Cu and CuO. These are among the most heavily used in a number of applications ranging from uses in the construction industry to cosmetic formulation. Therefore they are produced in large scale and have been detected in the environment. There is debate within the scientific community related to their safety as a result of the lack of understanding on the surface interactions that arise from the detailed nature of the surfaces

  7. [Changes in the collagen amino acid composition of calf skin after gamma-irradiation in an aqueous solution].

    PubMed

    Duzhenkova, N A; Savich, A V

    1983-01-01

    A study was made of the amino acid composition of calf skin collagen after gamma-irradiation (60Co) of 2.5 X 10(-6) M aerated aqueous protein solution within the dose range from 30 to 2000 Gy. The radiosensitivity of amino acid residues was compared. PMID:6657935

  8. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    NASA Astrophysics Data System (ADS)

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-02-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range.

  9. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid.

    PubMed

    Niskanen, Johannes; Sahle, Christoph J; Ruotsalainen, Kari O; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  10. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    PubMed Central

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  11. Competitive adsorption of boric acid and chromate onto alumina in aqueous solutions.

    PubMed

    Demetriou, A; Pashalidis, I

    2014-01-01

    The competitive adsorption of boric acid and chromate from aqueous solutions by alumina has been investigated by spectrophotometry at pH 8, ionic strength = 0.0, 0.1 and 1.0 M NaClO4, T = 22 ± 3 °C and under normal atmospheric conditions. The experimental data show that addition of excess boric acid in the system leads to the increase of Cr(VI) concentration in solution, indicating the replacement of adsorbed chromate by boron on the alumina surface. Data evaluation results in the determination of the competition reaction constant and the formation constant of the Cr(VI) surface complexes, which are logKCr(VI)-B(III) = -3.5 ± 0.2 and logβ*Cr = 7.6 ± 0.3, respectively. PMID:24473309

  12. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    SciTech Connect

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  13. Electrochemistry of poly(vinylferrocene) modified electrodes in aqueous acidic media

    NASA Astrophysics Data System (ADS)

    Issa, Touma B.; Singh, Pritam; Baker, Murray V.

    A cyclic voltammetric study of the electrochemistry and chemical stability of the poly(vinylferrocene) (PVFc) redox couple, coated on a gold substrate, in aqueous solutions of H 2SO 4, HClO 4 and HCl was carried out. It was found that the anodic peak potential ( Epa) did not depend on the acid concentration in the range (1.0 × 10 -2 to 1.0 × 10 -7 mol L -1). However, the Epa values shifted linearly to less positive potentials when investigated in more concentrated acid solutions in the range 1-5 mol L -1. The slope of the Epa versus acid concentration graph was found to be in the order H 2SO 4 > HCl > HClO 4. In this regard PVFc behaved very similar to 1,1'-bis(11-mercaptoundecyl)ferrocene (Fc(C 11SH) 2) except for its chemical stability. In H 2SO 4 media the PVFc was found to be much less stable than 1,1'-Fc(C 11SH) 2. The dependence of Epa on acid concentration could be used to monitor state of charge of lead-acid batteries. However, for this application Fc(C 11SH) 2 would be a better choice because of its superior chemical stability.

  14. Influence of charge exchange in acidic aqueous and alcoholic titania dispersions on viscosity.

    PubMed

    Rosenholm, Jarl B; Dahlsten, Per

    2015-12-01

    Charging effects resulting from adsorption of acid, acid anions, and protons on titania (anatase) surfaces in anhydrous or mixed alcohol-water dispersions is summarized. The suddenly enhanced conductivity as compared to titania-free solutions has previously been modeled and explained as surface-induced electrolytic dissociation (SIED) of weak acids. This model and recently published results identifying concurrent surface-induced liquid (solvent) dissociation (SILD) are evaluated with experimentally determined conductivity and pH of solutions, zeta-potential of particles, and viscosity of dispersions. Titania (0-25wt%)-alcohol (methanol, ethanol, and propanol) dispersions mixed with (0-100wt%) water were acidified with oxalic, phosphoric, and sulfuric acids. It was found that the experimental results could in many cases be condensed to master curves representing extensive experimental results. These curves reveal that major properties of the systems appear within three concentration regions were different mechanisms (SILD, surface-induced liquid dissociation; SIAD, surface-induced acid dissociation) and charge rearrangement were found to be simultaneously active. In particular, zeta-potential - pH and viscosity - pH curves are in acidified non-polar solvents mirror images to those dependencies observed in aqueous dispersions to which hydroxyl is added. The results suggest that multiple dispersion and adsorption equilibria should be considered in order to characterize the presented exceptionally extensive and complex experimental results. PMID:26520241

  15. Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Earl, Lyndsey D.

    2005-01-01

    The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

  16. Sulfate Formation From Acid-Weathered Phylosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.

    2014-01-01

    Most phyllosilicates on Mars are thought to have formed during the planet's earliest Noachian era, then Mars underwent a global change making the planet's surface more acidic [e.g. 1]. Prevailing acidic conditions may have affected the already existing phyllosilicates, resulting in the formation of sulfates. Both sulfates and phyllosilicates have been identified on Mars in a variety of geologic settings [2] but only in a handful of sites are these minerals found in close spatial proximity to each other, including Mawrth Vallis [3,4] and Gale Crater [5]. While sulfate formation from the acidic weathering of basalts is well documented in the literature [6,7], few experimental studies investigate sulfate formation from acid-weathered phyllosilicates [8-10]. The purpose of this study is to characterize the al-teration products of acid-weathered phyllosilicates in laboratory experiments. We focus on three commonly identified phyllosilicates on Mars: nontronite (Fe-smectite), saponite (Mg-smectite), and montmorillonite (Al-smectite) [1, and references therein]. This information will help constrain the formation processes of sulfates observed in close association with phyllosilicates on Mars and provide a better understanding of the aqueous history of such regions as well as the planet as a whole.

  17. Dissolution of nickel ferrite in aqueous solutions containing oxalic acid and ferrous salts

    SciTech Connect

    Figueroa, C.A.; Sileo, E.E.; Morando, P.J.; Blesa, M.A.

    2000-05-15

    The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni{sub 1.06}Fe{sub 1.96}O{sub 4}. The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite. It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel.

  18. Ulcer healing activity of Mumijo aqueous extract against acetic acid induced gastric ulcer in rats

    PubMed Central

    Shahrokhi, Nader; Keshavarzi, Zakieh; Khaksari, Mohammad

    2015-01-01

    Objective: Gastric ulcer is an important clinical problem, chiefly due to extensive use of some drugs. The aim was to assess the activity of Mumijo extract (which is used in traditional medicine) against acetic acid induced gastric ulcer in rats. Materials and Methods: The aqueous extract of Mumijo was prepared. Animals were randomly (n = 10) divided into four groups: Control, sham-operated group (received 0.2 ml of acetic acid to induce gastric ulcer), Mumijo (100 mg/kg/daily) were given for 4 days postacetic acid administration, and ranitidine group (20 mg/kg). The assessed parameters were pH and pepsin levels (by Anson method) of gastric contents and gastric histopathology. Ranitidine was used as reference anti-ulcer drug. Results: The extract (100 mg/kg/daily, p.o.) inhibited acid acetic-induced gastric ulceration by elevating its pH versus sham group (P < 0.01) and decreasing the pepsin levels compared to standard drug, ranitidine (P < 0.05). The histopathology data showed that the treatment with Mumijo extract had a significant protection against all mucosal damages. Conclusion: Mumijo extract has potent antiulcer activity. Its anti-ulcer property probably acts via a reduction in gastric acid secretion and pepsin levels. The obtained results support the use of this herbal material in folk medicine. PMID:25709338

  19. Contribution of diffuse inputs to the aqueous mass load of perfluoroalkyl acids in river and stream catchments in Korea.

    PubMed

    Kim, Seung-Kyu; Li, Dong-Hao; Shoeib, Mahiba; Zoh, Kyung-Duk

    2014-02-01

    Recent studies disagree regarding the contributions of point versus non-point sources to the aqueous mass loads of perfluoroalkyl acids (PFAAs). This study investigated the longitudinal change in PFAA mass load from upstream to downstream stations along rivers and/or streams to assess the relative contributions of point versus nonpoint inputs. With concentrations 10 to 100 times higher than running water, point sources such as wastewater treatment plants (WWTPs) effluent and airport ditch-outlet (ADO) water were separated from neighboring upstream and downstream running waters using principal component analysis. Source waters were characterized by certain predominant components [e.g., perfluorobutylsulfonate (PFBS) and perfluorooctanoic acid (PFOA) in WWTP effluent and perfluorohexylsulfonate (PFHxS) and perfluorooctylsulfonate (PFOS) in ADO water], which were minor components of running water. From a mass balance assessment of PFAA mass load, certain compounds such as PFOA and PFBS dominated the contribution of point sources to the mass load in the running water at downstream stations or in small catchment basins with high levels of industrial activity. Most of the mass load in the investigated catchments was attributable to upstream running water with a minor influence from industrial, commercial, and domestic human activities. Furthermore, the negative relationship of per capita emission factors (hereafter, EFs) with population density and a lower contribution of PFAA from WWTPs (~30% on average) compared to the running water-derived mass load at the national level indicated that diffuse inputs were more important contributors to aqueous PFAA contamination in each catchment basin as well as the entire watershed of the country (Korea). Volatile precursor compounds, which are readily dispersed to neighboring basins and transformed to PFAAs in the ambient environment, can be an important source of these diffuse inputs and will become more significant over time

  20. Adsorption of Crystal violet on raw and acid-treated montmorillonite, K10, in aqueous suspension.

    PubMed

    Sarma, Gautam Kumar; Sen Gupta, Susmita; Bhattacharyya, Krishna G

    2016-04-15

    Crystal violet is used as a dye in cotton and silk textiles, paints and printing ink. The dye is hazardous and exposure to it may cause permanent injury to the cornea and conjunctiva including permanent blindness, and in severe cases, may lead to respiratory and kidney failure. The present work describes removal of Crystal violet from aqueous solution by adsorption on raw and acid-treated montmorillonite, K10. The clay mineral was treated with 0.25 and 0.50 M sulfuric acid and the resulting materials were characterized by XRD, zeta potential, SEM, FTIR, cation exchange capacity, BET surface area and pore volume measurements. The influences of pH, interaction time, adsorbent amount, and temperature on adsorption were monitored and explained on the basis of physico-chemical characteristics of the materials. Basic pH generally favors adsorption but considerable removal was possible even under neutral conditions. Adsorption was very rapid and equilibrium could be attained in 180 min. The kinetics conformed to second order model. Langmuir monolayer adsorption capacity of raw montmorillonite K10 was 370.37 mg g(-1) whereas 0.25 M and 0.50 M acid treated montmorillonite K10 had capacities of 384.62 and 400.0 mg g(-1) respectively at 303 K. Adsorption was exothermic and decreased in the temperature range of 293-323 K. Thermodynamically, the process was spontaneous with Gibbs energy decreasing with rise in temperature. The results suggest that montmorillonite K10 and its acid treated forms would be suitable for removing Crystal violet from aqueous solution. PMID:26866669

  1. Bile acid-surfactant interactions at the liquid crystal/aqueous interface.

    PubMed

    He, Sihui; Liang, Wenlang; Cheng, Kung-Lung; Fang, Jiyu; Wu, Shin-Tson

    2014-07-14

    The interaction between bile acids and surfactants at interfaces plays an important role in fat digestion. In this paper, we study the competitive adsorption of cholic acid (CA) at the sodium dodecyl sulfate (SDS)-laden liquid crystal (LC)/aqueous interface formed with cyanobiphenyl (nCB, n = 5-8) and the mixture of 5CB with 4-(4-pentylcyclohexyl)benzonitrile (5PCH). We find that the critical concentration of CA required to displace SDS from the interface linearly decreases from 160 μM to 16 μM by reducing the alkyl chain length of nCB from n = 8 to n = 5 and from 16 μM to 1.5 μM by increasing the 5PCH concentration from 0 wt% to 19 wt% in the 5PCH-5CB binary mixture. Our results clearly demonstrate that the sensitivity of 5PCH-5CB mixtures for monitoring the interaction between CA and SDS at the LC/aqueous interface can be increased by one order of magnitude, compared to 5CB. PMID:24825535

  2. EXAFS study of the speciation of protactinium(V) in aqueous hydrofluoric acid solutions.

    PubMed

    De Sio, Stéphanie M; Wilson, Richard E

    2014-12-01

    The speciation of protactinium(V) in hydrofluoric acid (HF) solutions was studied using X-ray absorption spectroscopy. Extended X-ray absorption fine structure measurements were performed on an aqueous solution of 0.05 M protactinium(V) with various HF concentrations ranging from 0.5 to 27 M in order to probe the protactinium coordination sphere with respect to the identity and number of coordinating ligands. The resulting fits to the spectra suggest the presence of an eight-coordinate homoleptic fluoro complex in highly concentrated fluoride solutions (27 M), with equilibrium between seven- and eight-coordinate fluoro complexes at moderate acidities, and in more dilute solutions, results indicate that one water molecule is likely to replace a fluoride in the first coordination sphere, at a distance of 2.54-2.57 Å. Comparisons of this chemistry with group V metals, niobium and tantalum, are presented, and the potential implications for these results on the hydrolytic behavior of protactinium in aqueous systems are discussed. PMID:25389749

  3. Adsorptions of some heavy metal ions in aqueous solutions by acrylamide/maleic acid hydrogels

    SciTech Connect

    Saraydin, D.; Karadag, E.; Gueven, O.

    1995-10-01

    In this study, acrylamide-maleic acid (AAm/MA) hydrogels in the form of rod have been prepared by {gamma}-radiation. They have been used for adsorption of some heavy metal ions such as uranium, iron, and copper. For the hydrogel containing 40 mg of maleic acid and irradiated at 3.73 kGy, maximum and minimum swellings in the aqueous solutions of the heavy metal ions have been observed with water (1480%) and the aqueous solution of iron(III) nitrate (410%), respectively. Diffusions of water and heavy metal ions onto hydrogels have been found to be of the non-Fickian type of diffusion. In experiments of uranyl ions adsorption, Type II adsorption has been found. One gram of AAa/MA hydrogels sorbed 14-86 mg uranyl ions from solutions of uranyl acetate, 14-90 mg uranyl ions from solutions of uranyl nitrate, 16-39 mg iron ions from solutions of iron(IV) nitrate, and 28-81 mg copper ions from solutions of copper acetate, while acrylamide hydrogel did not sorb any heavy metals ions.

  4. Effect of Humic Acid on Migration, Distribution and Remediation of Dense Non-aqueous Phase Liquids: A laboratory investigation

    NASA Astrophysics Data System (ADS)

    Cheng, Z.; Wu, J.; Xu, H.; Gao, Y.

    2014-12-01

    Over the last decades, dense non-aqueous phase liquids (DNAPLs) contamination in the subsurface increases with the rapid development of oil industry and becomes the focus of many studies. The migration, distribution and remediation efficiency of DNAPLs in the subsurface environment are greatly affected by the solution chemistry besides the physical heterogeneities of aquifers. Humic acid (HA), which is ubiquitous in natural environments, is a surface active substance exhibiting solubility enhancement behavior for hydrophobic organic compounds such as DNAPLs. Here we reported a laboratory investigation to study the effects of HA on the infiltration, immobilization and subsequent recovery of DNAPL in porous media. Tetrachloroethylene (PCE) was selected as the representative DNAPL in this study. Two-dimensional (2-D) sandbox experiments were conducted to investigate the effects of different HA concentrations on the transport, distribution of PCE and the remediation of PCE using surfactant (Tween 80) flushing in a saturated porous media system. The surfactant flushing of PCE was performed after the PCE transport and distribution had reached equilibrium. A light transmission visualization method with charge-coupled device (CCD) camera was adopted to visualize PCE distribution and quantify its saturation. In addition, the experiments were also designed to gather data for the validation of multiphase flow models. Effluent samples were collected to determine dissolved PCE concentrations. PCE solubilization and PCE-water interfacial tension were experimentally determined in aqueous solutions of varying HA concentrations. The experimental results showed that the presence of HA can have a dramatic impact on PCE flow and entrapment, and significantly improved the recovery of PCE during surfactant enhanced aquifer remediation (SEAR). The findings are of use for better understanding of the migration and entrapment of DNAPLs and developing of SEAR technology.

  5. Effects of frequency and temperature on short fatigue crack growth in aqueous environments

    NASA Astrophysics Data System (ADS)

    Nakai, Y.; Alavi, A.; Wei, R. P.

    1988-03-01

    The growth of short fatigue cracks in a NiCrMoV steel forging was examined, under constant applied stress intensity range (ΔK = 31 MPa-m1/2) in deaerated deionized water and 0.3 M Na2SO4 solution, as a function of frequency and temperature. Measurements were also made of the kinetics of electrochemical reactions of bare steel surfaces with the deaerated 0.3 M Na2SO4 solution, under free corrosion, to provide for comparison and correlation. Fatigue crack growth rate increased with reductions in frequency and with increases in temperature. The maximum amount of crack growth enhancement by the different environments appeared to be equal, although the crack growth response in deionized water appeared to be consistent with a faster reaction rate. The temperature and frequency dependence for corrosion fatigue crack growth corresponded directly with that for charge transfer between the “bare” and “filmed” metal surfaces under free corrosion. The results showed that shortcrack growth in the aqueous environments is controlled by the rate of electrochemical reactions, and is thermally activated with an apparent activation energy of about 40 kJ/M.

  6. Extraction and isolation of TPE from other elements on ion exchangers in aqueous and aqueous-organic solutions of phosphoric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-07-01

    The behavior of Am-Es and other actinides on anion and cation exchange resins in aqueous and aqueous-organic solutions of phosphoric acid has been studied in a wide range of concentration of various components of the solution. The sorptivity of transplutonium elements (TPE) on anion exchangers from dilute H/sub 3/PO/sub 4/ with a concentration less than or equal to 1 M in presence of organic solvents (alcohols, ketones, etc.) and on cation exchangers from concentrated H/sub 3/PO/sub 4/ has been found to be significant. The possibility of use of phosphoric acid solutions for isolation of TPE from Th, Pa, U, Np, Pu, and Zr and separation of TPE in different oxidation states in presence of a high-purity oxidant has been shown.

  7. Permeability of acetic acid through organic films at the air-aqueous interface.

    PubMed

    Gilman, Jessica B; Vaida, Veronica

    2006-06-22

    Recent field studies of collected aerosol particles, both marine and continental, show that the outermost layers contain long-chain (C >or= 18) organics. The presence of these long-chain organics could impede the transport of gases and other volatile species across the interface. This could effect the particle's composition, lifetime, and heterogeneous chemistry. In this study, the uptake rate of acetic acid vapor across a clean interface and through films of long-chain organics into an aqueous subphase solution containing an acid-base indicator (bromocresol green) was measured under ambient conditions using visible absorption spectroscopy. Acetic acid is a volatile organic compound (VOC) and is an atmospherically relevant organic acid. The uptake of acetic acid through single-component organic films of 1-octadecanol (C(18)H(38)O), 1-triacontanol (C(30)H(62)O), cis-9-octadecen-1-ol (C(18)H(36)O), and nonacosane (C(29)H(60)) in addition to two mixed films containing equimolar 1-triacontanol/nonacosane and equimolar 1-triacontanol/cis-9-octadecen-1-ol was determined. These species represent long-chain organic compounds that reside at the air-aqueous interface of atmospheric aerosols. The cis-9-octadecen-1-ol film had little effect on the net uptake rate of acetic acid vapor into solution; however, the uptake rate was reduced by almost one-half by an interfacial film of 1-triacontanol. The measured uptake rates were used to calculate the permeability of acetic acid through the various films which ranged from 1.5 x 10(-3) cm s(-1) for 1-triacontanol, the least permeable film, to 2.5 x 10(-2) cm s(-1) for cis-9-octadecen-1-ol, the most permeable film. Both mixed films had permeabilities that were between that of the single-component films comprising the mixture. This shows that the permeability of a mixed film may not be solely determined by the most permeable species in the mixture. The permeabilities of all the films studied here are discussed in relation to their

  8. Visible Wavelength Spectroscopy of Ferric Minerals: A Key Tool for Identification of Ancient Martian Aqueous Environments

    NASA Technical Reports Server (NTRS)

    Murchie, Scott L.; Bell, J. F., III; Morris, Richard V.

    2000-01-01

    The mineralogic signatures of past aqueous alteration of a basaltic Martian crust may include iron oxides and oxyhydroxides, zeolites, carbonates, phyllosilicates, and silica. The identities, relative abundances, and crystallinities of the phases formed in a particular environment depend on physicochemical conditions. At one extreme, hot spring environments may be characterized by smectite-chlorite to talc-kaolinite silicate assemblages, plus crystalline ferric oxides dominated by hematite. However, most environments, including cold springs, pedogenic layers, and ponded surface water, are expected to deposit iron oxides and oxyhydroxides, carbonates, and smectite-dominated phyllosilicates. A substantial fraction of the ferric iron is expected to occur in nanophase form, with the exact mineralogy strongly influenced by Eh-pH conditions. Detection of these phases has been an objective of a large body of terrestrial telescopic, Mars orbital, and landed spectral investigations and in situ compositional measurements. However, clear identifications of many of these phases is lacking. Neither carbonate nor silica has been unequivocally detected by any method. Although phyllosilicates may occur near the limit of detection by remote sensing, in general they appear to occur in only poorly crystalline form. In contrast, compelling evidence for ferric iron minerals has been gathered by recent telescopic investigations, the Imager for Mars Pathfinder (IMP), and the Thermal Emission Spectrometer (TES) on the Mars Global Surveyor (MGS). These data yield two crucial findings: (1) In the global, high spatial resolution TES data set, highly crystalline ferric iron (as coarse-grained 'gray' hematite) has been recognized but with only very limited spatial occurrence and (2) Low-resolution telescopic reflectance spectroscopy, very limited orbital reflectance spectroscopy, and landed multispectral imaging provide strong indications that at least two broad classes of ferric iron minerals

  9. Reactivity of alanylalanine diastereoisomers in neutral and acid aqueous solutions: a versatile stereoselectivity.

    PubMed

    Plasson, Raphaël; Tsuji, Maika; Kamata, Masazumi; Asakura, Kouichi

    2011-10-01

    A good comprehension of the reactivity of peptides in aqueous solution is fundamental in prebiotic chemistry, namely for understanding their stability and behavior in primitive oceans. Relying on the stereoselectivity of the involved reactions, there is a huge interest in amino acid derivatives for explaining the spontaneous emergence of homochirality on primitive Earth. The corresponding kinetic and thermodynamic parameters are however still poorly known in the literature. We studied the reactivity of alanylalanine in acidic to neutral conditions as a model system. The hydrolysis into amino acids, the epimerization of the N-terminal residue, and the cyclization into diketopiperazine could be successfully identified and studied. This kinetic investigation highlighted interesting behaviors. Complex mechanisms were observed in very acidic conditions. The relative kinetic stability of the diastereoisomers of the dipeptide is highly dependent of the pH, with the possibility to dynamically destabilize the thermodynamically more stable diastereoisomers. The existence of the cyclization of dipeptides adds complexity to the system. On one hand it brings additional stereoselectivities; on the other hand fast racemization of heterochiral dipeptides is obtained. PMID:21562847

  10. Vanillic and syringic acids from biomass burning: Behaviour during Fenton-like oxidation in atmospheric aqueous phase and in the absence of light.

    PubMed

    Santos, Gabriela T A D; Santos, Patrícia S M; Duarte, Armando C

    2016-08-01

    Biomass combustion is a threat to the environment since it emits to the atmosphere organic compounds, which may react and originate others more aggressive. This work studied the behaviours of vanillic and syringic acids, small aromatic tracers of biomass burning, during Fenton-like oxidation in aqueous phase and absence of light. For both compounds, the extent of oxidation increased with pH decrease from neutral to acid in atmospheric waters, but for vanillic acid the neutral pH was not able of promoting the oxidation. With the oxidation of both acids were formed chromophoric compounds, and the formation rate increased with the degree of electron-donator substituents in benzene ring. The initial and produced compounds were not totally degraded up to 24h of reaction at pH 4.5, suggesting that the night period may be not sufficient for their full degradation in atmospheric waters. The major compounds formed were the 3,4-dihydroxybenzoic acid for vanillic acid, and the 1,4-dihydroxy-2,6-dimethoxybenzene for syringic acid. These findings suggest the occurrence of an ipso attack by the hydroxyl radical preferential to the methoxy and carboxyl groups of vanillic and syringic acids, respectively. It is important to highlight that for both aromatic acids the main compounds produced are also small aromatic compounds. PMID:27085101

  11. Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol.

    PubMed

    Tan, Yi; Perri, Mark J; Seitzinger, Sybil P; Turpin, Barbara J

    2009-11-01

    Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30-3000 microM) and the presence of acidic sulfate (0-840 microM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 microM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA. PMID:19924930

  12. Degradation of hydroxycinnamic acid mixtures in aqueous sucrose solutions by the Fenton process.

    PubMed

    Nguyen, Danny M T; Zhang, Zhanying; Doherty, William O S

    2015-02-11

    The degradation efficiencies and behaviors of caffeic acid (CaA), p-coumaric acid (pCoA), and ferulic acid (FeA) in aqueous sucrose solutions containing the mixture of these hydroxycinnamic acids (HCAs) were studied by the Fenton oxidation process. Central composite design and multiresponse surface methodology were used to evaluate and optimize the interactive effects of process parameters. Four quadratic polynomial models were developed for the degradation of each individual acid in the mixture and the total HCAs degraded. Sucrose was the most influential parameter that significantly affected the total amount of HCA degraded. Under the conditions studied there was a <0.01% loss of sucrose in all reactions. The optimal values of the process parameters for a 200 mg/L HCA mixture in water (pH 4.73, 25.15 °C) and sucrose solution (13 mass %, pH 5.39, 35.98 °C) were 77% and 57%, respectively. Regression analysis showed goodness of fit between the experimental results and the predicted values. The degradation behavior of CaA differed from those of pCoA and FeA, where further CaA degradation is observed at increasing sucrose and decreasing solution pH. The differences (established using UV/vis and ATR-FTIR spectroscopy) were because, unlike the other acids, CaA formed a complex with Fe(III) or with Fe(III) hydrogen-bonded to sucrose and coprecipitated with lepidocrocite, an iron oxyhydroxide. PMID:25585639

  13. Interactions of chromium ions with starch granules in an aqueous environment.

    PubMed

    Szczygieł, Jadwiga; Dyrek, Krystyna; Kruczała, Krzysztof; Bidzińska, Ewa; Brożek-Mucha, Zuzanna; Wenda, Elżbieta; Wieczorek, Jerzy; Szymońska, Joanna

    2014-06-26

    In this study, interactions of dichromate ions with potato starch granules in highly acidic aqueous solutions and at different temperatures were investigated. It was found that the process underwent a reduction of Cr(2)O(7)(2-) to Cr(3+) accompanied by the formation of intermediate Cr(5+) ions detected by electron paramagnetic resonance (EPR) spectroscopy. The reactions took place after the attachment of dichromate anions to the granules and resulted in a lowering of the Cr(2)O(7)(2-) initial content in the solution. The newly formed Cr(3+) ions were both accumulated by the granules or remained in the solution. It was observed for the first time that the quantity of such ions taken by the granules from the solution was noticeably higher than that delivered by trivalent chromium salt solution. It was revealed by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX) that the chromium ions were not only adsorbed on the granule surface but also introduced into the granule interior and evenly distributed there. An activation energy of the reduction reaction equal to 65 kJ·mol(-1) and the optimal parameters of the process were established. The proposed mechanism could be useful for the bioremediation of industrial effluents polluted by hexavalent chromium compounds. PMID:24878058

  14. EXAFS Study on the Reactions Between Iron And Fulvic Acid in Acid Aqueous Solutions

    SciTech Connect

    Schaik, J.W.J.van; Persson, I.; Kleja, D.B.; Gustafsson, J.P.

    2009-05-26

    Iron(III) competes with trace metals for binding sites on organic ligands. We used X-ray absorption fine structure (EXAFS) spectroscopy to determine the binding mode and oxidation state of iron in solutions initially containing only iron(III) and fulvic acid at pHs 2 and 4. EXAFS spectra were recorded at different times after sample preparation. Iron was octahedrally configured with inner-sphere Fe-O interactions at 1.98-2.10 {angstrom}, depending on the oxidation state of iron. Iron(III) formed complexes with fulvic acid within 15 min. Iron(III) was reduced to iron(II) with time at pH 2, whereas no significant reduction occurred at pH 4. No signs of dimeric/trimeric hydrolysis products were found in any of the solution samples (<0.45 {mu}m). However, the isolated precipitate of the pH 2 sample (>0.45 {mu}m) showed Fe{hor_ellipsis}Fe distances, indicating the presence of tightly packed iron(III) trimers and/or clusters of corner-sharing octahedra. It is suggested that the binding mode of iron(III) to fulvic acid at low pH may be phase-dependent: in solution mononuclear complexes predominate, whereas in the solid phase hydrolyzed polynuclear iron(III) complexes form, even at very low pH values. The observed pH dependence of iron(III) reduction was consistent with expected results based on thermodynamic calculations for model ligands.

  15. Volatility and oxidative aging of aqueous maleic acid aerosol droplets and the dependence on relative humidity.

    PubMed

    Dennis-Smither, Benjamin J; Marshall, Frances H; Miles, Rachael E H; Preston, Thomas C; Reid, Jonathan P

    2014-07-31

    The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapor pressure determined to be (1.7 ± 0.2) × 10(-3) Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the subcooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size, and refractive index have been made during ozonolysis at RHs in the range 50-80%, providing insight into the volatility of organic products, changes in the droplet hygroscopicity, and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al. ( J. Geophys. Res. 2011 , 116 , D15204 ). Once oxidized, particles are shown to form amorphous phases on drying rather than crystallization, with slow evaporation kinetics of residual water. PMID:25003240

  16. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    SciTech Connect

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  17. Adsorptive removal of nickel(II) ions from aqueous environment: A review.

    PubMed

    Raval, Nirav P; Shah, Prapti U; Shah, Nisha K

    2016-09-01

    Among various methods adsorption can be efficiently employed for the treatment of heavy metal ions contaminated wastewater. In this context the authors reviewed variety of adsorbents used by various researchers for the removal of nickel(II) ions from aqueous environment. One of the objectives of this review article is to assemble the scattered available enlightenment on a wide range of potentially effective adsorbents for nickel(II) ions removal. This work critically assessed existing knowledge and research on the uptake of nickel by various adsorbents such as activated carbon, non-conventional low-cost materials, nanomaterials, composites and nanocomposites. The system's performance is evaluated with respect to the overall metal removal and the adsorption capacity. In addition, the equilibrium adsorption isotherms, kinetics and thermodynamics data as well as various optimal experimental conditions (solution pH, equilibrium contact time and dosage of adsorbent) of different adsorbents towards Ni(II) ions were also analyzed. It is evident from a literature survey of more than 190 published articles that agricultural solid waste materials, natural materials and biosorbents have demonstrated outstanding adsorption capabilities for Ni(II) ions. PMID:27149285

  18. Stress-corrosion behavior of aluminum-lithium alloys in aqueous environments

    NASA Technical Reports Server (NTRS)

    Pizzo, P. P.; Galvin, R. P.; Nelson, H. G.

    1983-01-01

    The stress corrosion susceptibility of two powder metallurgy (P/M) alloys, Al-Li-Cu and Al-Li-Cu-Mg two mechanically attrited (M/A) alloys, Al-Li-Cu and Al-Li-Mg; and two wrought, ingot alloys, X-2020 and AA7475, are compared. Time-dependent fracture in an aqueous sodium chloride environment under alternate immersion condition was found to vary significantly between alloys. The stress corrosion behavior of the two powder metallurgy processed alloys was studied in detail under conditions of crack initiation, static crack growth, and fatigue crack growth. A variety of stress corrosion tests were performed including smooth surface, time-to-failure tests; potentiostatic tests on smooth surfaces exposed to constant applied strain rates; and fracture mechanics-type tests under static and cyclic loads. Both alloys show surface pitting and subsequent intergranular corrosion. Pitting is more severe in the magnesium-bearing alloy and is associated with stringer particles strung along the extrusion direction as a result of P/M processing.

  19. Stress-corrosion behavior of aluminum-lithium alloys in aqueous salt environments

    NASA Technical Reports Server (NTRS)

    Pizzo, P. P.; Galvin, R. P.; Nelson, H. G.

    1984-01-01

    The stress corrosion susceptibility of two powder metallurgy (P/M) alloys, Al-Li-Cu and Al-Li-Cu-Mg; two mechanically attrited (M/A) alloys, Al-Li-Cu and Al-Li-Mg; and two wrought, ingot alloys, X-2020 and AA7475, are compared. Time-dependent fracture in an aqueous sodium chloride environment under alternate immersion condition was found to vary significantly between alloys. The stress corrosion behavior of the two powder metallurgy processed alloys was studied in detail under conditions of crack initiation, static crack growth, and fatigue crack growth. A variety of stress corrosion tests were performed including smooth surface, time-to-failure tests; potentiostatic tests on smooth surfaces exposed to constant applied strain rates; and fracture mechanics-type tests under static and cyclic loads. Both alloys show surface pitting and subsequent intergranular corrosion. Pitting is more severe in the magnesium-bearing alloy and is associated with stringer particles strung along the extrusion direction as a result of P/M processing.

  20. Pressure waves generated by metastable intermolecular composites in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Maines, G.; Radulescu, M.; Bacciochini, A.; Jodoin, B.; Lee, J. J.

    2014-05-01

    In the present study, pressure waves generated by a metastable intermolecular composite (MIC) have been measured experimentally in an aqueous environment and correlated with flame speed measurements. Underwater experiments were performed in a 1.0 L high-pressure chamber mounted with high-resolution pressure transducers and designed with optical access. Samples consisting of a stoichiometric mixture of aluminium and copper(II)-oxide particles were evaluated. Two types of samples were synthesized; a mixture of micron-sized raw powders, and ball-milled powders with a fine-scale nano-structure. A planetary mill was used to refine reactant powders from micron- to nano-scale dimensions. The dynamics of the pressure wave and high-pressure gas bubble were monitored via pressure histories and high-speed Schlieren visualization. The effect of reactant particle size has been evaluated quantitatively. The dynamics of the pressure wave were correlated with the rate of expansion of the high-pressure gas bubble.

  1. Pressure waves generated by metastable intermolecular composites in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Maines, Geoff; Radulescu, Matei; Bacciochini, Antoine; Jodoin, Bertrand; Lee, Julian

    2013-06-01

    In the present study, pressure waves generated by a metastable intermolecular composite (MIC) have been measured experimentally in an aqueous environment. Experiments were performed in a 1.0 L high pressure chamber mounted with high resolution pressure transducers and designed with optical access. Samples consisting of a stoichiometric mixture of aluminum and copper(II)oxide particles were evaluated. Two types of samples were constructed; a mixture of micron-sized raw powders, and ball milled powders with a lamellated nanostructure. A planetary mill was used to refine reactant powders from micron- to nano-scale dimensions. Manual compaction and cold spray deposition techniques were used to consolidate powders in various densities. The dynamics of the pressure wave and high pressure gas bubble were monitored via pressure data and high-speed Schlieren visualization. The effects of reactant particle size and sample density have been evaluated quantitatively and compared with equilibrium calculations. Dynamics of the pressure wave were correlated with the amount of gas released and the rate of burning of the sample material. Work supported by DRDC Suffield (Dr. Julian J. Lee).

  2. Aqueous phase hydration and hydrate acidity of perfluoroalkyl and n:2 fluorotelomer aldehydes.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program and comparative density functional theory (DFT) calculations were used to investigate the aqueous phase hydration equilibrium constants (Khyd) of perfluoroalkyl aldehydes (PFAlds) and n:2 fluorotelomer aldehydes (FTAlds). Both classes are degradation products of known industrial compounds and environmental contaminants such as fluorotelomer alcohols, iodides, acrylates, phosphate esters, and other derivatives, as well as hydrofluorocarbons and hydrochlorofluorocarbons. Prior studies have generally failed to consider the hydration, and subsequent potential hydrate acidity, of these compounds, resulting in incomplete and erroneous predictions as to their environmental behavior. In the current work, DFT calculations suggest that all PFAlds will be dominantly present as the hydrated form in aqueous solution. Both SPARC and DFT calculations suggest that FTAlds will not likely be substantially hydrated in aquatic systems or in vivo. PFAld hydrates are expected to have pKa values in the range of phenols (ca. 9 to 10), whereas n:2 FTAld hydrates are expected to have pKa values ca. 2 to 3 units higher (ca. 12 to 13). In order to avoid spurious modeling predictions and a fundamental misunderstanding of their fate, the molecular and/or dissociated hydrate forms of PFAlds and FTAlds need to be explicitly considered in environmental, toxicological, and waste treatment investigations. The results of the current study will facilitate a more complete examination of the environmental fate of PFAlds and FTAlds. PMID:26980678

  3. Dissociation quotient of benzoic acid in aqueous sodium chloride media to 250{degrees}C

    SciTech Connect

    Kettler, R.M.; Palmer, D.A.; Wesolowski, D.J.

    1995-04-01

    The dissociation quotient of benzoic acid was determined potentiometrically in a concentration cell fitted with hydrogen electrodes. The hydrogen ion molality of benzoic acid/benzoate solutions was measured relative to a standard aqueous HCl solution at seven temperatures from 5 to 250{degrees}C and at seven ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The molal dissociation quotients and selected literature data were fitted in the isocoulombic (all anionic) form by a six-term equation. This treatment yielded the following thermodynamic quantities for the acid dissociation equilibrium at 25{degrees}C and 1 bar: logK{sub a} = -4.206{+-}0.006, {Delta}H{sub a}{sup 0} = 0.3{+-}0.3 kJ-mol{sup {minus}1}, {Delta}S{sub a}{sup 0} = -79.6{+-}1.0 J-mol{sup {minus}1}-K{sup {minus}1}, and {Delta}C{sub p;a}{sup 0} = -207{+-}5 J-mol{sup {minus}1}-K{sup {minus}1}. A five-term equation derived to describe the dependence of the dissociation constant on solvent density is accurate to 250{degrees}C and 200 MPa.

  4. An ATR-FTIR study of different phosphonic acids in aqueous solution.

    PubMed

    Zenobi, María C; Luengo, Carina V; Avena, Marcelo J; Rueda, Elsa H

    2008-07-01

    An ATR-FIR study of the vibrational spectra of 1-hydroxyethane-1,1'-diphosphonic acid (HEDP), nitrilotris(methylenephosphonic acid) (NTMP) and N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid (BHAMP) in aqueous solution is presented. The study was performed in the range of pH from 5 to 9, and bands assignments are given in the 2000-890 cm(-1) range. However, as phosphonates display bands due to the PO stretching vibration mainly in the 900-1200 cm(-1) range, the study is focused in this midinfrared region, which shows important changes as the pH changes, specially the nu(POH) at approximately 925 cm(-1) and nu(PO(3)(2-)) at approximately 970 cm(-1) vibrations. IR analyses give also evidences for the zwitterionic nature of BHAMP and NTMP in solution with a strong indication that the zwitterion in both compounds remains intact throughout the pH range investigated. The successive protonation steps with the decrease of pH were evidenced in the IR spectra of the three studied phosphonates. PMID:17826311

  5. An ATR-FTIR study of different phosphonic acids in aqueous solution

    NASA Astrophysics Data System (ADS)

    Zenobi, María C.; Luengo, Carina V.; Avena, Marcelo J.; Rueda, Elsa H.

    2008-07-01

    An ATR-FIR study of the vibrational spectra of 1-hydroxyethane-1,1'-diphosphonic acid (HEDP), nitrilotris(methylenephosphonic acid) (NTMP) and N, N-bis(2-hydroxyethyl)aminomethylphosphonic acid (BHAMP) in aqueous solution is presented. The study was performed in the range of pH from 5 to 9, and bands assignments are given in the 2000-890 cm -1 range. However, as phosphonates display bands due to the P sbnd O stretching vibration mainly in the 900-1200 cm -1 range, the study is focused in this midinfrared region, which shows important changes as the pH changes, specially the ν(P sbnd OH) at ˜925 cm -1 and ν(PO 32-) at ˜970 cm -1 vibrations. IR analyses give also evidences for the zwitterionic nature of BHAMP and NTMP in solution with a strong indication that the zwitterion in both compounds remains intact throughout the pH range investigated. The successive protonation steps with the decrease of pH were evidenced in the IR spectra of the three studied phosphonates.

  6. Removal of boron from aqueous solution using magnetic carbon nanotube improved with tartaric acid

    PubMed Central

    2014-01-01

    Boron removal capacity of multi-walled carbon nanotubes (MWCNTs) modified with tartaric acid was investigated in this study. Modification of MWCNTs with tartaric acid was confirmed by Boehm surface chemistry method and fourier transform infra-red (FT-IR) spectroscopy. Experiments were performed to determine the adsorption isotherm and adsorption thermodynamic parameters of boron adsorption on tartaric acid modified MWCNTs (TA-MWCNTs). The effect of variables including initial pH, dosage of adsorbent, contact time and temperature was investigated. Analysis of data showed that adsorption equilibrium could be better described by Freundlich isotherm and the maximum adsorption capacities obtained at the pH of 6.0 was 1.97 mg/g. The estimated thermodynamic values of free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated a spontaneous and an endothermic process. Furthermore, the TA-MWCNTs was magnetized for separation of boron-contaminated adsorbent from aqueous solution by applying magnetic field. The results showed that magnetic TA-MWCNTs particles were separated effectively after adsorption from contaminated water. PMID:24393401

  7. The adsorption of cationic dye from aqueous solution onto acid-activated andesite.

    PubMed

    Tsai, Wen-Tien; Hsu, Hsin-Chieh; Su, Ting-Yi; Lin, Keng-Yu; Lin, Chien-Ming; Dai, Tzong-Hung

    2007-08-25

    The adsorption of cationic dye (i.e., methylene blue) onto acid-activated andesite in aqueous solution was studied in a batch system with respect to its kinetics as a function of agitation speed, initial adsorbate concentration, pH, and adsorbent mass. It was found that the resulting acid-activated adsorbent possessed a mesoporous structure with BET surface areas at around 60m(2)/g. The surface characterization of acid-activated andesite was also performed using the zeta-potential measurements, indicating that the charge sign on the surface of the andesite should be negative in a wide pH range (i.e., 3-11). Furthermore, a simplified kinetic model, pseudo-second-order, was tested to investigate the adsorption behaviors of methylene blue onto the clay samples treated under different process conditions. It was found that the adsorption process could be well described with the model. The adsorption capacity parameter of the model obtained in the present work was significantly in line with the process parameters. PMID:17363150

  8. The effect of fatty acid surfactants on the uptake of ozone to aqueous halogenide particles

    NASA Astrophysics Data System (ADS)

    Rouvière, A.; Ammann, M.

    2010-06-01

    The reactive uptake of ozone to deliquesced potassium iodide aerosol particles coated with linear saturated fatty acids (C9, C12, C15, C18 and C20) as surfactants was studied. The experiments were performed in an aerosol flow tube at 293 K and atmospheric pressure. The uptake coefficient on pure deliquesced KI aerosol was γ=(1.10±0.20)×10-2 at 72-75% relative humidity. In presence of organic coatings, the uptake coefficient decreased significantly for long straight chain surfactants (>C15), while it was only slightly reduced for the short ones (C9, C12). We linked the kinetic results to the monolayer properties of the surfactants, and specifically to the phase state of the monolayer formed (liquid expanded or liquid condensed state). We also investigated the effect of organic films to mixed deliquesced aerosol composed of a variable mixture of KI and NaCl, which allowed determining the resistance exerted to O3 at the aqueous surface by the two longer chained surfactants pentadecanoic acid (C15) and stearic acid (C18). Finally, the effect of two-component coatings, consisting of a mixture of long and short chained surfactants, was also studied.

  9. Effects of ultrasonic processing on degradation of salvianolic acid B in aqueous solution.

    PubMed

    Guo, Y X; Zhang, L; Lu, L; Liu, E H; Shi, C Z

    2016-09-10

    To evaluate the stability of salvianolic acid B (Sal B) under ultrasound-assisted extraction in the pharmaceutical industry, degradation of Sal B under ultrasonic irradiation was investigated as the function of buffer concentration, pH, and temperature. With regard to Sal-B concentration, a first-order degradation process was determined, with 10% change in assay from its initial concentration as t90=4.81h, under maximum stability acidic conditions (pH 2.0) and at 25°C. The logkpH-pH profile described by specific acid-base catalysis and water molecules supported the experimental results. Liquid chromatography-mass spectrometry (LC-MS) analyses revealed 7 major degradation products whose structures were characterized by electrospray ionization/mass spectrometry. A primary degradation pathway involved cleavage of the ester bond and ring-opening of benzofuran in Sal B was proposed. The complete degradation pathway of Sal B was also proposed. Results showed that ultrasonic irradiation leads to degradation of Sal B in aqueous solution. PMID:27442887

  10. Removal of Basic Violet 14 from aqueous solution using sulphuric acid activated materials.

    PubMed

    Suresh, S

    2016-01-01

    In this study the adsorption of Basic Violet, 14 from aqueous solution onto sulphuric acid activated materials prepared from Calophyllum inophyllum (CS) and Theobroma cacao (TS) shells were investigated. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models. The results showed that CS has a superior adsorption capacity compared to the TS. The adsorption capacity was found to be 1416.43 mg/g for CS and 980.39 mg/g for TS. The kinetic data results at different concentrations were analysed using pseudo first-order and pseudo-second order model. Boyd plot indicates that the dye adsorption onto CS and TS is controlled by film diffusion. The adsorbents were characterised by scanning electron microscopy. The materials used in this study were economical waste products and hence can be an attractive alternative to costlier adsorbents for dye removal in industrial wastewater treatment processes. PMID:27330899

  11. Equilibrium phase diagrams and water absorption properties of aqueous mixtures of malonic acid and inorganic salts.

    NASA Astrophysics Data System (ADS)

    Salcedo, D.; Salgado-Olea, G.

    2006-12-01

    Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. Solubility in water, water activity of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid with ammonium sulfate, ammonium bisulfate, and ammonium nitrate at 25oC over the full range of composition (from 0 wt% to the solubility limit of the mixture components). The data was used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity. Measured water activity of liquid solutions was compared with an extended Zdanovskii-Stokes-Robinson (ZSR) expression, which then was used to predict water absorption of the mixtures.

  12. Fixed bed adsorption of 2-naphthalenesulfonic acid from aqueous solution by composite resin.

    PubMed

    Jia, Dong M; Li, Ya P; Li, Yue J; Li, Yong G; Li, Chang H

    2014-02-01

    Adsorption behavior of the iron impregnated, weakly basic resin D301 (Fe-D301) for removal of 2-naphthalenesulfonic acid (2-NSA) from aqueous solution was studied by using a fixed-bed column. The effects of process variables such as bed height, flow rate, and coexisting ions were investigated. The results indicated that the breakpoint and exhaustion point increased with increasing bed height and decreased with increasing 2-NSA flowrate. Experimental data showed a strong fit to the Bed Depth Service Time model. The coexisting ions in the 2-NSA solution had a clear effect on the breakthrough volume. The high extent of recovery of 2-NSA with good reproducibility provided an effective method for the separation of 2-NSA by the adsorbent Fe-D301. PMID:24645539

  13. Optical properties of colloidal aqueous synthesized 3 mercaptopropionic acid stabilized CdS quantum dots

    NASA Astrophysics Data System (ADS)

    Sumanth Kumar, D.; Jai Kumar, B.; Mahesh H., M.

    2016-05-01

    We have explored an easiest and simplest aqueous route to synthesize bright green luminescent CdS QDs using 3-Mercaptopropionic acid (MPA) as a stabilizer in air ambient for solar cell applications. The CdS quantum dots showed a strong quantum confinement effect with good stability, size and excellent photoluminescence. MPA Capping on CdS QDs was confirmed through FTIR. The Optical absorption spectrum revealed the CdS quantum dots are highly transparent in the visible region with absorption peak at 380 nm, confirming the quantum confinement. Photoluminescence showed an emission peak at 525 nm wavelength. The optical band gap energy was found to be 3.19 eV and CdS quantum dots radius calculated using Brus equation is 1.5 nm. The results are presented and discussed in detail.

  14. Prompt formation of organic acids in pulse ozonation of terpenes on aqueous surfaces

    NASA Astrophysics Data System (ADS)

    Hoffmann, M. R.; Colussi, A. J.; Enami, S.

    2010-12-01

    A major atmospheric process, the gas-phase ozonation of terpenes yields suites of products via a cascade of chemically activated intermediates that ranges from primary ozonides to dioxiranes. If a similar mechanism operated in water, as it is generally assumed, such intermediates would be deactivated within picoseconds and, henceforth, unable to produce carboxylic acids in microseconds. Herein we report the online electrospray mass spectrometric detection of (M + 2O - H+) and (M + 3O - H+) carboxylates on the surface of aqueous β-caryophyllene (C15H24, M = 204 Da) microjets exposed to a few ppmv O3(g) for < 10 μs. Since neither species is formed on dry solvent microjets, and both incorporate deuterium from D2O, we infer that carboxylates ensue from the interaction of nascent intermediates with interfacial water via a heretofore unreported mechanism. These interfacial events proceed much faster than in bulk liquids saturated with ozone.

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

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

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

  16. Microfluidic study on CNT dispersion during breakup of aqueous alginic acid drop in continuous PDMS phase

    NASA Astrophysics Data System (ADS)

    Choi, Jae Hong; Nam, Young Woo; Hong, Joung Sook

    2013-02-01

    Microfluidic study is performed to investigate how multi-walled carbon nanotube (CNTs) aggregates disperse in blend system during morphology evolution. As the dispersed phase, a drop containing CNT is generated at the flow focusing and it deforms through a contraction channel (gap and width of contraction ˜ 100 μm). When an aqueous polymeric drop (2 wt% alginic acid) with CNT (0.05 wt% or 0.5 wt%) is stretched through a 4:1 contraction channel, CNT aggregates enhances breakup of the stretched drop. Also, small droplets including CNTs are pinched off during relaxation of the stretched drop. Based on these observations, it is found that CNTs disperse in a multiphase system by repetitive breakup process during mixing rather than migration driven by chemical affinity.

  17. The aqueous photolysis of α-pinene in solution with humic acid

    NASA Astrophysics Data System (ADS)

    Goldberg, Marvin C.; Cunningham, Kirkwood M.; Aiken, George R.; Weiner, Eugene R.

    1992-01-01

    Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.

  18. Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Veres, P. R.; Warneke, C.; Roberts, J. M.; Gilman, J. B.; Koss, A.; Edwards, P. M.; Graus, M.; Kuster, W. C.; Li, S.-M.; Wild, R. J.; Brown, S. S.; Dubé, W. P.; Lerner, B. M.; Williams, E. J.; Johnson, J. E.; Quinn, P. K.; Bates, T. S.; Lefer, B.; Hayes, P. L.; Jimenez, J. L.; Weber, R. J.; Zamora, R.; Ervens, B.; Millet, D. B.; Rappenglück, B.; de Gouw, J. A.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that

  19. Sailing into uncharted waters: recent advances in the in situ monitoring of catalytic processes in aqueous environments

    SciTech Connect

    Shi, Hui; Lercher, Johannes A.; Yu, Xiao-Ying

    2015-01-01

    Catalysis in aqueous environments is attracting enormous interest. Many characterization methods are well established at gas-solid interfaces and a majority of the surface-science approaches were historically limited to model surfaces and vacuum conditions. However, practical scenarios with complex catalyst structures, elevated temperatures and pressures, as well as the presence of two or more condensed phases, can pose significant challenges to these techniques, particularly for catalysts at their dynamic working states. In such contexts, this review highlights the advances over the past five years in the in situ and real-time detection of catalytic processes and related phenomena in aqueous media, ideally under realistic conditions. We underline latest technical innovations, describe novel chemistries that are made accessible by recently developed toolboxes, and discuss future directions of in situ and time-resolved analytical approaches applicable to aqueous phase catalysis.

  20. Hydroxyl radical (OH•) reaction with guanine in an aqueous environment: a DFT study.

    PubMed

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D

    2011-12-22

    The reaction of hydroxyl radical (OH(•)) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH(•) with DNA proceeds mainly through the addition of OH(•) to the C═C bonds of the DNA bases. However, recently it has been reported that the principal reaction of OH(•) with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH(•) to the C═C bonds. In the present work, these two reaction pathways of OH(•) attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH(•) at C(4)═C(5) double bond of guanine is barrier free and the adduct radical (G-OH(•)) has only a small activation barrier of ca. 1-6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G(•+)---OH(-)). The formation of ion-pair is a result of the highly oxidizing nature of the OH(•) in aqueous media. The resulting ion-pair (G(•+)---OH(-)) deprotonates to form H(2)O and neutral G radicals favoring G(N(1)-H)(•) with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C(4))-OH(•) (adduct) to G(N(1)-H)(•) and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH(•)), (G(•+)---OH(-)), and G(N(1)-H)(•) were further characterized by the CAM-B3LYP calculations of their UV-vis spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N(1) and N(2) sites of guanine by the OH(•) show that this is also a competitive route to produce G(N(2)-H)(•), G(N(1)-H)(•) and H(2)O. PMID:22050033

  1. Sphingosine-1-Phosphate as an Amphipathic Metabolite: Its Properties in Aqueous and Membrane Environments

    PubMed Central

    García-Pacios, Marcos; Collado, M. Isabel; Busto, Jon V.; Sot, Jesús; Alonso, Alicia; Arrondo, José-Luis R.; Goñi, Félix M.

    2009-01-01

    Abstract Sphingosine-1-phosphate (S1P) is currently considered to be an important signaling molecule in cell metabolism. We studied a number of relevant biophysical properties of S1P, using mainly Langmuir balance, differential scanning calorimetry, 31P-NMR, and infrared (IR) spectroscopy. We found that, at variance with other, structurally related sphingolipids that are very hydrophobic, S1P may occur in either an aqueous dispersion or a bilayer environment. S1P behaves in aqueous media as a soluble amphiphile, with a critical micelle concentration of ≈12 μM. Micelles give rise to larger aggregates (in the micrometer size range) at and above a 1 mM concentration. The aggregates display a thermotropic transition at ∼60°C, presumably due to the formation of smaller structures at the higher temperatures. S1P can also be studied in mixtures with phospholipids. Studies with dielaidoylphosphatidylethanolamine (DEPE) or deuterated dipalmitoylphosphatidylcholine (DPPC) show that S1P modifies the gel-fluid transition of the glycerophospholipids, shifting it to lower temperatures and decreasing the transition enthalpy. Low (<10 mol %) concentrations of S1P also have a clear effect on the lamellar-to-inverted hexagonal transition of DEPE, i.e., they increase the transition temperature and stabilize the lamellar versus the inverted hexagonal phase. IR spectroscopy of natural S1P mixed with deuterated DPPC allows the independent observation of transitions in each molecule, and demonstrates the existence of molecular interactions between S1P and the phospholipid at the polar headgroup level that lead to increased hydration of the carbonyl group. The combination of calorimetric, IR, and NMR data allowed the construction of a temperature-composition diagram (“partial phase diagram”) to facilitate a comparative study of the properties of S1P and other related lipids (ceramide and sphingosine) in membranes. In conclusion, two important differences between S1P and ceramide

  2. Hydroxyl Radical (OH•) Reaction with Guanine in an Aqueous Environment: A DFT Study

    PubMed Central

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D.

    2011-01-01

    The reaction of hydroxyl radical (OH•) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH• with DNA proceeds mainly through the addition of OH• to the C=C bond of the DNA bases. However, recently it has been reported that the principal reaction of OH• with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH• to the C=C bond. In the present work, these two reaction pathways of OH• attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH• at C4=C5 double bond of guanine is barrier free and the adduct radical (G-OH•) has only a small activation barrier of ca. 1 – 6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G•+---OH−). The formation of ion-pair is a result of the highly oxidizing nature of the OH• in aqueous media. The resulting ion-pair (G•+---OH−) deprotonates to form H2O and neutral G radicals favoring G(N1-H)• with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C4)-OH• (adduct) to G(N1-H)• and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH•), (G•+---OH−), and G(N1-H)• were further characterized by the CAM-B3LYP calculations of their UV-visible spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N1 and N2 sites of guanine by the OH• show that this is also a competitive route to produce G(N2-H)•, G(N1-H)• and H2O. PMID:22050033

  3. Sphingosine-1-phosphate as an amphipathic metabolite: its properties in aqueous and membrane environments.

    PubMed

    García-Pacios, Marcos; Collado, M Isabel; Busto, Jon V; Sot, Jesús; Alonso, Alicia; Arrondo, José-Luis R; Goñi, Félix M

    2009-09-01

    Sphingosine-1-phosphate (S1P) is currently considered to be an important signaling molecule in cell metabolism. We studied a number of relevant biophysical properties of S1P, using mainly Langmuir balance, differential scanning calorimetry, (31)P-NMR, and infrared (IR) spectroscopy. We found that, at variance with other, structurally related sphingolipids that are very hydrophobic, S1P may occur in either an aqueous dispersion or a bilayer environment. S1P behaves in aqueous media as a soluble amphiphile, with a critical micelle concentration of approximately 12 muM. Micelles give rise to larger aggregates (in the micrometer size range) at and above a 1 mM concentration. The aggregates display a thermotropic transition at approximately 60 degrees C, presumably due to the formation of smaller structures at the higher temperatures. S1P can also be studied in mixtures with phospholipids. Studies with dielaidoylphosphatidylethanolamine (DEPE) or deuterated dipalmitoylphosphatidylcholine (DPPC) show that S1P modifies the gel-fluid transition of the glycerophospholipids, shifting it to lower temperatures and decreasing the transition enthalpy. Low (<10 mol %) concentrations of S1P also have a clear effect on the lamellar-to-inverted hexagonal transition of DEPE, i.e., they increase the transition temperature and stabilize the lamellar versus the inverted hexagonal phase. IR spectroscopy of natural S1P mixed with deuterated DPPC allows the independent observation of transitions in each molecule, and demonstrates the existence of molecular interactions between S1P and the phospholipid at the polar headgroup level that lead to increased hydration of the carbonyl group. The combination of calorimetric, IR, and NMR data allowed the construction of a temperature-composition diagram ("partial phase diagram") to facilitate a comparative study of the properties of S1P and other related lipids (ceramide and sphingosine) in membranes. In conclusion, two important differences

  4. Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

    USGS Publications Warehouse

    Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

    1993-01-01

    Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

  5. Chemistry in the Venus clouds: Sulfuric acid reactions and freezing behavior of aqueous liquid droplets

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, K. H.

    2015-11-01

    Venus has a thick cloud deck at 40-70 km altitude consisting of liquid droplets and solid particles surrounded by atmospheric gases. The liquid droplets are highly concentrated aqueous solutions of sulfuric acid ranging in concentration from 70-99 wt%. Weight percent drops off with altitude (Imamura and Hashimoto 2001). There will be uptake of atmospheric gases into the droplet solutions and the ratios of gas-phase to liquid-phase species will depend on the Henry’s Law constant for those solutions. Reactions of sulfuric acid with these gases will form products with differing solubilities. For example, uptake of HCl by H2SO4/H2O droplets yields chlorosulfonic acid, ClSO3H (Robinson et al 1998) in solution. This may eventually decompose to thionyl- or sulfuryl chlorides, which have UV absorbances. HF will also uptake, creating fluorosulfonic acid, FSO3H, which has a greater solubility than the chloro- acid. As uptake continues, there will be many dissolved species in the cloudwaters. Baines and Delitsky (2013) showed that uptake will have a maximum at ~62 km and this is very close to the reported altitude for the mystery UV absorber in the Venus atmosphere. In addition, at very strong concentrations in lower altitude clouds, sulfuric acid will form hydrates such as H2SO4.H2O and H2SO4.4H2O which will have very different freezing behavior than sulfuric acid, with much higher freezing temperatures (Carslaw et al, 1997). Using temperature data from Venus Express from Tellmann et al (2009), and changes in H2SO4 concentrations as a function of altitude (James et al 1997), we calculate that freezing out of sulfuric acid hydrates can be significant down to as low as 56 km altitude. As a result, balloons, aircraft or other probes in the Venus atmosphere may be limited to flying below certain altitudes. Any craft flying at altitudes above ~55 km may suffer icing on the wings, propellers, balloons and instruments which could cause possible detrimental effects (thermal

  6. Acidic Alteration Environments on Mars and Implications for Habitability

    NASA Astrophysics Data System (ADS)

    Bishop, J. L.; Flahaut, J.; Weitz, C. M.; Gross, C.; Parente, M.; Horgan, B. H. N.

    2014-12-01

    Unique surface materials have been discovered recently at Valles Marineris (Roach et al., 2010; Weitz et al., 2014; Flahaut et al., 2014), Noctis Labyrinthus (Weitz et al., 2011), Mawrth Vallis (Bishop et al., 2013), and elsewhere that have CRISM features distinct from those of any known minerals. Typically these unusual sites are found in light-toned outcrops or interior layered deposits associated with phyllosilicates, sulfates or both. Frequently these units are called "doublet" materials because they exhibit a doublet absorption in CRISM spectra between 2.2 and 2.3 µm. We are investigating the spectral signatures of these martian materials compared to our library of minerals and alteration materials. We are also evaluating the stratigraphy of these unique alteration phases compared with neighboring phyllosilicate and sulfate units. A similar 2.2-2.3 µm doublet has been observed in spectra taken of acid altered clays produced in the laboratory (Madejova et al., 2009; Tosca et al., 2009). The band centers and relative intensities of these martian doublet features vary greatly suggesting that a process such as acid weathering could be acting on OH-bearing minerals to produce altered phases that differ depending on the type of substrate, water/rock ratio, solution chemistry, and duration of aqueous processes. Because these unique materials occur in many regions across a range of times on Mars, acidic alteration may have been a key process at local and regional scales throughout martian geologic history. Constraining the types of acidic alteration that have taken place on Mars will assist in defining the aqueous geochemistry at these sites and whether habitable conditions were possible. References: Bishop et al. (2013) PSS, 86, 130-149. Flahaut et al. (2014) EPSC, #211. Madejová et al. (2009) Vibrational Spectroscopy, 49, 211-218. Roach et al. (2010) Icarus, 206, 253-268. Tosca & Knoll (2009) 40th LPSC, #1538. Weitz et al. (2011) Geology, 39, 899-902. Weitz et al

  7. Electrochemical treatment of acidic aqueous ferrous sulfate and copper sulfate as models for acid mine drainage.

    PubMed

    Bunce, N J; Chartrand, M; Keech, P

    2001-12-01

    Acid mine drainage (AMD) is a serious environmental problem in the mining industry. The present work describes electrolytic reduction of solutions of synthetic AMD, comprising FeSO4/H2SO4 and CuSO4/H2SO4, in flow-through cells whose anode and cathode compartments were separated using ion exchange membranes. In the case of FeSO4/H2SO4 at constant flow rate, the pH of the effluent from the catholyte increased progressively with current at a variety of cathodes, due to electrolytic reduction of H+ ions to elemental hydrogen. Near-quantitative removal of iron was achieved by sparging air into the catholyte effluent, thereby precipitating iron outside the electrochemical cell, and avoiding fouling of the electrodes. The anode reaction was the oxidation of water to O2, a proton-releasing process. Using cation exchange membranes and sodium sulfate as the supporting electrolyte in the anode compartment, the efficiency of the process was compromised at high currents by transport of H+ competitively with Na+ from the anode to the cathode compartments. Higher efficiencies were obtained when anion exchange membranes were used, and in this case no additional supporting electrolyte other than dilute H2SO4 was needed, the net reaction being the electrochemically driven transfer of the elements of H2SO4 from the cathode to the anode compartments. Current efficiencies approximately 50% were achieved, the loss of efficiency being accounted for by ohmic heating of the solutions. In the case of CuSO4/H2SO4 and anion exchange membranes at high currents, reduction of Cu2+ and H+ ions and transport of SO4(2-) ions out of the catholyte caused unacceptably high potentials to be generated. PMID:11763043

  8. Novel acid resistance genes from the metagenome of the Tinto River, an extremely acidic environment.

    PubMed

    Guazzaroni, María-Eugenia; Morgante, Verónica; Mirete, Salvador; González-Pastor, José E

    2013-04-01

    Microorganisms that thrive in acidic environments are endowed with specialized molecular mechanisms to survive under this extremely harsh condition. In this work, we performed functional screening of six metagenomic libraries from planktonic and rhizosphere microbial communities of the Tinto River, an extremely acidic environment, to identify genes involved in acid resistance. This approach has revealed 15 different genes conferring acid resistance to Escherichia coli, most of which encoding putative proteins of unknown function or previously described proteins not known to be related to acid resistance. Moreover, we were able to assign function to one unknown and three hypothetical proteins. Among the recovered genes were the ClpXP protease, the transcriptional repressor LexA and nucleic acid-binding proteins such as an RNA-binding protein, HU and Dps. Furthermore, nine of the retrieved genes were cloned and expressed in Pseudomonas putida and Bacillus subtilis and, remarkably, most of them were able to expand the capability of these bacteria to survive under severe acid stress. From this set of genes, four presented a broad-host range as they enhance the acid resistance of the three different organisms tested. These results expand our knowledge about the different strategies used by microorganisms to survive under extremely acid conditions. PMID:23145860

  9. A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

    EPA Science Inventory

    A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

  10. Context of ancient aqueous environments on Mars from in situ geologic mapping at Endeavour Crater

    NASA Astrophysics Data System (ADS)

    Crumpler, L. S.; Arvidson, R. E.; Bell, J.; Clark, B. C.; Cohen, B. A.; Farrand, W. H.; Gellert, R.; Golombek, M.; Grant, J. A.; Guinness, E.; Herkenhoff, K. E.; Johnson, J. R.; Jolliff, B.; Ming, D. W.; Mittlefehldt, D. W.; Parker, T.; Rice, J. W., Jr.; Squyres, S. W.; Sullivan, R.; Yen, A. S.

    2015-03-01

    Using the Mars Exploration Rover Opportunity, we have compiled one of the first field geologic maps on Mars while traversing the Noachian terrain along the rim of the 22 km diameter Endeavour Crater (Latitude -2°16'33", Longitude -5°10'51"). In situ mapping of the petrographic, elemental, structural, and stratigraphic characteristics of outcrops and rocks distinguishes four mappable bedrock lithologic units. Three of these rock units predate the surrounding Burns formation sulfate-rich sandstones and one, the Matijevic Formation, represents conditions on early Mars predating the formation of Endeavour Crater. The stratigraphy assembled from these observations includes several geologic unconformities. The differences in lithologic units across these unconformities record changes in the character and intensity of the Martian aqueous environment over geologic time. Water circulated through fractures in the oldest rocks over periods long enough that texturally and elementally significant alteration occurred in fracture walls. These oldest pre-Endeavour rocks and their network of mineralized and altered fractures were preserved by burial beneath impact ejecta and were subsequently exhumed and exposed. The alteration along joints in the oldest rocks and the mineralized veins and concentrations of trace metals in overlying lithologic units is direct evidence that copious volumes of mineralized and/or hydrothermal fluids circulated through the early Martian crust. The wide range in intensity of structural and chemical modification from outcrop to outcrop along the crater rim shows that the ejecta of large (>8 km in diameter) impact craters is complex. These results imply that geologic complexity is to be anticipated in other areas of Mars where cratering has been a fundamental process in the local and regional geology and mineralogy.

  11. Context of ancient aqueous environments on Mars from in situ geologic mapping at Endeavour Crater

    USGS Publications Warehouse

    Crumpler, L.S.; Arvidson, R. E.; Bell, J.; Clark, B. C.; Cohen, B. A.; Farrand, W. H.; Gellert, Ralf; Golombek, M.; Grant, J. A.; Guinness, E.; Herkenhoff, Kenneth E.; Johnson, J. R.; Jolliff, B.; Ming, D. W.; Mittlefehldt, D. W.; Parker, T.; Rice, J. W., Jr.; Squyres, S. W.; Sullivan, R.; Yen, A. S.

    2015-01-01

    Using the Mars Exploration Rover Opportunity, we have compiled one of the first field geologic maps on Mars while traversing the Noachian terrain along the rim of the 22 km diameter Endeavour Crater (Latitude −2°16′33″, Longitude −5°10′51″). In situ mapping of the petrographic, elemental, structural, and stratigraphic characteristics of outcrops and rocks distinguishes four mappable bedrock lithologic units. Three of these rock units predate the surrounding Burns formation sulfate-rich sandstones and one, the Matijevic Formation, represents conditions on early Mars predating the formation of Endeavour Crater. The stratigraphy assembled from these observations includes several geologic unconformities. The differences in lithologic units across these unconformities record changes in the character and intensity of the Martian aqueous environment over geologic time. Water circulated through fractures in the oldest rocks over periods long enough that texturally and elementally significant alteration occurred in fracture walls. These oldest pre-Endeavour rocks and their network of mineralized and altered fractures were preserved by burial beneath impact ejecta and were subsequently exhumed and exposed. The alteration along joints in the oldest rocks and the mineralized veins and concentrations of trace metals in overlying lithologic units is direct evidence that copious volumes of mineralized and/or hydrothermal fluids circulated through the early Martian crust. The wide range in intensity of structural and chemical modification from outcrop to outcrop along the crater rim shows that the ejecta of large (>8 km in diameter) impact craters is complex. These results imply that geologic complexity is to be anticipated in other areas of Mars where cratering has been a fundamental process in the local and regional geology and mineralogy.

  12. Preferred conformation of endomorphin-1 in aqueous and membrane-mimetic environments.

    PubMed

    Fiori, S; Renner, C; Cramer, J; Pegoraro, S; Moroder, L

    1999-08-01

    The newly discovered endomorphin-1 (Tyr-Pro-Trp-Phe-NH2) and endomorphin-2 (Tyr-Pro-Phe-Phe-NH2) are potent opioid peptides with the highest affinity and selectivity for the mu receptor among all known endogenous ligands. To investigate a possible correlation between these biological properties and the conformational preferences of the small peptides, a comparative structural analysis was performed of endomorphin-1 in aqueous buffer and in membrane-mimicking SDS and AOT normal and reverse micelles by the use of CD, FT-IR, fluorescence and(1)H-NMR spectroscopy. It is well established for opioid peptides that, independently of the receptor selectivity, the Tyr1 residue plays the role of the primary pharmacophore and that the orientation of the second aromatic pharmacophore relative to the tyrosine side-chain dictates the mu or delta-receptor selectivity. By varying the environment of endomorphin-1 from water to the amphipathic SDS micelles and even more efficiently to the AOT reverse micelles, the display of the aromatic side-chains changes from an interaction of the Tyr1 and Phe4 residues to a switch of the Trp3 indole group into close contact with the phenolic moiety to prevent this type of interaction and to force an orientation of the Phe4 side-chain into the opposite direction. This conformational switch is accompanied by a stabilization of the cis -Pro2 isomer and the resulting spatial array of the pharmacophoric groups correlate well with the structural model of mu receptor-bound opioid peptides. The results indicate that AOT reverse micelles with a woof 10, where almost exclusively ordered water is secluded in the cavity, constitute with their electrostatic and hydrophobic potential an excellent mimetic of amphipathic surfaces as present on lipid bilayers and on ligand-recognition and ligand-binding sites of proteins. PMID:10438613

  13. Fabrication and characterization of ultrathin dextran layers: Time dependent nanostructure in aqueous environments revealed by OWLS.

    PubMed

    Saftics, Andras; Kurunczi, Sándor; Szekrényes, Zsolt; Kamarás, Katalin; Khánh, Nguyen Quoc; Sulyok, Attila; Bősze, Szilvia; Horvath, Robert

    2016-10-01

    Surface coatings of the polysaccharide dextran and its derivatives are key ingredients especially in label-free biosensors for the suppression of non-specific binding and for receptor immobilization. Nevertheless, the nanostructure of these ultrathin coatings and its tailoring by the variation of the preparation conditions have not been profoundly characterized and understood. In this work carboxymethylated dextran (CMD) was prepared and used for fabricating ultrathin surface coatings. A grafting method based on covalent coupling to aminosilane- and epoxysilane-functionalized surfaces was applied to obtain thin CMD layers. The carboxyl moiety of the CMD was coupled to the aminated surface by EDC-NHS reagents, while CMD coupling through epoxysilane molecules was performed without any additional reagents. The surface analysis following the grafting procedures consisted of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared spectroscopy (ATR-IR), spectroscopic ellipsometry, atomic force microscopy (AFM) and optical waveguide lightmode spectroscopy (OWLS). The XPS and AFM measurements showed that the grafting resulted in a very thin dextran layer of a few nanometers. The OWLS method allowed devising the structure of the interfacial dextran layers by the evaluation of the optogeometrical parameters. The alteration in the nanostructure of the CMD layer with the chemical composition of the silane coverage and the pH of the grafting solution was revealed by in situ OWLS, specifically, lain down chains were found to be prevalent on the surface under neutral and basic conditions on epoxysilylated surfaces. The developed methodologies allowed to design and fabricate nanometer scale CMD layers with well-controlled surface structure, which are very difficult to characterize in aqueous environments using present instrumentations and highly hydrated surface layers. PMID:27455406

  14. Biodegradation of ethylene vinyl alcohol by aerobic organisms in an aqueous environment

    SciTech Connect

    Rhoades, J.J. Jr.; Young, J.C.

    1996-11-01

    Ethylene vinyl alcohol (EVOH) is a thermoplastic used extensively in laminates for food containers. This study investigates the biodegradability of EVOH utilizing ASTM Test Method D5271. This method indicates the extent and rate of biodegradation of plastic materials by aerobic microorganisms in an aqueous environment and is performed in a respirometer. The ethylene derived segments of the EVOH contain {sup 14}C which acts as tracer to measure biodegradation as indicated by the {sup 14}C-CO{sub 2} given off by microbial metabolism. Liquid scintillation counting measured the activity of the respired {sup 14}C-CO{sub 2} converted from the ethylene segments of the EVOH. Three physical forms of EVOH were tested: a pure EVOH, a high surface area EVOH, and a blended form of EVOH with polyvinyl alcohol (PVOH). The reactors with these EVOH forms were set up to receive a weekly influx of microorganisms (inoculum), or various amounts of POH as a co-substrate. Results to date have indicated that an increased surface area for the EVOH increases conversion of {sup 14}C relative to the pure EVOH. Some cases with blended EVOH/PVOH reactors have also showed increased conversion of {sup 14}C relative to the pure EVOH cases. The addition of inoculum to the reactors did not seem to significantly increase the conversion of {sup 14}C as compared to the effect of PVOH addition. PVOH co-substrate addition increased {sup 14}C conversion. Also, increasing the amount of PVOH co-substrate addition further increases the conversion of {sup 14}C.

  15. Biosorption of methyl blue onto tartaric acid modified wheat bran from aqueous solution

    PubMed Central

    2012-01-01

    Tartaric acid modified wheat bran was utilized as adsorbent to remove methyl blue, a basic dye from aqueous solution. Batch experiments were carried out to study the effect of various experimental parameters such as initial solution pH, contact time, initial dye concentration and adsorbent dosage, on dye adsorption. The results showed that the modification of wheat bran by tartaric acid significantly improved its adsorption capacity, and made this material a suitable adsorbent to remove methyl blue. The adsorption capacity of modified wheat bran was about 1.6 times higher than that of unmodified one. The amount of methyl blue adsorbed was found to vary with initial solution pH, adsorbent dosage, contact time and initial methyl blue concentration. Kinetics study showed that the overall adsorption rate of methyl blue was illustrated by pseudo-second-order kinetic model. The applicability of the Langmuir and Freundlich models for the data was tested. Both models adequately described the experimental data of the biosorption of methyl blue. The maximum adsorption capacity for methyl blue calculated from Langmuir model was 25.18 mg/g. The study has shown the effectiveness of modified wheat bran in the removal of methyl blue, and that it can be considered as an attractive alternative to the more expensive technologies used in wastewater treatment. PMID:23369295

  16. HCN, Formamidic Acid, and Formamide in Aqueous Solution: A Free-Energy Map.

    PubMed

    Kua, Jeremy; Thrush, Kyra L

    2016-08-25

    What chemical species might be found if water or ammonia reacts with HCN in aqueous solution under neutral conditions? Is it energetically favorable for formamidic acid, the first hydration product of HCN, to tautomerize into formamide under standard conditions? Do these molecules form stable oligomers in solution? To answer these questions, we constructed a Gibbs free-energy map of the molecules that might be present to evaluate their relative thermodynamic and kinetic stability. Our protocol utilizes density functional theory calculations, Poisson-Boltzmann implicit solvent, and thermodynamic corrections. We find that for C1 species, formamide is indeed the thermodynamic sink, although the initial barrier to hydration is ∼30 kcal/mol. Molecules with one carbon and three heteroatoms are less stable. We also find that for HCN trimerization, although the planar sp(2) six-membered ring is more stable compared to its monomers, the reverse is true for the nonplanar sp(3) six-membered rings formed by trimerization of formamidic acid or formamide. PMID:27016454

  17. Preparation of aqueous alpha-lipoic acid dispersions with octenylsuccinylated high amylose starch.

    PubMed

    Li, Yi-Xuan; Lim, Seung-Taik

    2016-04-20

    Aqueous dispersions prepared with OSA-modified high amylose starch were investigated in comparison with native high amylose starch and beta-cyclodextrin using alpha-lipoic acid as a model substance. Alpha-lipoic acid (ALA), a lipophilic antioxidant essential for energy metabolism in human, was dispersed in gelatinized starch solutions (1.0% w/v) at different temperatures (50-90°C) and times (3-12h). High amylose starch modified with 3% OSA (dry starch base) was most favored in maximizing the dispersibility of ALA (84% recovery) under mild heating (70°C for 3h). The optimally prepared dispersion was milky white and contained particles with a narrow size distribution (200-300nm). The precipitate isolated from the dispersion contained crystalline V-complexes of ALA and amylose while the supernatant contained free ALA accounting for 1/3 of total ALA, indicating OSA-modified high amylose starch stabilized ALA either by complexing with amylose or by retarding aggregation of ALA. PMID:26876852

  18. Biosorption of methyl blue onto tartaric acid modified wheat bran from aqueous solution.

    PubMed

    Yao, Shuhua; Lai, Hong; Shi, Zhongliang

    2012-01-01

    Tartaric acid modified wheat bran was utilized as adsorbent to remove methyl blue, a basic dye from aqueous solution. Batch experiments were carried out to study the effect of various experimental parameters such as initial solution pH, contact time, initial dye concentration and adsorbent dosage, on dye adsorption. The results showed that the modification of wheat bran by tartaric acid significantly improved its adsorption capacity, and made this material a suitable adsorbent to remove methyl blue. The adsorption capacity of modified wheat bran was about 1.6 times higher than that of unmodified one. The amount of methyl blue adsorbed was found to vary with initial solution pH, adsorbent dosage, contact time and initial methyl blue concentration. Kinetics study showed that the overall adsorption rate of methyl blue was illustrated by pseudo-second-order kinetic model. The applicability of the Langmuir and Freundlich models for the data was tested. Both models adequately described the experimental data of the biosorption of methyl blue. The maximum adsorption capacity for methyl blue calculated from Langmuir model was 25.18 mg/g. The study has shown the effectiveness of modified wheat bran in the removal of methyl blue, and that it can be considered as an attractive alternative to the more expensive technologies used in wastewater treatment. PMID:23369295

  19. Removal of aqueous perfluorooctanoic acid (PFOA) using starch-stabilized magnetite nanoparticles.

    PubMed

    Gong, Yanyan; Wang, Lin; Liu, Juncheng; Tang, Jingchun; Zhao, Dongye

    2016-08-15

    Fully stabilized magnetite (Fe3O4) nanoparticles were prepared with a water-soluble starch as a stabilizer and tested for removal of aqueous perfluorooctanoic acid (PFOA). The presence of starch at ≥0.2wt% can fully stabilize 0.1g/L as Fe of the Fe3O4 nanoparticles. The particle stabilization technique resulted in 2.4 times higher PFOA uptake. Fourier transform infrared spectra suggested that the main PFOA removal mechanism was inner-sphere complexation. Batch kinetic experiments revealed that the starch-stabilized nanoparticles facilitated a rapid PFOA uptake with a sorption equilibrium time of 30min, and the sorption process followed a pseudo-second-order kinetic model. The Langmuir model was able to well interpret the adsorption isotherm, with a maximum adsorption capacity of 62.5mg/g. Increasing pH from 4.7 to 9.6 led to a sharp increase (by 2.6 times) in PFOA uptake. The presence of 12mg/L humic acid inhibited PFOA uptake by 96%, while effect of ionic strength (CaCl2=0-2mmol/L) was negligible. The nanoparticles significantly reduced the biological toxicity of PFOA. The results demonstrated promise of starch-stabilized Fe3O4 nanoparticles as a "green" adsorbent for effective removal of PFOA in soil and groundwater. PMID:27100000

  20. A chemiluminescence-based continuous flow aqueous ozone analyzer using photoactivated chromotropic acid.

    PubMed

    Takayanagi, Toshio; Dasgupta, Purnendu K

    2005-05-15

    Ozone has become the oxidant of choice for water disinfection, especially in large water treatment facilities. This paper describes a fast and sensitive method for the determination of ozone content by reaction with photoactivated chromotropic acid (CA, 4,5-dihydroxynaphthalene-2,7-disulfonic acid), which results in intense chemiluminescence (CL). Freshly ozonated water from a recirculating ozonizer/reservoir is injected into a carrier stream of deionized water in the flow-injection mode. This flow mixes with a stream of photoactivated CA solution in a spiral cell placed directly on top of an inexpensive miniature (8mm diameter active area) photomultiplier tube (PMT). Alkaline CA is photoactivated by passing it through a FEP-Teflon((R)) coil (residence time approximately 50s) wrapped around a 1W UV lamp emitting at 254nm; without photoactivation, the signal is approximately 70-fold lower. The S/N=3 limit of detection for aqueous ozone is 3mugl(-1) and good response slope is obtained up to an ozone concentration of 1.4mgl(-1), the highest that could be made in this study. The response obeyed a quadratic equation with r(2)=0.9984. No interference from permanganate ion is observed. The proposed system was applied to the monitoring of ozonation status of a playa lake water that exhibited significant ozone demand. PMID:18970059

  1. Ultrasonic absorption in aqueous solutions of amino acids at neutral pH

    NASA Astrophysics Data System (ADS)

    Nishikawa, S.; Ohno, T.; Huang, H.; Yoshizuka, K.; Jordan, F.

    2003-05-01

    Ultrasonic absorption coefficients in aqueous solutions of glycine, L-alanine, imidazole, L-phenylalanine, L-histidine and L-tryptophan at neutral pH were measured in the range from 0.8 to 220 MHz at 25 °C. A characteristic ultrasonic relaxation phenomenon was observed only in the solution of L-histidine with a relaxation frequency at around 2 MHz at neutral pH. It was proposed from the concentration independent relaxation frequency and the linear concentration dependence of the maximum absorption per wavelength that the relaxation mechanism was associated with a perturbation of the rotational isomeric equilibrium of the L-histidine molecule. The existence of two rotational isomeric forms of L-histidine in water was examined by semiempirical quantum chemical methods, in order to determine the free energy difference between the two states. The forward and backward rate constants were determined from the relaxation frequency and the energy change. Also, the standard volume change of the reaction was estimated from the concentration dependence of the maximum absorption per wavelength. It was speculated that L-histidine fulfills a specific function among amino acids because of the rotational motion in the molecule, in addition to its well-established acid-base properties.

  2. Turbulent acidic jets and plumes injected into an alkaline environment

    NASA Astrophysics Data System (ADS)

    Ulpre, Hendrik

    2012-11-01

    The characteristics of a strong acidic turbulent jet or plume injected into an alkaline environment comprising of a weak/strong base are examined theoretically and experimentally. A chemistry model is developed to understand how the pH of a fluid parcel of monoprotic acid changes as it is diluted and reacts with the ambient fluid. A standard fluid model, based on a top-hat model for acid concentration and velocity is used to express how the dilution of acid varies with distance from the point of discharge. These models are applied to estimate the point of neutralisation and the travel time with distance within the jet/plume. An experimental study was undertaken to test the theoretical results. These experiments involved injecting jets or vertical plumes of dilute nitric acid into a large tank containing a variety of base salts dissolved in water. The injected fluid contained litmus indicator dye which showed a change in colour from red to blue close to the point of neutralisation. In order to obtain a range of neutralisation distances, additional basic salts were added to the water to increase its pH buffering capacity. The results are applied to discuss the environmental implications of an acidic jet/plume injected into the sea off the South East coast of Great Britain.

  3. Defect effect on tribological behavior of diamond-like carbon films deposited with hydrogen diluted benzene gas in aqueous environment

    NASA Astrophysics Data System (ADS)

    Yi, Jin Woo; Park, Se Jun; Moon, Myoung-Woon; Lee, Kwang-Ryeol; Kim, Seock-Sam

    2009-05-01

    This study examined the friction and wear behavior of diamond-like carbon (DLC) films deposited from a radio frequency glow discharge using a hydrogen diluted benzene gas mixture. The DLC films were deposited on Si (1 0 0) and polished stainless steel substrates by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) at hydrogen to benzene ratios, or the hydrogen dilution ratio, ranging from 0 to 2.0. The wear test was carried out in both ambient and aqueous environments using a homemade ball-on-disk type wear rig. The stability of the DLC coating in an aqueous environment was improved by diluting the benzene precursor gas with hydrogen, suggesting that hydrogen dilution during the deposition of DLC films suppressed the initiation of defects in the film and improved the adhesion of the coating to the interface.

  4. Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

    PubMed

    Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

    2016-07-01

    Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC. PMID:26660507

  5. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  6. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments.

    PubMed

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids. PMID:25796392

  7. Poorly crystalline hydroxyapatite: A novel adsorbent for enhanced fulvic acid removal from aqueous solution

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Yang, Lei; Zhong, Wenhui; Cui, Jing; Wei, Zhenggui

    2015-03-01

    In this study, poorly crystalline hydroxyapatite (HAP) was developed as an efficient adsorbent for the removal of fulvic acid (FA) from aqueous solution. Surface functionality, crystallinity, and morphology of the synthetic adsorbent were studied by Fourier-transformation infrared (FT-IR) spectroscopy, powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of various parameters such as crystallinity of adsorbent, contact time, adsorbent dosage, pH, initial adsorbate concentration, temperature, ionic strength and the presence of alkaline earth metal ions on FA adsorption were investigated. Results indicated that the nanosized HAP calcined at lower temperature was poorly crystalline (Xc = 0.23) and had better adsorption capacity for FA than those (Xc = 0.52, 0.86) calcined at higher temperature. FA removal was increased with increases of adsorbent dosage, temperature, ionic strength and the presence of alkali earth metal ions, but decreased as the pH increased. Kinetic studies showed that pseudo-second-order kinetic model better described the adsorption process. Equilibrium data were best described by Sips models, and the estimated maximum adsorption capacity of poorly crystalline HAP was 90.20 mg/g at 318 K, displaying higher efficiency for FA removal than previously reported adsorbents. FT-IR results revealed that FA adsorption over the adsorbent could be attributed to the surface complexation between the oxygen atom of functional groups of FA and calcium ions of HAP. Regeneration studies indicated that HAP could be recyclable for a long term. Findings of the present work highlight the potential for using poorly crystalline HAP nanoparticles as an effective and recyclable adsorbent for FA removal from aqueous solution.

  8. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    SciTech Connect

    Gonzalez Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James A.; Curtiss, Larry A.

    2012-02-14

    The conversion of furfuryl alcohol (FAL) to levulinic acid over Amberlyst TM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5- trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  9. Effects of low molecular weight organic acids on the immobilization of aqueous Pb(II) using phosphate rock and different crystallized hydroxyapatite.

    PubMed

    Wei, Wei; Cui, Jing; Wei, Zhenggui

    2014-06-01

    Understanding the effects of low molecular weight organic acids (LMWOAs) on the transformation of Pb(II) to geochemically stable pyromorphite (PY) by apatite materials (AMs), has considerable benefits for risk assessment and remediation strategies for contaminated water and soil. In this study, we systematically investigated the immobilization of Pb(II) from aqueous solution by natural phosphate rock (PR) and different crystallized hydroxyapatite (HAp) in the absence and presence of LMWOAs (oxalic, malic and citric acids). The results indicated that the effectiveness of PR and HAp in immobilizing Pb(II) followed in descending order by HAp2 (the poorly crystallized HAp), HAp1 (the well crystallized HAp) and PR, regardlessof the presence of LMWOAs. The presence of malic and citric acids significantly decreased the immobilizationefficiency of Pb(II) by HAp1 and PR, clarifying the lower adsorption affinities of Pb(II)-organic acid complexes on HAp1 and PR rather than Pb(II) ion. On thecontrary, oxalic acid could markedly enhance the removal of Pb(II) from aqueous solution by HAp1 and PR through the formation of lead oxalate, which was confirmed by FT-IR and XRDanalysis. Results also showed that LMWOAs had little promoting or inhibiting effect on the immobilization of Pb(II) by HAp2. This study suggested that the ubiquity of LMWOAs in natural environments could retard the transformation efficiency of Pb(II) to PY by AMs, especiallyin thepresenceof oxalic acid, and the poorly crystallized HAp2 had great potential to remediate Pb(II)-contaminated water and soil due to its insusceptibility to LMWOAs. PMID:24216261

  10. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    SciTech Connect

    Roman, Yuriy

    2015-09-14

    The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathways for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through

  11. Photocatalytic CO2 reduction to formic acid using a Ru(II)-Re(I) supramolecular complex in an aqueous solution.

    PubMed

    Nakada, Akinobu; Koike, Kazuhide; Nakashima, Takuya; Morimoto, Tatsuki; Ishitani, Osamu

    2015-02-16

    In an aqueous solution, photophysical, photochemical, and photocatalytic abilities of a Ru(II)-Re(I) binuclear complex (RuReCl), of which Ru(II) photosensitizer and Re(I) catalyst units were connected with a bridging ligand, have been investigated in details. RuReCl could photocatalyze CO2 reduction using ascorbate as an electron donor, even in an aqueous solution. The main product of the photocatalytic reaction was formic acid in the aqueous solution; this is very different in product distribution from that in a dimethylformamide (DMF) and triethanolamine (TEOA) mixed solution in which the main product was CO. A (13)CO2 labeling experiment clearly showed that formic acid was produced from CO2. The turnover number and selectivity of the formic acid production were 25 and 83%, respectively. The quantum yield of the formic acid formation was 0.2%, which was much lower, compared to that in the DMF-TEOA mixed solution. Detail studies of the photochemical electron-transfer process showed back-electron transfer from the one-electron-reduced species (OERS) of the photosensitizer unit to an oxidized ascorbate efficiently proceeded, and this should be one of the main reasons why the photocatalytic efficiency was lower in the aqueous solution. In the aqueous solution, ligand substitution of the Ru(II) photosensitizer unit proceeded during the photocatalytic reaction, which was a main deactivation process of the photocatalytic reaction. The product of the ligand substitution was a Ru(II) bisdiimine complex or complexes with ascorbate as a ligand or ligands. PMID:25654586

  12. Understanding the interaction of amorphous calcium polyphosphate with aqueous environments to optimize its use as a localized drug delivery matrix

    NASA Astrophysics Data System (ADS)

    Djogbenou, Nancy

    Amorphous calcium polyphosphate (CPP) shows potential as an implantable drug delivery matrix through a simple gelling protocol that has been shown to eliminate burst release and extend drug release time from the matrix. The nature of the interaction of CPP with aqueous environments and different drugs is not yet well understood. For this reason, CPP samples were manufactured using two different methods: the established gelation protocol, with and without drug, and mixing CPP with different volumes of aqueous solutions to better understand the effect of water exposure on the structural and drug release properties of CPP. Exposure to aqueous systems caused a reduction in the chain length of CPP that was dependant on gel time and mode of exposure. Longer gel times or increased volume of water used during exposure also caused the formation of crystalline material upon drying. In general, drug release was a function of aqueous exposure and the therapeutic agent used. Drug elution studies showed an increase in the burst release of vancomycin (VCM) from CPP gelled for extended periods. When total gel time was 10 hours or below samples that were gelled for only a short time during drug loading performed best. CPP loaded with BSA had a much slower release rate than VCM and appeared to release BSA by a different mechanism. Overall, this thesis shows that CCP drug delivery matrices can be produced with tailored properties simply by controlling processing conditions.

  13. Influence of aqueous environment on agglomeration and dissolution of thiol-functionalised mesoporous silica-coated magnetite nanoparticles.

    PubMed

    Hakami, Othman; Zhang, Yue; Banks, Charles J

    2015-03-01

    The purpose of the present research work is to investigate the stability and dissolution of magnetite (Fe3O4) nanoparticles (NPs) and thiol-functionalised mesoporous silica-coated magnetite NPs (TF-SCMNPs). The state of NPs in an aqueous environment was investigated under different pH conditions. Changes in the NPs' mean diameter due to aggregation were measured over a specific time. The effects of contact time and pH on the dissolution of NPs were also investigated. In order to avoid possible aggregation, Fe3O4 NPs were coated with silica and functionalised further with thiol organic groups. These methods imparted excellent stability to magnetite NPs in an aqueous medium over a wide range of pH values with reasonable hydrodynamic size. The organic group bound magnetite NPs allowed these particles to circulate over a long time in the aqueous system, and particle aggregation and sedimentation did not occur. The trend of decreasing zeta potential was observed after grafting thiol onto the surface of the SCMNPs. The results also revealed that silica exhibited a noteworthy efficient in eliminating the pH dependence and enhancing the NP stability of SCMNPs and SH-SCMNPs in aqueous medium. On the other hand, the dissolution of Fe3O4 NPs was found to be detrimental at pH 2.0 and 4.0 or had a long contact time. PMID:24898295

  14. Removal of Cr(VI) from Aqueous Environments Using Micelle-Clay Adsorption

    PubMed Central

    Qurie, Mohannad; Khamis, Mustafa; Manassra, Adnan; Ayyad, Ibrahim; Nir, Shlomo; Scrano, Laura; Bufo, Sabino A.; Karaman, Rafik

    2013-01-01

    Removal of Cr(VI) from aqueous solutions under different conditions was investigated using either clay (montmorillonite) or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI) from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI) removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI) from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques. PMID:24222757

  15. The cleaning and disinfecting of hemodialysis equipment using electrolyzed strong acid aqueous solution.

    PubMed

    Tanaka, N; Fujisawa, T; Daimon, T; Fujiwara, K; Yamamoto, M; Abe, T

    1999-04-01

    In general, sodium hypochlorite, formalin, and Dialox (Teijin Gambro Medical, Ltd., Tokyo, Japan [main ingredients: H2O2, CH3CHOOOH, CH3COOH, H2O]) are used to clean and disinfect hemodialysis pipelines. In this study, the suitability of electrolyzed strong acid aqueous solution (ESAAS), which has attracted considerable interest in Japan because of its strong disinfecting properties, was examined. The crossover method was used to investigate the effectiveness of ESAAS in disinfecting the dialysis pipelines in comparison to that of sodium hypochlorite (200 ppm) used alternately with 1% acetic acid. The number of bacteria and the concentration of endotoxin (Et) were measured over an approximately 3 year period, starting in September 1994. Until then, 200 ppm sodium hypochlorite had been used alternately with 1% acetic acid, and the contamination of the pipeline had been marked. However, after switching to the ESAAS disinfection method, the dialysis pipelines very rapidly became cleaner. Therefore, the decision to develop an automated ESAAS cleaning system for long-term use was made. During the development period, the original disinfectants (200 ppm sodium hypochlorite used alternately with 1% acetic acid) were used as a stopgap. After confirmation of its performance and safety, the automated ESAAS cleaning system was introduced. To find out whether the decrease in bacteria secondarily caused a decrease in the Et concentration or whether the ESAAS directly inactivated the Et, an in vitro experiment was carried out. Highly concentrated Et, which had been left in the reverse osmosis (RO) drainage pipeline, was used as a sample to investigate the effects of ESAAS on Et at various concentrations and temperatures and on the recovery test. The results showed that ESAAS directly inactivated Et. This paper reports the results of the crossover test. The results of parallel tests carried out over an approximately 4 year period have already been reported. No significant problems

  16. Adsorption of Benzoic Acid in Aqueous Solution by Bagasse Fly Ash

    NASA Astrophysics Data System (ADS)

    Suresh, S.

    2012-09-01

    This paper reports the studies on the benzoic acid (BA) onto bagasse fly ash (BFA) was studied in aqueous solution in a batch system. Physico-chemical properties including surface area, surface texture of the GAC before and after BA adsorption onto BFA were analysed using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The optimum initial pH for the adsorption of BA was found to be 5.56. The adsorbent dose was 10 g/l for BFA and the equilibrium time 8 h of reaction. Pseudo first and second order models were used to find the adsorption kinetics. It was found that intraparticle diffusion played important role in the adsorption mechanisms of BA and the adsorption kinetics followed pseudo-second order kinetic model rather than the pseudo first order kinetic model. Isotherm data were generated for BA solution having initial concentrations of BA in the range of 10-200 mg/l for the BFA dosage of 10 g/l at temperatures of 288, 303, and 318 K. The adsorption of BA onto BFA was favorably influenced by an increase in temperature. Equilibrium data were well represented by the Redlich-Peterson isotherm model. Values of the change in entropy ( ΔS 0), heat of adsorption ( ΔH 0) for adsorption of BA on BFA was found to be 120.10 and 19.61 kJ/mol respectively. The adsorption of BA onto BFA was an endothermic reaction. Desorption of BA from BFA was studied by various solvents method. Acetic acid was found to be a better eluant for desorption of BA with a maximum desorption efficiency of 55.2 %. Owing to its heating value, spent BFA can be used as a co-fuel for the production of heat in boiler furnaces.

  17. Zirconium(IV) tetramer/octamer hydrolysis equilibrium in aqueous hydrochloric acid solution

    SciTech Connect

    Singhal, A.; Toth, L.M.; Lin, J.S.; Affholter, K.

    1996-11-20

    Small-angle X-ray scattering measurements were performed on zirconium acidic aqueous solutions to investigate the structure and the size of polynuclear species larger than the previously identified tetrameric species. Solutions with [H{sup +}]{sub added} and [OH{sup -}]{sub added} ranging from 0.0 to 1.0 M and 0.0 to 0.02 M, respectively, were analyzed. This study demonstrates that an octameric species, Zr{sub 8}(OH){sub 20}(H{sub 2}O){sub 24}Cl{sub 12}, exists in equilibrium with the tetrameric species, Zr{sub 4}(OH){sub 8}(H{sub 2} O){sub 16}Cl{sub 6}{sup 2+}, such that, for 0.05 M Zr(IV) in highly acidic solutions ([H{sup +}]{sub added} = 0.6 M), the tetramer in the dominant species; and at conditions with [H{sup +}] added =0.05 M, the octameric species becomes predominant. The estimated value of the equilibrium quotient obtained for the tetramer/octamer equilibrium is 0.20 {+-} 0.05 M{sup 3}. The tetramer and octamer have radii of gyration of 3.8 and 5.1 {+-} 0.2 A and a hydrolysis ratio of 2.0 and 2.5, respectively. The octamer forms by stacking two tetramers on top of each other. At conditions where small amounts of NaOH are added, unidentified polymeric Zr(IV) species larger in size than the octameric species appear. 26 refs., 7 figs.

  18. Aqueous Growth of Gold Clusters with Tunable Fluorescence Using Photochemically Modified Lipoic Acid-Based Ligands.

    PubMed

    Mishra, Dinesh; Aldeek, Fadi; Lochner, Eric; Palui, Goutam; Zeng, Birong; Mackowski, Sebastian; Mattoussi, Hedi

    2016-06-28

    We report a one-phase aqueous growth of fluorescent gold nanoclusters (AuNCs) with tunable emission in the visible spectrum, using a ligand scaffold that is made of poly(ethylene glycol) segment appended with a metal coordinating lipoic acid at one end and a functional group at the other end. This synthetic scheme exploits the ability of the UV-induced photochemical transformation of LA-based ligands to provide DHLA and other thiol byproducts that exhibit great affinity to metal nanoparticles, obviating the need for chemical reduction of the dithiolane ring using classical reducing agents. The influence of various experimental conditions, including the photoirradiation time, gold precursor-to-ligand molar ratios, time of reaction, temperature, and the medium pH, on the growth of AuNCs has been systematically investigated. The photophysical properties, size, and structural characterization were carried out using UV-vis absorption and fluorescence spectroscopy, TEM, DOSY-NMR, and X-ray photoelectron spectroscopy. The hydrodynamic size (RH) obtained by DOSY-NMR indicates that the size of these clusters follows the trend anticipated from the absorption and PL data, with RH(red) > RH(yellow) > RH(blue). The tunable emission and size of these gold nanoclusters combined with their high biocompatibility would make them greatly promising for potential use in imaging and sensing applications. PMID:27254320

  19. Near-Infrared Electrogenerated Chemiluminescence from Aqueous Soluble Lipoic Acid Au Nanoclusters.

    PubMed

    Wang, Tanyu; Wang, Dengchao; Padelford, Jonathan W; Jiang, Jie; Wang, Gangli

    2016-05-25

    Strong electrogenerated chemiluminescence (ECL) is detected from dithiolate Au nanoclusters (AuNCs) in aqueous solution under ambient conditions. A novel mechanism to drastically enhance the ECL is established by covalent attachment of coreactants N,N-diethylethylenediamine (DEDA) onto lipoic acid stabilized Au (Au-LA) clusters with matching redox activities. The materials design reduces the complication of mass transport between the reactants during the lifetime of radical intermediates involved in conventional ECL generation pathway. The intracluster reactions are highly advantageous for applications by eliminating additional and high excess coreactants otherwise needed. The enhanced ECL efficiency also benefits uniquely from the multiple energy states per Au cluster and multiple DEDA ligands in the monolayer. Potential step and sweeping experiments reveal an onset potential of 0.78 V for oxidative-reduction ECL generation. Multifolds higher efficiency is found for the Au clusters alone in reference to the standard Rubpy with high excess TPrA. The ECL in near-IR region (beyond 700 nm) is highly advantageous with drastically reduced interference signals over visible ones. The features of ECL intensity responsive to electrode potential and solution pH under ambient conditions make Au-LA-DEDA clusters promising ECL reagents for broad applications. The strategy to attach coreactants on Au clusters is generalizable for other nanomaterials. PMID:27172252

  20. Preparation and characterization of aqueous dispersions of high amylose starch and conjugated linoleic acid complex.

    PubMed

    Seo, Tae-Rang; Kim, Hee-Young; Lim, Seung-Taik

    2016-11-15

    Crystalline starch-CLA complexes were prepared by blending an alcoholic solution of conjugated linoleic acid (CLA) in an aqueous high-amylose maize starch dispersion. Recovery yield of CLA in the precipitates obtained by centrifuging the dispersion was dependent on reaction conditions such as temperature, time and pH. The CLA recovery reached a maximum when the reaction was performed at 90°C for 6h at neutral pH, with 67.7% of the initial CLA being co-precipitated with starch. The precipitates contained amylose-CLA complex exhibiting a V6I-type crystalline structure under X-ray diffraction analysis and a type II polymorph under DSC analysis. Ultrasonic treatment for the re-dispersed starch-CLA complex in water resulted in the reduction of hydrodynamic diameter of the complex particles to 201.5nm. The dispersion exhibited a zeta potential of -27.0mV and remained stable in an ambient storage without forming precipitates for more than 4weeks. PMID:27283663

  1. Removal of acid blue 062 on aqueous solution using calcinated colemanite ore waste.

    PubMed

    Atar, Necip; Olgun, Asim

    2007-07-19

    Colemanite ore waste (CW) has been employed as adsorbent for the removal of acid blue 062 anionic dye (AB 062) from aqueous solution. The adsorption of AB 062 onto CW was examined with respect to contact time, calcination temperature, particle size, pH, adsorbent dosage and temperature. The physical and chemical properties of the CW, such as particle sizes and calcinations temperature, play important roles in dye adsorption. The dye adsorption largely depends on the initial pH of the solution with maximum uptake occurring at pH 1. Three simplified kinetics models, namely, pseudo-first order, pseudo-second order, and intraparticle diffusion models were tested to investigate the adsorption mechanisms. The kinetic adsorption of AB 062 on CW follows a pseudo-second order equation. The adsorption data have been analyzed using Langmuir and Freundlich isotherms. The results indicate that the Langmuir model provides the best correlation of the experimental data. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of the adsorption of dye onto CW. PMID:17197077

  2. Aqueous solution deposition kinetics of iron oxyhydroxide on sulfonic acid terminated self-assembled monolayers

    SciTech Connect

    Rieke, P.C.; Marsh, B.D.; Wood, L.L.; Tarasevich, B.J.; Liu, J.; Song, L.; Fryxell, G.E. )

    1995-01-01

    The deposition kinetics of iron oxyhydroxide on sulfonic acid terminated self-assembled monolayers were studied. The thin films of FeOOH were formed on the substrates by thermal hydrolysis of millimolar aqueous solutions of Fe(NO[sub 3])[sub 3] at a pH of approximately 2.0. The thickness of the films was measured ellipsometrically at various times. Both Fe(NO[sub 3])[sub 3] and HNO[sub 3] concentrations were independently varied to provide varying degrees of solution supersaturation. Depending on these concentrations, an induction time was observed before film growth commenced. The correlation between supersaturation and induction time was modeled using classical nucleation theory. Very good agreement was observed regardless of whether supersaturation was varied via the concentration of Fe(NO[sub 3])[sub 3] or HNO[sub 3]. From these results an interfacial free energy for nucleation of 148 mJ/m[sup 2] was calculated. The critical nucleus species was identified as a tetrameric iron species by considering the order of nucleation. 49 refs., 11 figs., 1 tab.

  3. Complete mineralization of perfluorooctanoic acid (PFOA) by γ-irradiation in aqueous solution

    NASA Astrophysics Data System (ADS)

    Zhang, Ze; Chen, Jie-Jie; Lyu, Xian-Jin; Yin, Hao; Sheng, Guo-Ping

    2014-12-01

    Decomposition of perfluorooctanoic acid (C7F15COOH, PFOA) has been gaining increasing interests because it is a ubiquitous environmental contaminant and resistant to the most conventional treatment processes. In this work, the rapid and complete mineralization of PFOA and simultaneous defluorination were achieved by γ-ray irradiation with a 60Co source. The degradation rate of PFOA by γ-ray irradiation would be high, and a pseudo-first-order kinetic rate constant of 0.67 h-1 could be achieved in the N2 satured condition at pH 13.0. The experimental results and quantum chemical calculation confirmed that two radicals, i.e., hydroxyl radical (.OH) and aqueous electrons (eaq-), were responsible for the degradation of PFOA, while only either eaq- or .OH might not be able to accomplish complete mineralization of PFOA. The synergistic effects of .OH and eaq- involved in the cleavage of C-C and C-F bonds, and therefore complete mineralization of PFOA were achieved. The intermediate products were identified and the degradation pathway was also proposed. The results of this study may offer a useful, high-efficient approach for complete mineralizing fluorochemicals and other persistent pollutants.

  4. [Mechanism of action of combined extremely weak magnetic field on aqueous solution of amino acid].

    PubMed

    Zhadin, M N; Bakharev, B V; Bobkova, N V

    2014-01-01

    The fundamental physical mechanisms of resonance action of an extremely weak (40 nT) alternating magnetic field at the cyclotron frequency combined with a weak (40 μT) static magnetic field, on living systems are analyzed in the present work. The experimental effects of such sort of magnetic fields were described in different papers: the very narrow resonant peaks in electrical conductivity of the aqueous solutions in the in vitro experiments and the biomedical in vivo effects on living animals of magnetic fields with frequencies tuned to some amino acids. The existing experimental in vitro data had a good repeatability in different laboratories and countries. Unfortunately, for free ions such sort of effects are absolutely impossible because the dimensions of an ion rotation radius should be measured by meters at room temperature and at very low static magnetic fields used in all the above experiments. Even for bound ions these effects should be also absolutely impossible from the positions of classic physics because of rather high viscosity of biological liquid media (blood plasma, cerebrospinal liquid, cytoplasm). Only modern quantum electrodynamics of condensed media opens the new ways for solving these problems. The proposed article is devoted to analysis of quantum mechanisms of these effects. PMID:25707253

  5. Complete mineralization of perfluorooctanoic acid (PFOA) by γ-irradiation in aqueous solution

    PubMed Central

    Zhang, Ze; Chen, Jie-Jie; Lyu, Xian-Jin; Yin, Hao; Sheng, Guo-Ping

    2014-01-01

    Decomposition of perfluorooctanoic acid (C7F15COOH, PFOA) has been gaining increasing interests because it is a ubiquitous environmental contaminant and resistant to the most conventional treatment processes. In this work, the rapid and complete mineralization of PFOA and simultaneous defluorination were achieved by γ-ray irradiation with a 60Co source. The degradation rate of PFOA by γ-ray irradiation would be high, and a pseudo-first-order kinetic rate constant of 0.67 h−1 could be achieved in the N2 satured condition at pH 13.0. The experimental results and quantum chemical calculation confirmed that two radicals, i.e., hydroxyl radical (·OH) and aqueous electrons (eaq−), were responsible for the degradation of PFOA, while only either eaq− or ·OH might not be able to accomplish complete mineralization of PFOA. The synergistic effects of ·OH and eaq− involved in the cleavage of C-C and C-F bonds, and therefore complete mineralization of PFOA were achieved. The intermediate products were identified and the degradation pathway was also proposed. The results of this study may offer a useful, high-efficient approach for complete mineralizing fluorochemicals and other persistent pollutants. PMID:25492109

  6. Lipase in biphasic alginate beads as a biocatalyst for esterification of butyric acid and butanol in aqueous media.

    PubMed

    Ng, Choong Hey; Yang, Kun-Lin

    2016-01-01

    Esterification of organic acids and alcohols in aqueous media is very inefficient due to thermodynamic constraints. However, fermentation processes used to produce organic acids and alcohols are often conducted in aqueous media. To produce esters in aqueous media, biphasic alginate beads with immobilized lipase are developed for in situ esterification of butanol and butyric acid. The biphasic beads contain a solid matrix of calcium alginate and hexadecane together with 5 mg/mL of lipase as the biocatalyst. Hexadecane in the biphasic beads serves as an organic phase to facilitate the esterification reaction. Under optimized conditions, the beads are able to catalyze the production of 0.16 mmol of butyl butyrate from 0.5 mmol of butyric acid and 1.5 mmol of butanol. In contrast, when monophasic beads (without hexadecane) are used, only trace amount of butyl butyrate is produced. One main application of biphasic beads is in simultaneous fermentation and esterification (SFE) because the organic phase inside the beads is very stable and does not leach out into the culture medium. SFE is successfully conducted with an esterification yield of 6.32% using biphasic beads containing iso-octane even though the solvent is proven toxic to the butanol-producing Clostridium spp. PMID:26672465

  7. Sorption of carboxylic acid from carboxylic salt solutions at pHs close to or above the pK[sub a] of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C.J.; Tung, L.A.

    1992-07-21

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.

  8. Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C. Judson; Tung, Lisa A.

    1992-01-01

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.

  9. Factors affecting the removal of chlorendic acid from aqueous solutions using high energy electron irradiation

    SciTech Connect

    Taylor, T.C.; Cooper, W.J.; Nickelsen, M.G. ); Kurucz, C.N.; Waite, T.D. )

    1990-01-01

    Irradiation of water has been studied for many years. In pure water, the product distribution is well known and results in the formation of several highly reactive radical species. These radical species, e{sup {minus}} ag, H{sup {sm bullet}} and OH{sup {sm bullet}}, are known to react with many organic compounds. Thus, it appears that this treatment may be of interest in treating waste streams which contain compounds of known threat to the environment. This paper will provide initial results of experiments on the removal of chlorendic acid in wastewater.

  10. MODELING SMALL-SCALE SPILLS OF AQUEOUS SOLUTIONS IN THE INDOOR ENVIRONMENT

    EPA Science Inventory

    A mass transfer model is proposed to estimate the rates of chemical emissions from aqueous solutions spilled on hard surfaces inside buildings. The model is presented in two forms: a set of four ordinary differential equations and a simplified exact solution. The latter can be ...

  11. Aqueous Synthesis of Peptide Thioesters from Amino Acids and a Thiol Using 1,1‧-Carbonyldiimidazole

    NASA Astrophysics Data System (ADS)

    Weber, Arthur L.

    2005-10-01

    A new method was developed for the synthesis of peptide thioesters from free amino acids and thiols in water. This one-pot simple method involves two steps: (1) activation in water of an amino acid presumably as its N-carboxyanhydride (NCA) using 1,1‧-carbonyldiimidazole (CDI), and (2) subsequent condensation of the activated amino acid-NCA in the presence of a thiol. With this method citrulline peptide thioesters containing up to 10 amino acid residues were prepared in a single reaction. This aqueous synthetic method provides a simple way to prepare peptide thioesters for studies of peptide replication involving ligation of peptide thioesters on peptide templates. The relevance of peptide replication to the origin-of-life process is supported by previous studies showing that amino acid thioesters (peptide thioester precursors) can be synthesized under prebiotic conditions by reaction of small sugars with ammonia and a thiol.

  12. Conductometric and fluorometric studies of sodium dodecyl sulphate in aqueous solution and in the presence of amino acids

    NASA Astrophysics Data System (ADS)

    Ali, Anwar; Malik, Nisar Ahmad; Uzair, Sahar; Ali, Maroof

    2014-10-01

    The critical micelle concentration (CMC) of sodium dodecyl sulphate (SDS) in pure water and in the presence of amino acids (0.01, 0.02 and 0.03 mol kg-1), L-valine (Val) and L-leucine (Leu) was determined from conductometric and fluorometric methods using pyrene as luminescence probe. Depression in the CMC at low concentration of amino acids is attributed to the increased hydrophobic-hydrophobic interaction between the non-polar groups of the surfactant, while, at high concentration, amino acids bind strongly with the anion, DS-, head groups of SDS, thereby, delaying the micelle formation, resulting in increased CMC. A pronounced decrease in the CMC, while a marked increase in λ0+, with decrease in the solvated radius (rather than crystal radius) of the counterions is observed. Negative values of ΔG0m and ΔH0m indicate that micellisation of SDS in the presence of amino acids is thermodynamically spontaneous and exothermic. Highest negative value of ΔH0m in 0.01 m Val, with lowest CMC value, shows that 0.01 m aqueous Val is the most suitable medium favouring the micellisation of SDS. Decrease in I1/I3 from Val to Leu confirms the relative hydrophobicity of two amino acids. The observed values of the packing parameter, P, of SDS in water and in aqueous amino acids suggest that micelles formed are spherical in nature.

  13. Decolourization performance in C. I. Vat Yellow 1 aqueous suspension using hydrophobically modified poly(acrylic acid).

    PubMed

    Chen, J; Chen, M C

    2011-01-01

    A series of hydrophobically modified poly(acrylic acid) (PAA), poly(2-phenoxyethyl acrylate-co-acrylic acid) (poly(PHEA-co-AA)), have been synthesized and characterized by Ubbelohde type viscometry, Nuclear Magnetic Resonance (1H NMR) spectrometry and Differential Scanning Calorimetry (DSC). The shear thinning Non-Newtonian fluid behavior of their aqueous solution and the dependence on pH and hydrophobic group contents were found through apparent viscosity and rheological property investigating. Decolourization performance in C. I. Vat Yellow 1 aqueous suspension was evaluated through visible absorbance data. Decolourization performance of hydrophobically associated polymer indicates two times better than that of PAA. The quantitative relationship was mainly studied. PMID:21866762

  14. Copper Catalyzed Sodium Tetraphenylborate, Triphenylborane, Diphenylborinic Acid and Phenylboronic Acid Decomposition Kinetic Studies in Aqueous Alkaline Solutions

    SciTech Connect

    Crawford, C.L.

    1999-03-15

    This work studied the kinetics of copper-catalyzed decomposition of tetraphenylborate, triphenylborane, diphenylborinic acid and phenylboronic acid (NaTPB, 3PB, 2PB and 1PB, respectively) in aqueous alkaline solution over the temperature range of 25 to 70 degrees C. The statistically designed test matrices added copper sulfate to maximum concentrations of 10 mg/L. The relative rates of decomposition increase in the order of NaTPB < 1PB {tilde} 3PB < 2PB. Dependence of decomposition on the amount of added copper increases in the order of 3PB {tilde} 2PB < 1PB {tilde} NaTPB. Activation energies ranged from 82 to 143 kJ/mole over the temperature range studied. Final decomposition products predominately involved benzene and phenol. All 3PB, 2PB and 1PB intermediate phenylborate species proved relatively stable (< 8 percent decomposition over {tilde} 500 h) towards thermal hydrolysis in 1.5 M NaOH when contained in carbon-steel vessels sealed under air at ambient temperature (23 - 25 degrees C) with no added copper. Measurable (> 10-7 Mh-1) thermal hydrolysis of the phenylborate species occurs at 55 to 70 degrees C in alkaline (0.6-2.3 M OH-, 2-4.7 M Na+) solution with no added copper. The experiments suggest an important role for oxygen in copper-catalyzed phenylborate decomposition. NaTPB decomposes promptly under anoxic conditions while 3PB, 2PB and 1PB decompose faster in aerobic solutions. Benzene and phenol form as the predominant end-products from alkaline copper catalysis in static systems sealed under air. Both 2PB and 1PB decompose with near equal rates and quantitatively produce phenol under flowing air-purge conditions at 25 to 60 degrees C. Mechanisms for copper-catalyzed phenylborate decomposition likely involve a redox process giving loss of a phenyl group from the phenylborate with reduction of cupric ion, or dephenylation by reduced cuprous ion involving a phenylated copper intermediate.

  15. A CALPHAD study on the thermodynamic stability of calcium-, zinc-, and yttrium-doped magnesium in aqueous environments

    SciTech Connect

    Wu, Kaisheng; Dogan, Omar N.; Velikokhatnyl, Oleg I.; Kumta, Prashant N.

    2011-12-15

    Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg–Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.

  16. A CALPHAD Study on the Thermodynamic Stability of Calcium-, Zinc-, and Yttrium-Doped Magnesium in Aqueous Environments

    SciTech Connect

    Wu, Kaisheng

    2011-12-15

    Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg–Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.

  17. An efficient and sensitive fluorescent pH sensor based on amino functional metal-organic frameworks in aqueous environment.

    PubMed

    Xu, Xiao-Yu; Yan, Bing

    2016-04-19

    A pH sensor is fabricated via a reaction between an Al(III) salt and 2-aminoterephthalic acid in DMF which leads to a MOF (Al-MIL-101-NH2) with free amino groups. The Al-MIL-101-NH2 samples show good luminescence and an intact structure in aqueous solutions with pH ranging from 4.0 to 7.7. Given its exceptional stability and pH-dependent fluorescence intensity, Al-MIL-101-NH2 has been applied to fluorescent pH sensing. Significantly, in the whole experimental pH range (4.0-7.7), the fluorescence intensity almost increases with increasing pH (R(2) = 0.99688) which can be rationalized using a linear equation: I = 2.33 pH + 26.04. In addition, error analysis and cycling experiments have demonstrated the accuracy and utilizability of the sensor. In practical applications (PBS and lake water), Al-MIL-101-NH2 also manifests its analytical efficiency in pH sensing. And the samples can be easily isolated from an aqueous solution by incorporating Fe3O4 nanoparticles. Moreover, the possible sensing mechanism based on amino protonation is discussed in detail. This work is on of the few cases for integrated pH sensing systems in aqueous solution based on luminescent MOFs. PMID:27002862

  18. The Role of Hydrophobic Surfaces in Altering Water-Mediated Peptide-Peptide Interactions in an Aqueous Environment

    SciTech Connect

    Yoo, Soohaeng; Xantheas, Sotiris S

    2011-06-16

    Using Born-Oppenheimer molecular dynamics within the density functional framework, we calculated the effective force acting on water-mediated peptide-peptide interaction between antiparallel β-sheets in an aqueous environment and also in the vicinity of a hydrophobic surface. From the magnitude of the effective force (corresponding to the slope of the free energy as a function of the inter-peptide distance) and its sign (a negative value indicating an effective attraction whereas a positive value an effective repulsion) we can elucidate the fundamental differences of the water-mediated peptide-peptide interactions in those two environments. The computed effective forces indicate that the water-mediated interaction between peptides in an aqueous environment is attractive in the range of inter-peptide distance d=7-8 Å when hydrophobic surfaces are not nearby. Due to the stabilization of the water molecules bridging between the two β-sheets, a free energy barrier exists between the direct and indirect (water-mediated) inter-peptide interactions. However, when the peptides are in the proximity of hydrophobic surfaces, this free energy barrier decreases because the hydrophobic surfaces enhance the inter-peptide attraction by the destabilization and ease-to-libration of the bridging water molecules between them. This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, US Department of Energy. Battelle operates the Pacific Northwest National Laboratory for the U.S. Department of Energy.

  19. Modified Mesoporous Silica (SBA–15) with Trithiane as a new effective adsorbent for mercury ions removal from aqueous environment

    PubMed Central

    2014-01-01

    Background Removal of mercury from aqueous environment has been highly regarded in recent years and different methods have been tested for this purpose. One of the most effective ways for mercury ions (Hg+2) removal is the use of modified nano porous compounds. Hence, in this work a new physical modification of mesoporous silica (SBA-15) with 1, 3, 5 (Trithiane) as modifier ligand and its application for the removal of Hg+2 from aqueous environment has been investigated. SBA-15 and Trithiane were synthesized and the presence of ligand in the silica framework was demonstrated by FTIR spectrum. The amounts of Hg+2 in the samples were determined by cold vapor generation high resolution continuum source atomic absorption spectroscopy. Also, the effects of pH, stirring time and weight of modified SBA-15 as three major parameters for effective adsorption of Hg+2 were studied. Results The important parameter for the modification of the adsorbent was Modification ratio between ligand and adsorbent in solution which was 1.5. The results showed that the best Hg+2 removal condition was achieved at pH = 5.0, stirring time 15 min and 15.0 mg of modified adsorbent. Moreover, the maximum percentage removal of Hg+2 and the capacity of adsorbent were 85% and 10.6 mg of Hg+2/g modified SBA-15, respectively. Conclusions To sum up, the present investigation introduced a new modified nano porous compound as an efficient adsorbent for removal of Hg+2 from aqueous environment. PMID:25097760

  20. Catalytic and stoichiometric bromination of aromatic compounds in aqueous trifluoroacetic acid in the presence of nitrogen-containing oxidizing agents

    SciTech Connect

    Cheprakov, A.V.; Makhon'kov, D.I.; Rodkin, M.A.; Beletskaya, I.P.

    1988-07-10

    The mono- and polybromination of benzene, halogenobenzenes, toluene, p-xylene, anisole, biphenyl, benzotrifluoride, benzoic acid, p-nitro- and p-carboxytoluene, p-methoxybenzonitrile, tetralin, and naphthalene were studied in trifluoroacetic acid and its aqueous solutions in systems containing stoichiometric amounts of bromine or alkali-metal bromide and stoichiometric or catalytic (in the presence of oxygen or air) amounts of nitrogen-containing oxidizing agent (nitrogen(IV) oxide, alkali-metal nitrate or nitrite). It is suggested that the brominating agent under the investigated conditions is nitryl bromide NO/sub 2/Br. Under the conditions of catalytic bromination anthracene is oxidized to anthraquinone with a preparative yield.

  1. [sup 31]P and [sup 27]Al NMR investigations of highly acidic, aqueous solutions containing aluminum and phosphorus

    SciTech Connect

    Mortlock, R.F.; Bell, A.T.; Radke, C.J. Univ. of California, Berkeley )

    1993-01-21

    [sup 31]P and [sup 27]Al NMR spectroscopies have been used to characterize acidic, aqueous solutions of orthophosphoric acid, aluminum chloride, and tetramethylammonium (TMA) hydroxide. The final compositions of the solutions range from 0.1 to 1 mol % P, 0.0 to 20 mol % HCl, P/Al = 0.1 to 20, and P/(TMA)[sub 2]O = 2 to 20. Soluble aluminophosphate cations form reactions of hexaaqua Al monomeric cations, [Al(H[sub 2]O)[sub 6

  2. Unusual red shift of the sensor while detecting the presence of Cd2+ in aqueous environment.

    PubMed

    Sarkar, Santu; Shunmugam, Raja

    2013-08-14

    A norbornene derived 8-hydroxyquinoline (N8HQ) is designed and synthesized. A "turn-on" ratiometric fluorescent response is observed for Cd(2+) in aqueous solution upon binding with N8HQ with a characteristic huge red shift of 164 nm. A lowest detection limit of 1.6 nM of Cd(2+) is achieved in the presence of other heavy metals. PMID:23879449

  3. Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111).

    PubMed

    Montemore, Matthew M; Andreussi, Oliviero; Medlin, J Will

    2016-08-21

    Hydrocarbon chains are important intermediates in various aqueous-phase surface processes, such as CO2 electroreduction, aqueous Fischer-Tropsch synthesis, and aqueous phase reforming of biomass-derived molecules. Further, the interaction between water and adsorbed hydrocarbons represents a difficult case for modern computational methods. Here, we explore various methods for calculating the energetics of this interaction within the framework of density functional theory and explore trade-offs between the use of low water coverages, molecular dynamics approaches, and minima hopping for identification of low energy structures. An effective methodology for simulating low temperature processes is provided by using a unit cell in which the vacuum space is filled with water, employing the minima hopping algorithm to search for low-lying minima, and including dispersion (van der Waals) interactions. Using this methodology, we show that a high coverage of adsorbed alkyls is destabilized by the presence of water, while a low coverage of alkyls is stabilized. Solvation has a small effect on the energetics of hydrocarbon chain growth, generally decreasing its favorability at low temperatures. We studied higher temperatures by running molecular dynamics simulations starting at the minima found by the minima hopping algorithm and found that increased temperatures facilitate chain growth. The self-consistent continuum solvation method effectively describes the alkyl-water interaction and is in general agreement with the explicit solvation results in most cases, but care should be taken at high alkyl coverage. PMID:27544118

  4. Aqueous leaching of organic acids and dissolved organic carbon from various biochars prepared at different temperatures.

    PubMed

    Liu, Peng; Ptacek, Carol J; Blowes, David W; Berti, William R; Landis, Richard C

    2015-03-01

    Biochar has been used as a soil amendment, as a water treatment material, and for carbon (C) sequestration. Thirty-six biochars, produced from wood, agricultural residue, and manure feedstocks at different temperatures, were evaluated for the aqueous leaching of different forms of soluble C. The release of inorganic C (alkalinity), organic acids (OAs), and total dissolved organic C (DOC) was highly variable and dependent on the feedstock and pyrolysis temperature. The pH and alkalinity increased for the majority of samples. Higher pH values were associated with high-temperature (high-T) (600 and 700°C) biochars. Statistically significant differences in alkalinity were not observed between low-temperature (low-T) (300°C) and high-T biochars, whereas alkalinity released from wood-based biochar was significantly lower than from others. Concentrations of OAs and DOC released from low-T biochars were greater than from high-T biochars. The C in the OAs represented 1 to 60% of the total DOC released, indicating the presence of other DOC forms. The C released as DOC represented up to 3% (majority <0.1%) of the total C in the biochar. Scanning electron microscopy with energy dispersive X-ray spectroscopy showed the high-T biochars had a greater proportion of micropores. Fourier transform infrared spectroscopy showed that hydroxyl, aliphatic, and quinone were the predominant functional groups of all biochars and that the abundance of other functional groups was dependent on the feedstock. The release of DOC, especially bioavailable forms such as OAs, may promote growth of organisms and heavy metal complexation and diminish the potential effectiveness of various biochars for C sequestration. PMID:26023986

  5. Evidence for 13-carbon enrichment in oxalic acid via iron catalyzed photolysis in aqueous phase

    NASA Astrophysics Data System (ADS)

    Pavuluri, Chandra Mouli; Kawamura, Kimitaka

    2012-02-01

    To investigate the effect of photochemical aging on the stable carbon isotopic ratio (δ13C) of oxalic acid (OxA), a dominant organic species in atmospheric aerosols, we conducted a laboratory photolysis of OxA under H2O2-Fe3+(Fe2+)-UV system in aqueous phase and measured δ13C of remaining OxA. Our results showed that a significant photolysis of OxA occurred with OH radical but the isotopic fractionation of OxA was insignificant. In contrast, in the presence of Fe3+ (Fe2+), we found a significant enrichment of 13C in remaining OxA. We also found that kinetic isotope effect (KIE) of OxA largely depends on photochemical age (irradiation time) and concentration ratios of OxA to iron; 3.20 ± 0.49‰ (2.18 ± 1.18‰) and 21.62 ± 5.41‰ in 90 min and 180 min irradiation, in which OxA and Fe3+ (Fe2+) ratios were 50:1 and 200:1, respectively. The enrichment of 13C in remaining OxA was more significant during the photolysis catalyzed by Fe3+ (7‰) than by Fe2+ (3‰) in 90 min irradiation when OxA and iron ratios are the same (50:1). This study provides a laboratory evidence for the isotopic enrichment of 13C in OxA with photochemical aging. This approach is useful for better interpretation of atmospheric isotopic measurements in terms of the extent of atmospheric processing of aerosols.

  6. Comparison of CO2 and oxygen DC submerged thermal plasmas for decomposition of carboxylic acid in aqueous solution

    NASA Astrophysics Data System (ADS)

    Safa, S.; Hekmat-Ardakan, A.; Soucy, G.

    2014-11-01

    The feasibility of the carboxylic acid decomposition with two different direct current (DC) thermal plasma torches was investigated. An oxygen DC submerged thermal plasma torch and a newly designed submerged DC plasma torch operating with a mixture of carbon dioxide and methane (CO2/CH4) were used. Sebacic acid was selected as a representative of pollutants in the most wastewater produced by chemical process industries. The effect of different operational conditions including treatment time, the reactor pressure as well as the role of oxidizing agents such as (H2O2) were investigated on the decomposition rate of sebacic acid. Concentration of sebacic acid was quantified by Ion Chromatography/Mass Spectrometry (IC/MS). The oxygen plasma showed higher decomposition rate in basic medium. Adding H2O2 into aqueous solution enhanced the sebacic acid decomposition rate with the CO2/CH4 plasma up to the same decomposition rate of the oxygen plasma. Increasing the pressure also increased the decomposition rate for both plasmas with an increase twice higher for the CO2/CH4 plasma than that of the oxygen plasma. This work therefore presents the conditions in which these plasmas can provide the same decomposition rate for contaminants in aqueous solution.

  7. Boronic acid-containing aminopyridine- and aminopyrimidinecarboxamide CXCR1/2 antagonists: Optimization of aqueous solubility and oral bioavailability.

    PubMed

    Schuler, Aaron D; Engles, Courtney A; Maeda, Dean Y; Quinn, Mark T; Kirpotina, Liliya N; Wicomb, Winston N; Mason, S Nicholas; Auten, Richard L; Zebala, John A

    2015-09-15

    The chemokine receptors CXCR1 and CXCR2 are important pharmaceutical targets due to their key roles in inflammatory diseases and cancer progression. We have previously identified 2-[5-(4-fluoro-phenylcarbamoyl)-pyridin-2-ylsulfanylmethyl]-phenylboronic acid (SX-517) and 6-(2-boronic acid-5-trifluoromethoxy-benzylsulfanyl)-N-(4-fluoro-phenyl)-nicotinamide (SX-576) as potent non-competitive boronic acid-containing CXCR1/2 antagonists. Herein we report the synthesis and evaluation of aminopyridine and aminopyrimidine analogs of SX-517 and SX-576, identifying (2-{(benzyl)[(5-boronic acid-2-pyridyl)methyl]amino}-5-pyrimidinyl)(4-fluorophenylamino)formaldehyde as a potent chemokine antagonist with improved aqueous solubility and oral bioavailability. PMID:26248802

  8. Optimization of polyphenol extraction from red grape pomace using aqueous glycerol/tartaric acid mixtures and response surface methodology.

    PubMed

    Makris, Dimitris P; Passalidi, Vassiliki; Kallithraka, Stamatina; Mourtzinos, Ioannis

    2016-01-01

    Grape pomace is a food industry waste containing a high burden of antioxidant polyphenols and several methodologies have been developed for their efficient extraction. However, a sustainable and environmentally friendly process should involve recovery means composed of benign, non-toxic solvents, such as tartaric acid and glycerol, which are natural food constituents. In this line, this study examined the extraction of polyphenols using aqueous tartaric acid/glycerol solutions. The aim was to assess the role of acid and glycerol concentration in the extraction yield, employing a Box-Behnken experimental design and response surface methodology. The results showed that solutions containing only glycerol (20%, w/v) are more suitable for retrieving polyphenols, flavonoids, and pigments from grape pomace, while tartaric acid exerted a negative effect in this regard, when tested at concentrations up to 2% (w/v). PMID:25806718

  9. Acid gas treating by aqueous alkanolamines. Annual report, January-December 1993

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Ashour, S.

    1993-12-01

    The objective of the work is to investigate the simultaneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed thus far, density, viscosity, gas diffusivity, gas solubility, surface tension, and amine solution vapor pressure have been measured for aqueous MDEA, DEA, and MDEA/DEA mixtures over the temperature range 20 to 100 deg. C and for concentrations up to 50 weight %. A mathematical model, based on the penetration theory, for the simultaneous absorption (desorption) of CO2 and H2S into (from) aqueous solutions of MDEA and DEA has been developed.

  10. Lanthanide triflates as water-tolerant Lewis acids. Activation of commercial formaldehyde solution and use in the aldol reaction of silyl enol ethers with aldehydes in aqueous media

    SciTech Connect

    Kobayashi, Shue; Hachiya, Iwao

    1994-07-01

    The catalytic effects of lanthanide triflates in the hydroxymethylation and the aldol reaction of silyl enol ethers (w/aldehydes). The rare earth triflates served as Lewis acid catalysts in the aqueous reaction medium.

  11. Densities of L-Glutamic Acid HCl Drug in Aqueous NaCl and KCl Solutions at Different Temperatures

    NASA Astrophysics Data System (ADS)

    Ryshetti, Suresh; Raghuram, Noothi; Rani, Emmadi Jayanthi; Tangeda, Savitha Jyostna

    2016-04-01

    Densities (ρ ) of (0.01 to 0.07) {mol}{\\cdot } {kg}^{-1} L-Glutamic acid HCl (L-HCl) drug in water, and in aqueous NaCl and KCl (0.5 and 1.0) {mol}{\\cdot } {kg}^{-1} solutions have been reported as a function of temperature at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure. The accurate density (ρ ) values are used to estimate the various parameters such as the apparent molar volume (V_{2,{\\upphi }}), the partial molar volume (V2^{∞}), the isobaric thermal expansion coefficient (α 2), the partial molar expansion (E2^{∞}), and Hepler's constant (partial 2V2^{∞}/partial T2)P. The Cosphere overlap model is used to understand the solute-solvent interactions in a ternary mixture (L-HCl drug + NaCl or KCl + water). Hepler's constant (partial 2V2^{∞}/partial T2)_P is utilized to interpret the structure-making or -breaking ability of L-HCl drug in aqueous NaCl and KCl solutions, and the results are inferred that L-HCl drug acts as a structure maker, i.e., kosmotrope in aqueous NaCl solutions and performs as a structure breaker, i.e., chaotrope in aqueous KCl solutions.

  12. Removal characteristics of As(III) and As(V) from acidic aqueous solution by steel making slag.

    PubMed

    Oh, Chamteut; Rhee, Sungsu; Oh, Myounghak; Park, Junboum

    2012-04-30

    This study focused on the environmental risk of steel making slag itself, arsenic removal mechanism and re-leaching possibility of arsenic to aqueous state after the adsorption. The purpose of the study is to promote the use of steel making slag as a low-cost adsorbent for arsenic in aqueous system. Calcium was easily dissolved out from the slag and become the dominant substance in the leachate. Some of the calcium could form amorphous calcium carbonate in alkaline condition, and arsenic in the aqueous solution would be removed by being co-precipitated with or adsorbed onto the amorphous calcium carbonate. Most of the amorphous calcium carbonate containing arsenic would be bound to amorphous iron oxide of the slag. When the slag was used as an adsorbent for arsenic removal, a little amount of toxic chemicals were leached from the slag itself under pH 0.8 to 13.6. Also, 70-80% of arsenic laden on the slag was bound to amorphous iron oxide which would not easily desorb unless given a reducing and complexing condition. Showing 95-100% removal efficiency near initial pH 2, the slag, therefore, could be used as an appropriate adsorbent for eliminating arsenic in acidic aqueous solution. PMID:22349716

  13. Recombinant D. radiodurans cells for bioremediation of heavy metals from acidic/neutral aqueous wastes.

    PubMed

    Misra, Chitra Seetharam; Appukuttan, Deepti; Kantamreddi, Venkata Siva Satyanarayana; Rao, Amara S; Apte, Shree Kumar

    2012-01-01

    The stability and superior metal bioremediation ability of genetically engineered Deinococcus radiodurans cells, expressing a non-specific acid phosphatase, PhoN in high radiation environment has already been established. The lyophilized recombinant DrPhoN cells retained PhoN activity and uranium precipitation ability. Such cells also displayed an extended shelf life of 6 months during storage at room temperature and showed surface associated precipitation of uranium as well as other metals like cadmium. Lyophilized cells, immobilized in polyacrylamide gels could be used for uranium bioprecipitation in a flow through system resulting in 70% removal from 1mM input uranium solution and a loading of 1 g uranium/g dry weight cells. Compared with a batch process which achieved a loading of 5.7 g uranium/g biomass, the efficiency of the column process was low due to clogging of the column by the precipitate. PMID:22179144

  14. Spectrophotometric determination of Rare Earth Elements in aqueous nitric acid solutions for process control.

    PubMed

    Rodionova, Oxana Ye; Tikhomirova, Tatyana I; Pomerantsev, Alexey L

    2015-04-15

    Noninvasive analytical control is of special interest for the complicated and hazardous production processes. On-line monitoring provides a unique opportunity to determine critical concentrations rapidly and without serious risks to operating personnel and the environment. Models for quantitative determination of concentrations of Rare Earth Elements in complex mixtures in nitric acid serve for these purposes. Here, the feasibility of simultaneous determination of cerium, praseodymium, and neodymium using the whole UV-vis spectroscopic range, together with chemometric data processing, is studied. The predictability of two chemometric techniques, partial least squares regression and correlation constrained multivariate curve resolution-alternating least squares are compared. Models' performances are analyzed in out-of-control cases. PMID:25818140

  15. Theoretical study of adsorption of amino acids on graphene and BN sheet in gas and aqueous phase with empirical DFT dispersion correction.

    PubMed

    Singla, Preeti; Riyaz, Mohd; Singhal, Sonal; Goel, Neetu

    2016-02-21

    Understanding interactions of biomolecules with nanomaterials at the molecular level is crucial to design new materials for practical use. In the present study, adsorption of three distinct types of amino acids, namely, valine, arginine and aspartic acid, over the surface of structurally analogous but chemically different graphene and BN nanosheets has been explored within the formalism of DFT. The explicit dispersion correction incorporated in the computational methodology improves the accuracy of the results by accounting for long range van der Waals interactions and is essential for agreement with experimental values. The real biological environment has been mimicked by re-optimizing all the model structures in an aqueous medium. The study provides ample evidence in terms of adsorption energy, solvation energy, separation distance and charge analysis to conclude that both the nano-surfaces adsorb the amino acids with release of energy and there are no bonded interactions between the two. The polarity of the BN nanosheet provides it an edge over the graphene surface to have more affinity towards amino acids. PMID:26863069

  16. Mineralogy and chemistry of altered Icelandic basalts: Application to clay mineral detection and understanding aqueous environments on Mars

    NASA Astrophysics Data System (ADS)

    Ehlmann, B. L.; Bish, D. L.; Ruff, S. W.; Mustard, J. F.

    2012-10-01

    We used a suite of techniques, including those emulating compositional data sets obtained from Mars orbit and obtainable at the Mars surface, to examine aqueous alteration of basaltic rocks from Iceland as a mineralogic and geochemical analog for Noachian environments on Mars. A sample suite was collected for laboratory measurement of (1) whole-rock visible/near-infrared (VNIR) reflectance and thermal infrared (TIR) emission spectra; (2) VNIR and TIR reflectance spectra of particle-size separates derived from the bulk rock and from materials extracted from fractures/vesicles; (3) X-ray diffraction (XRD) patterns for determination of quantitative modal mineralogy; (4) major element chemistry using flux fusion of whole-rock powders; and (5) electron microprobe analyses of minerals in thin sections. Conclusions about aqueous alteration can be influenced by technique. For these basalts, whole-rock chemical data showed scant evidence for chemical fractionation, but TIR, VNIR, and XRD measurements identified distinctive assemblages of hydrous silicate minerals, differing by sample. XRD provided the most complete and accurate quantitative determination of sample mineralogy. However, VNIR spectroscopy was the technique most useful for determining composition of low-abundance smectite clays, and TIR spectroscopy was the most useful for recognizing hydrated silicates in thin surface coatings. High spatial resolution mineralogical and chemical data sets were useful for understanding the texture and distribution of alteration products and variations in fluid chemistry. No single approach provides a complete assessment of the environment of alteration, demonstrating the importance of employing multiple, synergistic mineralogical and geochemical techniques and instruments in exploration of rock strata from aqueous paleoenvironments on Mars.

  17. Reactions of aqueous glucose solution over solid-acid Y-zeolite catalyst at 110-160 C

    SciTech Connect

    Lourvanij, K.; Rorrer, G.L. )

    1993-01-01

    Reactions of glucose with solid-acid Y-zeolite catalyst were studied to see if this heterogeneous system could produce oxygenated hydrocarbons by shape-selective, acid-catalyzed processes at fairly low temperatures. Experimentally, aqueous solutions of glucose (12 wt %) were reacted with HY-zeolite powder in a well-mixed batch reactor at temperatures ranging from 110 to 160 C and catalyst concentrations ranging from 2 to 20 g/150 ml. Unreacted glucose and oxygenated hydrocarbon products were measured by HPLC as a function of reaction time (0-24 h) and process conditions. Glucose conversions of 100% were obtained at 160 C after an 8-h reaction time. The apparent activation energy based on glucose conversion was 23.25 [plus minus] 0.40 kcal/mol. Several acid-catalyzed reactions were identified, including isomerization of glucose to fructose, partial dehydration of glucose to 5-(hydroxymethyl)furfural (HMF), rehydration and cleavage of HMF to formic acid and 4-oxo-pentanoic acid, and carbonization . Polymers of HMF and seven minor additional products in the lower molecular weight organic acids/aldehydes/ketones elution range were also isolated by HPLC. High yields of organic acids relative to HMF and lowered selectivity of HMF in the bulk phase relative to the homogeneous acid-catalyzed reaction suggests the possibility of molecular sieving reactions within the Y-zeolite in addition to reactions on the outer surface of the Y-zeolite particle.

  18. A modular diffusion barrier based on phase separation for localized delivery of discrete drug volumes in aqueous environments.

    PubMed

    Steigert, Juergen; Strasser, Monika; Wangler, Nicolai; Brett, Olivia; Streule, Wolfgang; Koltay, Peter; Daub, Martina; Zengerle, Roland

    2009-06-21

    We present a new tool for the precisely controlled transfer of individual picoliter (pL) droplets in the range of 150-950 pL at user defined local positions within aqueous liquid environments while avoiding any leakage by diffusion. This is achieved by a low-cost, disposable and biocompatible cap that can be placed on top of any pL-dispenser and generates a phase-gap between dispensing agent and target liquid when the dispenser is dipped into the latter. We developed two different working modes: (i) the standard mode enables an instant injection (< 1 ms) of the droplet into the liquid environment and (ii) the focus mode further increases the spatial resolution from 100 microm to 50 microm at the cost of slowing down the injection time. For the phase-gap we have proven an excellent long-term stability of more than 30 hours against capillary priming. PMID:19495466

  19. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    PubMed

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  20. Chemical weathering of granite under acid rainfall environment, Korea

    NASA Astrophysics Data System (ADS)

    Lee, Seung Yeop; Kim, Soo Jin; Baik, Min Hoon

    2008-08-01

    Chemical weathering was investigated by collecting samples from five selected weathering profiles in a high elevation granitic environment located in Seoul, Korea. The overall changes of chemistry and mineralogical textures were examined reflecting weathering degrees of the samples, using polarization microscopy, X-ray diffraction (XRD), electron probe micro analysis (EPMA), X-ray fluorescence spectroscopy (XRF), and inductively coupled plasma-mass spectroscopy (ICP-MS). The chemical distribution in the weathering profiles shows that few trace elements are slightly immobile, whereas most major (particularly Ca and Na) and trace elements are mobile from the beginning of the granite weathering. On the other hand, there were mineralogical changes initiated from a plagioclase breakdown, which shows a characteristic circular dissolved pattern caused by a preferential leaching of Ca cation along grain boundaries and zoning. The biotite in that region is also supposed to be sensitive to exterior environmental condition and may be easily dissolved by acidic percolated water. As a result, it seems that some rock-forming minerals in the granitic rock located in Seoul are significantly unstable due to the environmental condition of acidic rainfall and steep slopes, where they are susceptible to be dissolved incongruently leading some elements to be highly depleted.

  1. Nondisruptive Dissolution of Hyperpolarized (129)Xe into Viscous Aqueous and Organic Liquid Crystalline Environments.

    PubMed

    Truxal, Ashley E; Slack, Clancy C; Gomes, Muller D; Vassiliou, Christophoros C; Wemmer, David E; Pines, Alexander

    2016-04-01

    Studies of hyperpolarized xenon-129 (hp-(129)Xe) in media such as liquid crystals and cell suspensions are in demand for applications ranging from biomedical imaging to materials engineering but have been hindered by the inability to bubble Xe through the desired media as a result of viscosity or perturbations caused by bubbles. Herein a device is reported that can be reliably used to dissolve hp-(129)Xe into viscous aqueous and organic samples without bubbling. This method is robust, requires small sample volumes (<60 μL), is compatible with existing NMR hardware, and is made from readily available materials. Experiments show that Xe can be introduced into viscous and aligned media without disrupting molecular order. We detected dissolved xenon in an aqueous liquid crystal that is disrupted by the shear forces of bubbling, and we observed liquid-crystal phase transitions in (MBBA). This tool allows an entirely new class of samples to be investigated by hyperpolarized-gas NMR spectroscopy. PMID:26954536

  2. Amino acid composition, antinutrients and allergens in the peanut protein fraction obtained by an aqueous enzymatic process.

    PubMed

    Latif, S; Pfannstiel, J; Makkar, H P S; Becker, K

    2013-01-01

    Enzyme-assisted aqueous extraction (EAE) of peanut kernel was used to extract oil and protein. The aqueous fraction (AF) obtained by EAE had a better essential amino acid profile than the residues obtained by solvent extraction (Rs) and cold pressing (Rc). No major difference in the trypsin inhibitor activity among AF, Rs and Rc was observed; however, the trypsin inhibitor activity was drastically reduced in the residue obtained after EAE. AF was subjected to MALDI-TOF/MS, revealing it to be rich in peptides (107) with molecular masses from m/z 700 to 2369Da. AF had an extremely low phytate content and was rich in peptides, which could be used as a food supplement. ESI-MS/MS data were used for the identification of major peanut allergens, viz., Ara h1, h3, h6-8. Their allergenic potential needs to be established. PMID:23017415

  3. Theoretical study of the hydrolysis of ethyl benzoate in acidic aqueous solution using the QM/MC/FEP method

    NASA Astrophysics Data System (ADS)

    Kaweetirawatt, Thanayuth; Kokita, Yohei; Iwai, Shiho; Sumimoto, Michinori; Hori, Kenji

    2012-09-01

    The hydrolysis of ethyl benzoate in acidic condition was theoretically studied for models with two (2W) or three water (3WA) molecules at the B3LYP/6-311++G(d,p) levels of theory. Activation free energy of solvation in aqueous solution (ΔG‡cal) was calculated using the QM/MC/FEP method. The value of the 2W model in aqueous solution was calculated to be smaller by more than 5.0 kcal mol-1 than the observed value (26.0 kcal mol-1 at 298 K). The position of the third water molecule in the 3WA model plays an essential role in producing the ΔG‡cal value (26.4 kcal mol-1) consistent with the experimental value.

  4. Equilibrium phase diagrams of aqueous mixtures of malonic acid and sulfate/ammonium salts.

    PubMed

    Salcedo, Dara

    2006-11-01

    Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. In this study, solubility in water, water activity (a(w)) of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid (MA) with ammonium sulfate (AS) and ammonium bisulfate (ABS) at 25 degrees C over the full range of composition (from 0 wt % to the solubility limit of the mixture components). The data were used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity (RH). This work complements previous reports on the thermodynamic properties of AS/MA mixtures because the range of concentrations investigated is larger than in any other published single study. On the other hand, this is the first report on the a(w), deliquescence, and water absorption of ABS/MA mixtures. The eutonic composition for AS/MA mixtures was found to be 66.8 MA dry wt % (MA dry wt % = MA mass x 100/(AS mass + MA mass) with a DRH of 0.437. The eutonic composition for the ABS/MA mixtures was lower than for the AS/MA mixtures: 20.9 MA dry wt % with a DRH of 0.327. Measured a(w) of liquid AS/MA and ABS/MA solutions is compared with an extended Zdanovskii-Stokes-Robinson expression, obtaining a good agreement (error < 5-6%). The expression was used to predict water uptake of mixtures and might be useful to interpret particle hygroscopic growth experiments. Comparison of the AS/MA and ABS/MA systems indicates that ABS reduces the DRH and enhances water uptake, relative to mixtures with AS. The results confirm that ambient particles containing sulfate and water-soluble organic compounds can remain liquid or partially liquid at very low ambient RH

  5. Surface Changes and Impurity Release Kinetics of Titanium Dioxide Nanoparticles in Aqueous Environment

    EPA Science Inventory

    Previous studies have found the significant role of impurities (i.e., silicon, phosphorus) in the aggregation and sedimentation of TiO2 nanoparticles in water environment. However, it is not understood whether dissolution of the impurities potentially impacts the environment or t...

  6. Removal and recovery of furfural, 5-hydroxymethylfurfural, and acetic acid from aqueous solutions using a soluble polyelectrolyte.

    PubMed

    Carter, Brian; Gilcrease, Patrick C; Menkhaus, Todd J

    2011-09-01

    In the cellulosic ethanol process, furfural, 5-hydroxymethylfurfural (HMF), and acetic acid are formed during the high temperature acidic pretreatment step needed to convert biomass into fermentable sugars. These compounds can inhibit cellulase enzymes and fermentation organisms at relatively low concentrations (≥ 1 g/L). Effective removal of these inhibitory compounds would allow the use of more severe pretreatment conditions to improve sugar yields and lead to more efficient fermentations; if recovered and purified, they could also be sold as valuable by-products. This study investigated the separation of aldhehydes (furfural and HMF) and organic acid (acetic acid) inhibitory compounds from simple aqueous solutions by using polyethyleneimene (PEI), a soluble cationic polyelectrolyte. PEI added to simple solutions of each inhibitor at a ratio of 1 mol of functional group to 1 mol inhibitor removed up to 89.1, 58.6, and 81.5 wt% of acetic acid, HMF, and furfural, respectively. Furfural and HMF were recovered after removal by washing the polyelectrolyte/inhibitor complex with dilute sulfuric acid solution. Recoveries up to 81.0 and 97.0 wt% were achieved for furfural and HMF, respectively. The interaction between PEI and acetic acid was easily disrupted by the addition of chloride ions, sulfate ions, or hydroxide ions. The use of soluble polymers for the removal and recovery of inhibitory compounds from biomass slurries is a promising approach to enhance the efficiency and economics of an envisioned biorefinery. PMID:21455937

  7. Behavior of transplutonium elements on ion-exchange materials in mixed aqueous-organic solutions of mineral acids

    SciTech Connect

    Guseva, L.I.; Tikhomirov, G.S.; Stepushkina, V.V.

    1987-03-01

    Systematic studies are reported on the behavior of transplutonium elements (TPE) on cation-exchange and anion-exchange materials in mixed aqueous-organic solutions of mineral acids (HClO/sub 4/, HCl, HNO/sub 3/, H/sub 2/SO/sub 4/, H/sub 3/PO/sub 4/) as affected by solution composition, nature of acid, and nature of organic solvent. With all these acids, replacing most of the water by alcohol increases the TPE uptake on the ion exchangers, and the effect occurs for the cation exchangers at lower contents of the organic component. Optimum conditions have been identified for concentrating and separating TPE from numerous elements. The most effective system consists of anion exchanger with HNO/sub 3/ and alcohol.

  8. Recovery of transplutonium elements from aqueous and water-ethanol solutions of sulfuric acid and their separation from other actinides

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-05-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on anion and cation exchangers in aqueous and water-ethanol solutions of sulfuric acid as a function of the various components of the solution has been investigated. It has been discovered that the presence of ethanol in sulfuric acid solutions causes an increase in the distribution coefficients both on cation exchangers and on anion exchangers. The possibility of the use of ion exchangers for the preconcentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements which form strong complexes with sulfate ions over a broad range of concentrations of sulfuric acid has been demonstrated.

  9. Simultaneous determination of nitric acid and uranium concentrations in aqueous solution from measurements of electrical conductivity, density, and temperature

    SciTech Connect

    Spencer, B.B.

    1991-01-01

    Nuclear fuel reprocessing plants handle aqueous solutions of nitric acid and uranium in large quantities. Automatic control of process operations requires reliable measurements of these solutes concentration, but this is difficult to directly measure. Physical properties such as solution density and electrical conductivity vary with solute concentration and temperature. Conductivity, density and temperature can be measured accurately with relatively simple and inexpensive devices. These properties can be used to determine solute concentrations will good correlations. This paper provides the appropriate correlations for solutions containing 2 to 6 Molar (M) nitric acid and 0 to 300 g/L uranium metal at temperatures from 25--90{degrees}C. The equations are most accurate below 5 M nitric acid, due to a broad maximum in the conductivity curve at 6 M. 12 refs., 9 figs., 6 tabs.

  10. Electrochemical noise measurements on carbon and stainless steels in high subcritical and supercritical aqueous environments

    SciTech Connect

    Macdonald, D.D.; Liu, C.; Manahan, M.P. Sr.

    1996-12-31

    The electrochemical noise induced in a pair of corroding carbon steel probes in simulated heat transport circuit fluids of a supercritical fossil-fueled power plant at temperatures up to 550 C and at pressures as high as 276 bar (4,000 psi) was measured as a function of oxygen concentration, flow rate, temperature, and pressure. Additionally, electrochemical noise measurement (ENM) was explored as a means of detecting and monitoring stress corrosion cracking in sensitized Type 304 SS in high-temperature water (up to 288 C). Experimental results from these studies indicate that the electrochemical noise induced from corrosion of steels in high-temperature aqueous systems can be measured in a reproducible manner. The magnitude of the electrochemical noise responds sensibly to changes in the chemical and physical properties of the fluid, and the pattern of the electrochemical noise contains information on the nature of the corrosion processes that occur, including general corrosion, pitting attack, and stress corrosion cracking.

  11. Biosensing for the Environment and Defence: Aqueous Uranyl Detection Using Bacterial Surface Layer Proteins

    PubMed Central

    Conroy, David J.R.; Millner, Paul A.; Stewart, Douglas I.; Pollmann, Katrin

    2010-01-01

    The fabrication of novel uranyl (UO22+) binding protein based sensors is reported. The new biosensor responds to picomolar levels of aqueous uranyl ions within minutes using Lysinibacillus sphaericus JG-A12 S-layer protein tethered to gold electrodes. In comparison to traditional self assembled monolayer based biosensors the porous bioconjugated layer gave greater stability, longer electrode life span and a denser protein layer. Biosensors responded specifically to UO22+ ions and showed minor interference from Ni2+, Cs+, Cd2+ and Co2+. Chemical modification of JG-A12 protein phosphate and carboxyl groups prevented UO22+ binding, showing that both moieties are involved in the recognition to UO22+. PMID:22399904

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

    USGS Publications Warehouse

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

    2004-01-01

    Sedimentary rocks at Eagle crater in Meridiani Planum are composed of fine-grained siliciclastic materials derived from weathering of basaltic rocks, sulfate minerals (including magnesium sulfate and jarosite) that constitute several tens of percent of the rock by weight, and hematite. Cross-stratification observed in rock outcrops indicates eolian and aqueous transport. Diagenetic features include hematite-rich concretions and crystal-mold vugs. We interpret the rocks to be a mixture of chemical and siliciclastic sediments with a complex diagenetic history. The environmental conditions that they record include episodic inundation by shallow surface water, evaporation, and desiccation. The geologic record at Meridiani Planum suggests that conditions were suitable for biological activity for a period of time in martian history.

  13. A potentiodynamic study of aluminum-lithium alloys in an aqueous sodium chloride environment

    NASA Technical Reports Server (NTRS)

    Tsao, C.-H. T.; Pizzo, P. P.

    1985-01-01

    The characteristics of the potentiodynamic curves for Al-Li alloys in 3.5 percent NaCl aqueous solution are explained and the electrochemical parameters of the potentiodynamic technique are correlated to observed pitting and intergranular cracking behavior. It is shown that the oxygen content of the sodium chloride electrolyte plays an important role in the electrochemical behavior of Al-Li alloys. The potentiodynamic behavior of the alloys is found to be insensitive to variation in compositional content and heat treatment, both of which affect the stress-corrosion behavior. Stringer oxide particle attack and random pitting are observed. It is shown that alternate-immersion exposure prior to potentiodynamic polarization may offer a means of assessing susceptibility to stress-corrosion cracking.

  14. Atmospheric pressure resistive barrier air plasma jet induced bacterial inactivation in aqueous environment

    NASA Astrophysics Data System (ADS)

    Thiyagarajan, Magesh; Sarani, Abdollah; Gonzales, Xavier

    2013-03-01

    An atmospheric pressure resistive barrier air plasma jet is designed to inactivate bacteria in aqueous media in direct and indirect exposure modes of treatment. The resistive barrier plasma jet is designed to operate at both dc and standard 50-60 Hz low frequency ac power input and the ambient air at 50% humidity level was used as the operating gas. The voltage-current characteristics of the plasma jet were analyzed and the operating frequency of the discharge was measured to be 20 kHz and the plasma power was measured to be 26 W. The plasma jet rotational temperatures (Trot) are obtained from the optical emission spectra, from the N2C-B(2+) transitions by matching the experimental spectrum results with the Spectra Air (SPECAIR) simulation spectra. The reactive oxygen and nitrogen species were measured using optical emission spectroscopy and gas analyzers, for direct and indirect treatment modes. The nitric oxides (NO) were observed to be the predominant long lived reactive nitrogen species produced by the plasma. Three different bacteria including Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative), and Neisseria meningitidis (Gram-negative) were suspended in an aqueous media and treated by the resistive barrier air plasma jet in direct and indirect exposure modes. The results show that a near complete bacterial inactivation was achieved within 120 s for both direct and indirect plasma treatment of S. aureus and E. coli bacteria. Conversely, a partial inactivation of N. meningitidis was observed by 120 s direct plasma exposure and insignificant inactivation was observed for the indirect plasma exposure treatment. Plasma induced shifts in N. meningitidis gene expression was analyzed using pilC gene expression as a representative gene and the results showed a reduction in the expression of the pilC gene compared to untreated samples suggesting that the observed protection against NO may be regulated by other genes.

  15. Multi-Scale Studies of Transport and Adsorption Phenomena of Cement-based Materials in Aqueous and Saline Environment

    NASA Astrophysics Data System (ADS)

    Yoon, Se Yoon

    The transport and adsorption phenomena in cement-based materials are the most important processes in the durability of concrete structures or nuclear waste containers, as they are precursors to a number of deterioration processes such as chloride-induced corrosion, sulfate attack, carbonation, etc. Despite this importance, our understanding of these processes remains limited because the pore structure and composition of concrete are complex. In addition, the range of the pore sizes, from nanometers to millimeters, requires the multi-scale modeling of the transport and adsorption processes. Among the various environments that cement-based materials are exposed to, aqueous and saline environments represent the most common types. Therefore, this dissertation investigates the adsorption and transport phenomena of cement-based materials exposed to an aqueous and saline environment from atomic to macro-scales using different arrays of novel spectroscopic techniques and simulation methods, such as scanning transmission X-ray microscopy (STXM), X-ray absorption near edge structure (XANES), molecular dynamics (MD), and finite element method (FEM). The structure and transport of water molecules through interlayer spacing of tobermorite was investigated using MD simulations because the interlayer water of calcium silicate hydrate (C-S-H) gel influences various material properties of concrete. The adsorption processes of cementitious phases interacting with sodium and chloride ions at the nano-scale were identified using STXM and XANES measurements. A mathematical model and FEM procedure were developed to identify the effect of surface treatments at macro-scale on ionic transport phenomena of surface-treated concrete. Finally, this dissertation introduced a new material, calcined layered double hydroxide (CLDH), to prevent chloride-induced deterioration.

  16. The effect of aqueous environments upon the initiation and propagation of fatigue cracks in low-alloy steels

    SciTech Connect

    James, L.A.; Van Der Sluys, W.A.

    1996-01-01

    The effect of elevated temperature aqueous environments upon the initiation and propagation of fatigue cracks in low-alloy steels is discussed in terms of the several parameters which influence such behavior. These parameters include water chemistry, impurities within the steels themselves, as well as factors such as the water flow rate, loading waveform and loading rates. Some of these parameters have similar effects upon both crack initiation and propagation, while others exhibit different effects in the two stages of cracking. In the case of environmentally-assisted crack (EAC) growth, the most important impurities within the steel are metallurgical sulfide inclusions which dissolve upon contact with the water. A ``critical`` concentration of sulfide ions at the crack tip can then induce environmentally-assisted cracking which proceeds at significantly increased crack growth rates over those observed in air. The occurrence, or non-occurrence, of EAC is governed by the mass-transport of sulfide ions to and from the crack-tip region, and the mass-transport is discussed in terms of diffusion, ion migration, and convection induced within the crack enclave. Examples are given of convective mass-transport within the crack enclave resulting from external free stream flow. The initiation of fatigue cracks in elevated temperature aqueous environments, as measured by the S-N fatigue lifetimes, is also strongly influenced by the parameters identified above. The influence of sulfide inclusions does not appear to be as strong on the crack initiation process as it is on crack propagation. The oxygen content of the environment appears to be the dominant factor, although loading frequency (strain rate) and temperature are also important factors.

  17. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part II. Recovery of Ammonia from Sour Waters

    SciTech Connect

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, SUCCiOlC acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  18. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    SciTech Connect

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  19. Acid gas treating by aqueous alkanolamines. Annual report, July-December 1992

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Tamimi, A.; Davis, R.A.; Oelschlager, D.W.

    1992-12-01

    The objective of the work is to investigate the simultaneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed thus far models have been developed for single gas (either H2S or CO2) absorption into a single amine solution (MDEA or DEA). Density and viscosity measurements have been made for aqueous MDEA, DEA and MDEA/DEA mixtures over the temperature range 20 to 100 C and for concentrations up to 50 weight %.

  20. Capillary electrophoresis of some free fatty acids using partially aqueous electrolyte systems and indirect UV detection. Application to the analysis of oleic and linoleic acids in peanut breeding lines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study has shown for the first time the suitability of CE with a partially aqueous electrolyte system for the analysis of free fatty acids (FFA's) in small portions of single peanut seeds. The partially aqueous electrolyte system consisted of 40 mM Tris, 2.5 mM adenosine-5'-monophosphate (AMP) ...

  1. An Optical Fiber-Based Sensor Array for the Monitoring of Zinc and Copper Ions in Aqueous Environments

    PubMed Central

    Kopitzke, Steven; Geissinger, Peter

    2014-01-01

    Copper and zinc are elements commonly used in industrial applications as aqueous solutions. Before the solutions can be discharged into civil or native waterways, waste treatment processes must be undertaken to ensure compliance with government guidelines restricting the concentration of ions discharged in solution. While currently there are methods of analysis available to monitor these solutions, each method has disadvantages, be it high costs, inaccuracy, and/or being time-consuming. In this work, a new optical fiber-based platform capable of providing fast and accurate results when performing solution analysis for these metals is described. Fluorescent compounds that exhibit a high sensitivity and selectivity for either zinc or copper have been employed for fabricating the sensors. These sensors demonstrated sub-part-per-million detection limits, 30-second response times, and the ability to analyze samples with an average error of under 10%. The inclusion of a fluorescent compound as a reference material to compensate for fluctuations from pulsed excitation sources has further increased the reliability and accuracy of each sensor. Finally, after developing sensors capable of monitoring zinc and copper individually, these sensors are combined to form a single optical fiber sensor array capable of simultaneously monitoring concentration changes in zinc and copper in aqueous environments. PMID:24549250

  2. Pattern recognition and data mining software based on artificial neural networks applied to proton transfer in aqueous environments

    NASA Astrophysics Data System (ADS)

    Amani, Tahat; Jordi, Marti; Ali, Khwaldeh; Kaher, Tahat

    2014-04-01

    In computational physics proton transfer phenomena could be viewed as pattern classification problems based on a set of input features allowing classification of the proton motion into two categories: transfer ‘occurred’ and transfer ‘not occurred’. The goal of this paper is to evaluate the use of artificial neural networks in the classification of proton transfer events, based on the feed-forward back propagation neural network, used as a classifier to distinguish between the two transfer cases. In this paper, we use a new developed data mining and pattern recognition tool for automating, controlling, and drawing charts of the output data of an Empirical Valence Bond existing code. The study analyzes the need for pattern recognition in aqueous proton transfer processes and how the learning approach in error back propagation (multilayer perceptron algorithms) could be satisfactorily employed in the present case. We present a tool for pattern recognition and validate the code including a real physical case study. The results of applying the artificial neural networks methodology to crowd patterns based upon selected physical properties (e.g., temperature, density) show the abilities of the network to learn proton transfer patterns corresponding to properties of the aqueous environments, which is in turn proved to be fully compatible with previous proton transfer studies.

  3. Chemiluminescence studies between aqueous phase synthesized mercaptosuccinic acid capped cadmium telluride quantum dots and luminol-H2O2.

    PubMed

    Kaviyarasan, Kulandaivelu; Anandan, Sambandam; Mangalaraja, Ramalinga Viswanathan; Asiri, Abdullah M; Wu, Jerry J

    2016-08-01

    Mercaptosuccinic acid capped Cadmium telluride quantum dots have been successfully synthesized via aqueous phase method. The products were well characterized by a number of analytical techniques, including FT-IR, XRD, HRTEM, and a corrected particle size analysis by the statistical treatment of several AFM measurements. Chemiluminescence experiments were performed to explore the resonance energy transfer between chemiluminescence donor (luminol-H2O2 system) and acceptor CdTe QDs. The combination of such donor and acceptor dramatically reduce the fluorescence while compared to pristine CdTe QDs without any exciting light source, which is due to the occurrence of chemiluminescence resonance energy transfer (CRET) processes. PMID:27131144

  4. Chemiluminescence studies between aqueous phase synthesized mercaptosuccinic acid capped cadmium telluride quantum dots and luminol-H2O2

    NASA Astrophysics Data System (ADS)

    Kaviyarasan, Kulandaivelu; Anandan, Sambandam; Mangalaraja, Ramalinga Viswanathan; Asiri, Abdullah M.; Wu, Jerry J.

    2016-08-01

    Mercaptosuccinic acid capped Cadmium telluride quantum dots have been successfully synthesized via aqueous phase method. The products were well characterized by a number of analytical techniques, including FT-IR, XRD, HRTEM, and a corrected particle size analysis by the statistical treatment of several AFM measurements. Chemiluminescence experiments were performed to explore the resonance energy transfer between chemiluminescence donor (luminol-H2O2 system) and acceptor CdTe QDs. The combination of such donor and acceptor dramatically reduce the fluorescence while compared to pristine CdTe QDs without any exciting light source, which is due to the occurrence of chemiluminescence resonance energy transfer (CRET) processes.

  5. Olivine alteration and H2 production in carbonate-rich, low temperature aqueous environments

    NASA Astrophysics Data System (ADS)

    Neubeck, Anna; Duc, Nguyen Thanh; Hellevang, Helge; Oze, Christopher; Bastviken, David; Bacsik, Zoltán; Holm, Nils G.

    2014-06-01

    Hydrous alteration of olivine is capable of producing molecular hydrogen (H2) under a wide variety of hydrothermal conditions. Although olivine hydrolysis (i.e., serpentinization) has commonly been assessed at elevated temperatures (>100 °C), the nature of these reactions in relation to H2 production at lower temperatures has not been systematically evaluated, especially with regard to carbonate-rich fluids. Specifically, carbonate formation may kinetically infringe on geochemical routes related to serpentinization and H2 production at lower temperatures. Here time-dependent interactions of solid, liquid, and gaseous phases with respect to olivine hydrolysis in a carbonate-rich solution (20 mM HCO3-) at 30, 50 and 70 °C for 315 days is investigated experimentally. Within the first two months, amorphous Si-rich (i.e., talc-like) and carbonate phases precipitated; however, no inhibition of olivine dissolution is observed at any temperature based on surface chemistry analyses. High-resolution surface analyses confirm that precipitates grew as spheroids or vertically to form topographic highs allowing further dissolution of the free olivine surfaces and exposing potential catalysts. Despite no magnetite (Fe3O4) being detected, H2 increased with time in experiments carried out at 70 °C, indicating an alternative coupled route for Fe oxidation and H2 production. Spectrophotometry analyses show that aqueous Fe(II) is largely converted to Fe(III) potentially integrating into other phases such as serpentine and talc, thus providing a viable pathway for H2 production. No increase in H2 production was observed in experiments carried out at 30 and 50 °C supporting observations that incorporation of Fe(II) into carbonates occurred faster than the intertwined processes of olivine hydrolysis and Fe(III) oxidation. Overall, carbonate formation is confirmed to be a major influence related to H2 production in low-temperature serpentinization systems. We studied low temperature

  6. Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

    NASA Astrophysics Data System (ADS)

    Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

    2014-12-01

    A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

  7. Biosorption of clofibric acid and carbamazepine in aqueous solution by agricultural waste rice straw.

    PubMed

    Liu, Zhanguang; Zhou, Xuefei; Chen, Xiaohua; Dai, Chaomeng; Zhang, Juan; Zhang, Yalei

    2013-12-01

    Due to their widespread use, clofibric acid (CA) and carbamazepine (CBZ) have been frequently detected simultaneously at relatively high concentrations in aquatic environments. In this study, agricultural waste rice straw was employed as a potentially low-cost, effective and easy-to-operate biosorbent (RSB) to remove CA and CBZ. The adsorption of both pharmaceuticals followed pseudo second-order kinetics, and intraparticle diffusion was an important rate-limiting step. The adsorption isotherms of both drugs were fit well with Freundlich model. The adsorption of CA onto RSB was exothermic and was more likely to be dominated by physical processes, while the adsorption of CBZ was endothermic. Solution pH was determined to be the most important factor for CA adsorption, such that the adsorption capacity of CA onto RSB increased with the decline of solution pH. In the lower range of solution pH below 3.1, the CA removal efficiency was enhanced with the increase of biosorbent dosage. The CBZ removal efficiency was enhanced with the increase of RSB dosage without pH control. The maximum adsorption capacities were 126.3 mg/g for CA and 40.0 mg/g for CBZ. PMID:24649668

  8. UV Irradiation and Humic Acid Mediate Aggregation of Aqueous Fullerene (nC60) Nanoparticles

    EPA Science Inventory

    The transport and fate of engineered nanomaterials is affected by multiple environmental factors, including sunlight and natural organic matter. In this study, the initial aggregation kinetics of aqueous fullerene (nC60) nanoparticles before and after UVA irradiation was investig...

  9. Robust Structure and Reactivity of Aqueous Arsenous Acid-Platinum(II) Anticancer Complexes**

    PubMed Central

    Miodragović, Ðenana U.; Quentzel, Jeremy A.; Kurutz, Josh W.; Stern, Charlotte L.; Ahn, Richard W.; Kandela, Irawati; Mazar, Andrew; O’Halloran, Thomas V.

    2014-01-01

    The first molecular adducts of platinum and arsenic based anticancer drugs - arsenoplatins - show unanticipated structure, substitution chemistry, and cellular cytotoxicity. The PtII-AsIII bonds in these complexes are stable in aqueous solution and strongly influence the lability of the trans ligand. PMID:24038962

  10. Synchrotron X-ray bio-imaging of natural and synthetic bone-graft materials in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Gun; Bark, Chung Wung

    2014-11-01

    Bone-graft materials in dentistry have osteoinductive and osteoconductive abilities, which depend on their microstructural characteristics, such as their porosity, particle size, micro channels, and absorption. These characteristics have been observed using various imaging techniques, such as optical microscopy and scanning electron microscopy (SEM). However, most techniques cannot provide images in water, even though graft materials in vivo are invariably in contact with different water-based fluids. Synchrotron X-ray imaging allows sample microenvironments to be controlled as X-ray beams easily penetrate air and water. In this report, we used the synchrotron X-ray imaging technique to provide in-situ images of various bone-graft materials in aqueous environments. We observed internal microstructural images of bone-graft materials in real-time in 0.9% saline solution and interactions between bone-graft materials and saline, that is, hydration patterns and bone-graft expansion.

  11. Effect of silty sand with different sizes on corrosion behavior of 3Cr steel in CO2 aqueous environment

    NASA Astrophysics Data System (ADS)

    Liu, Wei; Lu, Songle; Zhang, Peng; Dou, Juanjuan; Zhao, Qinghe

    2016-08-01

    Corrosion behavior of 3Cr steel in CO2 aqueous environment containing silty sand was investigated by immersion test. The results show that CO2 corrosion rate and morphology of 3Cr steel were obviously affected by the size of silty sand. 5000 mesh silty sand mixed with corrosion products, forming compact Cr-rich corrosion scale and resulting in low corrosion rate and uniform corrosion. 1000 mesh silty sand mixed with corrosion products, forming porous corrosion scale without Cr enrichment and resulting in high corrosion rate and pitting corrosion. 5000 mesh silty sand enhanced Cr enrichment in corrosion scale, leading to low anodic current. However, 1000 mesh silty sand deteriorated Cr enrichment in corrosion scale, leading to high anodic current. Cathodic current was reduced by silty sand, but was not affected by two sizes of silty sand. Cr enrichment in corrosion scale of 3Cr steel was obviously affected by separation effect of silty sand.

  12. Activities of microorganisms and enzymes in water-restricted environments: biological activities in aqueous compartments at micron scale

    NASA Astrophysics Data System (ADS)

    Hoppert, Michael; Mlejnek, Klaus; Seiffert, Beatrix; Mayer, Frank

    1997-07-01

    In water-in-oil microemulsions, microdroplets of water, surrounded by a layer of surfactant molecules (reversed micelles), are dispersed in an organic solvent. Various microorganisms (unicellular algae and cyanobacteria) and isolated enzymes were dispersed in microemulsions without loss of biological activity. Each biological system needed a defined quantity of water in the microemulsion for maximum activity. Under optimum conditions, microbial enzymes for various sources (hydrogenases, dehydrogenases) exhibited, besides ten-fold increase in specific activity, a temperature optimum up to 16 degree(s)C higher as compared to aqueous solutions. These experimental findings, together with theoretical considerations, imply that water structure inside reversed micelles is very different from free water, but similar to water in narrow compartments with polar or ionic surfaces. These compartments may represent a model system for environments, where (liquid) water is not available in bulk amounts, but embedded in an anhydrous matrix.

  13. TRANSFORMATION AND FATE OF MANUFACTURED METAL OXIDE AND METAL NANOPARTICLES IN AQUEOUS ENVIRONMENTS

    EPA Science Inventory

    As commercial manufactured nanomaterials become more commonplace, we can expect that these manufactured materials have the potential to get into the environment sometime during production, distribution, use or disposal, i.e. sometime during the lifecycle of these materials. In...

  14. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    NASA Astrophysics Data System (ADS)

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-05-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

  15. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst.

    PubMed

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  16. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    PubMed Central

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  17. L-ascorbic acid quenching of singlet delta molecular oxygen in aqueous media: generalized antioxidant property of vitamin C

    SciTech Connect

    Chou, P.T.; Khan, A.U.

    1983-09-30

    L-ascorbic acid quenches singlet (/sup 1/..delta../sub g/) molecular oxygen in aqueous media (pH 6.8 for (/sup 1/H)H/sub 2/O and pD 7.2 for (/sup 2/H)D/sub 2/O) as measured directly by monitoring (0,0) /sup 1/..delta../sub g/ ..-->.. /sup 3/..sigma../sub g//sup -/ emission at 1.28 micron. Singlet oxygen was generated at room temperature in the solutions via photosensitization of sodium chrysene sulfonate; this sulfonated polycyclic hydrocarbon was synthesized to provide a water soluble chromophore inert to usual dye-ascorbate photobleaching. A marked isotope effect is found; k/sub Q//sup H/sub 2/O/ is 3.3 times faster than k/sub Q//sup D/sub 2/O/, suggesting ascorbic acid is chemically quenching singlet oxygen.

  18. Structural study of very thin anodic alumina films on silicon by anodization in citric acid aqueous solution.

    PubMed

    Kokonou, M; Nassiopoulou, A G; Giannakopoulos, K P; Boukos, N; Travlos, A

    2005-03-01

    The formation of thin alumina films on a silicon substrate by anodization in a mild acid, specifically in 1% wt citric acid aqueous solution, is investigated by transmission electron microscopy (TEM). We present a comparative study between two cases of starting material: pure aluminum and an alloy of aluminum with 1% silicon. In both cases the thickness of the Al layer was less than 50 nm. It was observed that under exactly the same conditions, in the first case the anodization was stopping before anodizing the whole film and a remaining non-anodized Al layer was always present, while in the second case, the Al layer was fully anodized, resulting in an alumina matrix with a very high density of silicon nanocrystals of uniform sizes embedded in it. In both cases the alumina film was compact and amorphous. PMID:15913255

  19. Kinetics of catalytic hydrogenation of 4-nitroaniline in aqueous solutions of propan-2-ol with acid or base additives

    NASA Astrophysics Data System (ADS)

    Kha, Nguen Tkhi Tkhu; Merkin, A. A.; Komarov, A. A.; Korpatenkov, D. O.; Lefedova, O. V.

    2014-04-01

    The effect of addition of acetic acid and sodium hydroxide to an aqueous azeotropic solution of propan-2-ol on the rate of 4-nitroaniline hydrogenation is studied. The base additive accelerates the apparent rate of nitro group reduction, while the presence of acetic acid slows the reaction rate. It is experimentally established that the rate of nitro group conversion calculated from the amount of reacted 4-nitroaniline exceeds the rate of hydrogen uptake from the gas phase in all of the studied solvents. Hydrogen bound by active sites of the catalyst surface is found to participate notably in the reactions. It is proved both experimentally and theoretically that strongly bound atomic forms of adsorbed hydrogen are most active in the reduction of the nitro group.

  20. A semi-quantitative approach for the rapid screening and mass profiling of naphthenic acids directly in contaminated aqueous samples.

    PubMed

    Duncan, Kyle D; Letourneau, Dane R; Vandergrift, Gregory W; Jobst, Karl; Reiner, Eric; Gill, Chris G; Krogh, Erik T

    2016-01-01

    We report the use of a direct sampling, online analytical approach for the determination of acid extractable naphthenic acids in complex aqueous samples, known as condensed phase membrane introduction mass spectrometry (CP-MIMS). The technique employs a capillary hollow fibre semi-permeable membrane probe configured for immersion into a pH adjusted sample. A continuously flowing methanol acceptor phase transfers naphthenic acids to an electrospray ionization source, operated in negative ion mode, whereupon they are analysed by mass spectrometry as [M-H](-) ions. High-resolution mass spectrometry is used to characterize the influence of sample pH on membrane transport of multiple components of complex naphthenic acid mixtures. We demonstrate the use of CP-MIMS for semi-quantitative analysis of real-world samples using selected ion monitoring and full scan mass spectra at unit mass resolution. The technique has also been employed to continuously monitor the temporal evolution in the mass profile and concentrations of individual naphthenic acid isomer classes in heterogeneous solutions during adsorption processes. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26757071

  1. Non-aqueous capillary electrophoresis for the analysis of acidic compounds using negative electrospray ionization mass spectrometry.

    PubMed

    Bonvin, Grégoire; Schappler, Julie; Rudaz, Serge

    2014-01-01

    Non-aqueous capillary electrophoresis (NACE) is an attractive CE mode, in which water solvent of the background electrolyte (BGE) is replaced by organic solvent or by a mixture of organic solvents. This substitution alters several parameters, such as the pKa, permittivity, viscosity, zeta potential, and conductivity, resulting in a modification of CE separation performance (i.e., selectivity and/or efficiency). In addition, the use of NACE is particularly well adapted to ESI-MS due to the high volatility of solvents and the low currents that are generated. Organic solvents reduce the number of side electrochemical reactions at the ESI tip, thereby allowing the stabilization of the ESI current and a decrease in background noise. All these features make NACE an interesting alternative to the aqueous capillary zone electrophoresis (CZE) mode, especially in combination with mass spectrometry (MS) detection. The aim of this work was to evaluate the use of NACE coupled to negative ESI-MS for the analysis of acidic compounds with two available CE-MS interfaces (sheath liquid and sheathless). First, NACE was compared to aqueous CZE for the analysis of several pharmaceutical acidic compounds (non-steroidal anti-inflammatory drugs, NSAIDs). Then, the separation performance and the sensitivity achieved by both interfaces were evaluated, as were the impact of the BGE and the sample composition. Finally, analyses of glucuronides in urine samples subjected to a minimal sample pre-treatment ("dilute-and-shoot") were performed by NACE-ESI-MS, and the matrix effect was evaluated. A 20- to 100-fold improvement in sensitivity was achieved using the NACE mode in combination with the sheathless interface and no matrix effect was observed regardless of the interfaces. PMID:24315358

  2. THE ECOLOGICAL EFFECTS OF TRICHLORACETIC ACID (TCAA) IN THE ENVIRONMENT

    EPA Science Inventory

    Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. ...

  3. Gamma irradiation of isocitric and citric acid in aqueous solution: Relevance in prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Negrón-Mendoza, A.; Ramos-Bernal, S.

    2015-07-01

    The radiation chemistry of hydroxy acids like citric and isocitric acids is rather scarce, even though they are crucial compounds in biological systems and for food irradiation. The aim of this work is to study the radiolytic behavior of these acids focused on the interconversion induced by radiation of citric and isocitric acid into other members of the Krebs cycle. The results showed that among the products formed were succinic, malonic, malic and other acids related to metabolic pathways, and these results are correlated with its possible role in chemical evolution processes.

  4. Gamma irradiation of isocitric and citric acid in aqueous solution: Relevance in prebiotic chemistry

    SciTech Connect

    Negrón-Mendoza, A. Ramos-Bernal, S.

    2015-07-23

    The radiation chemistry of hydroxy acids like citric and isocitric acids is rather scarce, even though they are crucial compounds in biological systems and for food irradiation. The aim of this work is to study the radiolytic behavior of these acids focused on the interconversion induced by radiation of citric and isocitric acid into other members of the Krebs cycle. The results showed that among the products formed were succinic, malonic, malic and other acids related to metabolic pathways, and these results are correlated with its possible role in chemical evolution processes.

  5. Surface modification of alumina-coated silica nanoparticles in aqueous sols with phosphonic acids and impact on nanoparticle interactions.

    PubMed

    Pauly, Céline Schmitt; Genix, Anne-Caroline; Alauzun, Johan G; Sztucki, Michael; Oberdisse, Julian; Hubert Mutin, P

    2015-07-15

    It is often necessary to tailor nanoparticle (NP) interactions and their compatibility with a polymer matrix by grafting organic groups, but the commonly used silanization route offers little versatility, particularly in water. Herein, alumina-coated silica NPs in aqueous sols have been modified for the first time with low molecular-weight phosphonic acids (PAs) bearing organic groups of various hydrophobicities and charges: propyl, pentyl and octyl PAs, and two PAs bearing hydrophilic groups, either a neutral diethylene glycol (DEPA) or a potentially charged carboxylic acid (CAPA) group. The interactions and aggregation in the sols have been investigated using zeta potential measurements, dynamic light scattering, transmission electron microscopy, and small-angle scattering methods. The surface modification has been studied using FTIR and (31)P MAS NMR spectroscopies. Both high grafting density ρ and high hydrophobicity of the groups on the PAs induced aggregation, whereas suspensions of NPs grafted by DEPA remained stable up to the highest ρ. Unexpectedly, CAPA-modified NPs showed aggregation even at low ρ, suggesting that the carboxylic end group was also grafted to the surface. Surface modification of aqueous sols with PAs allows thus for the grafting of a higher density and a wider variety of organic groups than organosilanes, offering an increased control of the interactions between NPs, which is of interest for designing waterborne nanocomposites. PMID:26134150

  6. Atomic force microscopy based nanoindentation study of onion abaxial epidermis walls in aqueous environment

    NASA Astrophysics Data System (ADS)

    Xi, Xiaoning; Kim, Seong H.; Tittmann, Bernhard

    2015-01-01

    An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impacts on the cell wall modulus, and not the cellulose microfibril packing.

  7. Atomic force microscopy based nanoindentation study of onion abaxial epidermis walls in aqueous environment

    SciTech Connect

    Xi, Xiaoning; Tittmann, Bernhard; Kim, Seong H.

    2015-01-14

    An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impacts on the cell wall modulus, and not the cellulose microfibril packing.

  8. Determination of Arrhenius and Thermodynamic Parameters for the Aqueous Reaction of the Hydroxyl Radical with Lactic Acid

    SciTech Connect

    Leigh R. Martin; Stephen P. Mezyk; Bruce J. Mincher

    2009-01-01

    Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer, and also to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at pH~3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid this rate constant is given by the equation: ln k1 = (23.85 ± 0.19) – (1120 ± 54) / T, corresponding to an activation energy of 9.31 ± 0.45 kJ mol-1 and a room temperature reaction rate constant of (5.24 ± 0.09) x 108 M-1 s-1 (24.0oC). For the lactate ion, the temperature-dependent rate constant is given by: ln k2 = (24.83 ± 0.14) – (1295 ± 42) / T, for an activation energy of 10.76 ± 0.35 kJ mol-1 and a room temperature value of (7.77 ± 0.11) x 108 M-1 s-1 (22.2oC). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pKa value, allowing thermodynamic parameters for the acid dissociation to be calculated as ?Hº = -10.75 ± 1.77 kJ mol-1, ?Sº = -103.9 ± 6.0 J K-1 mol-1 and ?Gº = 20.24 ± 2.52 kJ mol-1 at low ionic strength.

  9. In-situ spectroscopic investigations of the redox behavior of poly(indole-5-carboxylic-acid) modified electrodes in acidic aqueous solutions.

    PubMed

    Talbi, H; Billaud, D; Louarn, G; Pron, A

    2001-03-01

    The oxidation of electrochemically grown poly(indole-5-carboxylic-acid) (P5CO2H) and its spectroscopic properties have been studied by in-situ spectroelectrochemical techniques. The purpose of this paper is to characterize the different modifications on the P5CO2H backbone, induced by the electrochemical oxidation in aqueous acidic solution. We have identified, on the basis of Raman spectra, the vibrational modes associated with neutral and oxidized segments of polymer. It was shown that at least three chemically and optically different species (perhaps other products too) are produced in different potential regimes upon oxidation of this polymer. The results obtained also indicate that the molecular properties of this conducting polymer are better revealed by in-situ resonant spectra than by ex-situ infrared and Raman studies. PMID:11300553

  10. AQUEOUS CO2 SOLUTIONS AT SILICA SURFACES AND WITHIN NANOPORE ENVIRONMENTS: Insights from isobaric-isothermal molecular dynamics

    SciTech Connect

    Chialvo, Ariel A; Vlcek, Lukas; Cole, David

    2012-01-01

    We present a detailed molecular-based characterization via isobaricisothermal molecular dynamics simulation of the microstructure and dynamics of water-rich aqueous CO2 solutions at silica surfaces and under extreme confinement between finite silica plates at state conditions relevant to geologic capture and sequestration of carbon dioxide. The study comprises three types of slit-pore plates to represent two extreme cases of surface polarity, and a mismatched pair of plates, to interrogate the fluid behavior at and confined between heterogeneous surfaces. We found layer formation of H2O and CO2 whose strength depends on the nature of the plate surface, i.e., stronger H2O layering at hydrophilic than at hydrophobic plates with a simultaneous weaker water mediated CO2 /hydrophilic-surface interactions. We observed the opposite behavior with the hydrophobic plates where the weaker water layering results from the CO2 mediated H2O/hydrophobicsurface interactions. Moreover, we illustrated how the interplay between these types of interactions and extreme fluid confinement, i.e., strong overlapping of interfacial structures, can induce a drying out of the pore environment whose immediate consequence is a significant CO2 concentration enhancement relative to that of the bulk environment. Finally, we assessed the effect of the nature of the plate surfaces on the translational diffusion coefficient of water, where we found that this property changes 2 monotonically at purely interfacial regions, but non-monotonically under confinement.

  11. Fast and highly-efficient removal of methylene blue from aqueous solution by poly(styrenesulfonic acid-co-maleic acid)-sodium-modified magnetic colloidal nanocrystal clusters

    NASA Astrophysics Data System (ADS)

    Song, Yu-Bei; Lv, Shao-Nan; Cheng, Chang-Jing; Ni, Guo-Li; Xie, Xiao-Wa; Huang, Wei; Zhao, Zhi-Gang

    2015-01-01

    Magnetic colloidal nanocrystal clusters (MCNCs) modified with different amounts of poly(4-styrenesulfonic acid-co-maleic acid) sodium (PSSMA) have been prepared through simple one-step solvothermal method for removal of methylene blue (MB) from aqueous solution. The prepared MCNCs are characterized by Fourier transform infrared (FT-IR) spectra, scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), X-ray diffraction (XRD), nitrogen adsorption-desorption technique and dynamic light scattering (DLS). Moreover, effects of the solution pH, contact time, adsorbent dosage, ionic strength and initial dye concentration on MB adsorption onto the MCNCs are systematically investigated. The PSSMA-modified MCNCs show fast and highly-efficient MB removal capacity, which dramatically depends on the immobilization amounts of PSSMA, solution pH and adsorbent dosage. Their adsorption kinetics and isotherms exhibit that the kinetics and equilibrium adsorptions can be well-described by pseudo-second-order kinetic and Langmuir model, respectively. These magnetic nanocomposites, with high separation efficiency, low production cost and recyclable property, are promising as functional adsorbents for efficient removal of cationic organic pollutants from aqueous solution.

  12. Simultaneous removal of acid green 25 and mercury ions from aqueous solutions using glutamine modified chitosan magnetic composite microspheres.

    PubMed

    Tao, Xue; Li, Kun; Yan, Han; Yang, Hu; Li, Aimin

    2016-02-01

    In this current work, the magnetic composite microsphere containing glutamine modified chitosan and silica coated Fe3O4 nanoparticles (CS-Gln-MCM) has been successfully prepared and extensively characterized, which is a kind of biodegradable materials. CS-Gln-MCM shows enhanced removal efficiency for both acid green 25 (AG25), an amphoteric dye, and mercury ions (Hg(2+)) from water in the respective while measured pH range compared with chitosan magnetic composite microsphere (CS-MCM) without modification. It is due to the fact that the grafted amino acid provides a variety of additional adsorption active sites and diverse adsorption mechanisms are involved. In AG25 and Hg(2+) aqueous mixture, the modified adsorbents bear preferential adsorption for AG25 over Hg(2+) in strong acidic solutions ascribed to multiple interactions between AG25 and CS-Gln-MCM, such as hydrogen bonding and electrostatic interactions. While, in weak acidic conditions, an efficient simultaneous removal is observed for different adsorption effects involved in aforementioned two pollutants. Besides, CS-Gln-MCM illuminates not only short equilibrium time for adsorption of each pollutant less than 20.0 min but also rapid magnetic separation from water and efficient regeneration after saturated adsorption. Therefore, CS-Gln-MCM bears great application potentials in water treatment. PMID:26618263

  13. Surface crystallographic dependence of voltammetric oxidation of polyhydric alcohols and related systems at monocrystalline gold-acidic aqueous interfaces

    NASA Astrophysics Data System (ADS)

    Hamelin, Antoinette; Ho, Yeunghaw; Chang, Si-Chung; Gao, Xiaoping; Weaver, Michael J.

    1992-02-01

    The voltammetric oxidation in aqueous 0.1 Molar perchloric acid of four polyhydric alcohols, ethylene glycol, glycerol, meso-erythritol, and d-mannitol, on seven oriented gold surfaces is reported with the objective of assessing the role of surface crystallographic orientation on the catalytic electrooxidation of such poly-functional reactants. The automatically well-ordered nature of these gold surfaces has been scrutinized by in-situ scanning tunneling microscopy. In particular, the Au(221) and (533) faces were selected since they provide stepped surfaces, 4(111)-(111) and 4(111)-(100), respectively. The results are compared with corresponding data for simple unifunctional reactants, specifically for formic acid oxidation and with results reported previously for carbon monoxide oxidation. In contrast to the last reaction, the electrooxidation rates for both the polyhydric alcoholic and formic acid are greatest on Au(111), with Au(110) displaying unusually low activity. While formic acid electrooxidation is insensitive to the presence of monoatomic surface steps, the polyhydric alcohols (especially mannitol) are substantially less reactive on AU(221) and (533) relative to Au(111).

  14. Corrosion characteristics of seven metals in three aqueous environments for forensic applications

    NASA Astrophysics Data System (ADS)

    Tong, Tianqi

    Corrosion characteristics of seven varieties of metals---zinc, brass C260, stainless steel 302, stainless steel 316, stainless steel 420, stainless steel 430, and stainless steel 440---in three aqueous media---Atlantic Ocean, Charles River, and deionized waters---were assessed via mass loss methods over 32 weeks, with supplemental data in the form of photomicrographic records. Concurrently, tests were conducted to determine the degree of measurement error resulting from the analytical scale used during corrosion assessment. This was accomplished by using reference samples of each type of metal and a glass vial as the container that held the metal and water samples. These error tests indicated that while the mass error associated with the metal samples was low, the error in mass associated with the vial displayed error margins two orders of magnitude larger than the error margins for the smaller metal samples. Further, control tests and statistical analysis indicated that this variation was the result of some quality inherent to the vial. The metal samples involved in the corrosion assessment experiment generally displayed corrosion characteristics in agreement with trends reported in the literature. Zinc produced the greatest quantity of corrosion residues out of all the metals studied. Brass C260 also developed visible corrosion. For example, brass C260 developed dark green/brown adherent residue and whitish blue-tinted nonadherent residue in Atlantic Ocean water, faint greenish tarnishing and some dark green spots and dots over time in Charles River water, and only faint greenish tarnish in deionized water. In contrast with zinc and brass C260, the stainless steels did not exhibit signs of significant corrosion rates excepting stainless steel 420 (SS420), which displayed pitted features surrounded by multi-colored rings on all of its Atlantic Ocean immersion samples and 25% of its Charles River immersion samples. Atlantic Ocean water generally caused the greatest

  15. Plasmon-driven dimerization via S-S chemical bond in an aqueous environment

    PubMed Central

    Cui, Lin; Wang, Peijie; Chen, Xiaowei; Fang, Yurui; Zhang, Zhenglong; Sun, Mengtao

    2014-01-01

    The surface-enhanced Raman scattering (SERS) spectra of thioanisole are experimentally investigated in an electrochemical environment in this study. Two Raman peaks, which depend strongly not only on electric potential but also on the local surface plasmon resonances (LSPR), have been observed. Theoretical calculations reveal that thioanisole is first dissociated from thiophenol via the S-CH3 bond; plasmons then drive the dimerisation of thiophenol via the S-S bond, which is strongly potential dependent. One Raman peak corresponds to the S-S vibrational mode of the thiophenol dimer, and the other corresponds to the asymmetric C-C stretching modes of the benzenyl of the thiophenol dimer. The potential-dependent two Raman modes is the potential-dependent dimerisation dynamics of thiophenol via the S-S bond. Our experimental findings provide insight into the structural elucidation of adsorbed molecules and molecular surface reaction dynamics. PMID:25427897

  16. Design of a Multisensory Probe for Measuring Carbon Cycle Processes in Aqueous Subterranean Environments

    SciTech Connect

    McIntyre, Timothy J; Kisner, Roger; Woodworth, Ken; Lenarduzzi, Roberto; Frank, Steven Shane; McKnight, Timothy E

    2015-01-01

    The global carbon cycle describes the exchange of carbon between the atmosphere, terrestrial vegetation, oceans, and soil. Mechanisms involving carbon in sub-terrestrial ecosystems and their impact on climate are not well understood. This lack of understanding limits current climate models and prevents accurate soil-carbon storage predications for future climate conditions. To address the lack of instrumentation for conducting high fidelity measurements of appropriate parameters in the field, a multi-sensory probe using a mix of optical, fiber optic, and electronic technologies to measure CO2, temperature, dissolved oxygen, redox potential, and water level in subsurface environments has been developed. Details of the design, fabrication and laboratory performance verification are presented. Use cases and the anticipated impacts of such measurements on climate models are discussed.

  17. Rare Earth Element - Humic Acid Interaction: Experimental Evidence for Kinetic and Equilibrium Fractionation in Aqueous Systems.

    NASA Astrophysics Data System (ADS)

    Sonke, J. E.; Salters, V. J.; Benedetti, M. F.

    2003-12-01

    Dissolved organic matter (DOM) is well known for it's strong binding capacity for trace metals. In order to better predict the role of DOM in the speciation and transport of trace metals in the environment we coupled capillary electrophoresis (CE), a molecular separation technique, to a Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). The combination of these two techniques allows for the study of non-labile metal speciation in aquatic samples. By separating Rare Earth Element (REE) complexes with EDTA and Humic Acid's (i.e. ligand competition) we have been able to determine conditional equilibrium binding constants (Kc) and kinetic rate constants for all 14 REE's with Humic (HA) and Fulvic Acids (FA) as a function of pH (6-9) and ionic strength (IS, 0.01-0.1 mol/L). Assuming a 1:1 binding mechanism, logKc values for REE-FA varied from 9.0 (La) to 10.5 (Lu) at pH 6, 0.1 mol/L IS, and 11.7 (La) to 14.6 (Lu) at pH 9, 0.1 mol/L IS. LogKc values for REE-HA were 10.6 (La) to 12.2 (Lu) at pH 6, 0.1 mol/L IS and 13.2 (La) to 16.5 (Lu) at pH 9, 0.1 mol/L IS. Slightly higher values for Kc were obtained at 0.01 mol/L IS. The general observations of stronger REE-HA binding compared to REE-FA, and stronger binding with increasing pH and decreasing IS correlate with our current understanding of metal-DOM interactions (1). Both Kc's as well as kinetic rate constants increase with increasing REE mass number (decreasing ionic radius); a reflection of the well-known lanthanide contraction. This is the first comprehensive metal binding dataset between REE and DOM, and the first experimental evidence for differential equilibrium and kinetic binding behavior between REE's and DOM. The 30-1000 fold increase in binding strength of heavy REE's with DOM provides for a an equilibrium fractionation mechanism that may explain features of the global geochemical REE cycle such as fractionation related to weathering, estuarine mixing, and REE scavenging in the deep ocean

  18. Structural and vibrational investigation on species derived from the cyclamic acid in aqueous solution by using HATR and Raman spectroscopies and SCRF calculations

    NASA Astrophysics Data System (ADS)

    Brizuela, Alicia B.; Raschi, Ana B.; Castillo, María V.; Davies, Lilian; Romano, Elida; Brandán, Silvia A.

    2014-09-01

    In this study, aqueous solutions at different molar concentrations of sodium cyclamate in water were completely characterized by HATR (Horizontal Attenuated Total Reflectance) and Raman spectroscopies. The theoretical structures of cyclamate ion, the zwitterionic and neutral forms of the cyclamic acid and its dimer were optimized in gas and aqueous solution phases by using the hybrid B3LYP/6-31G* method. The solvent effects for the four species in aqueous solutions were simulated by using self-consistent reaction field (SCRF) calculations employing the integral equation formalism variant (IEFPCM) model. The complete assignments of the vibrational spectra of all the forms of cyclamic acid were performed taking into account the factor group analysis with the Scaled Quantum Mechanics Force Field (SQMFF) methodology. The existence of the zwitterionic and neutral forms of the cyclamic acid and its dimer in a solution of cyclamate in water is evidenced by characteristic bands in the HATR and Raman spectra. The dimerization of cyclamate in aqueous solution was previously reported by conductimetric method. The natural population analysis (NPA) and Merz-Kollman (MK) charges, molecular electrostatic potential (MEP), natural bond orbital (NBO) and atoms in molecules (AIM) calculations predict for all the species the principal donor and acceptor sites for the H bonds formation in aqueous solution. The SQM force fields for the cyclamate ion, the zwitterionic and neutral species of the cyclamic acid were obtained and their corresponding force constants in both phases were reported. Additionally, the solvation energies for those species were reported.

  19. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    PubMed

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers. PMID:26652418

  20. Sensitization of the luminescence of europium and terbium ions by orotic acids in aqueous solutions

    SciTech Connect

    Davidenko, N.K.; Bukivskaya, G.A.

    1988-03-01

    The stability constants of the complexes of Eu/sup 3 +/ and Tb/sup 3 +/ with the dianions of orotic acid, 2-thioorotic acid, and 3-N-methylorotic acid have been determined at 20/sup 0/C and ..mu.. = 0.15 by a pH-potentiometric method. The influence of orotic acids on the luminescence properties of Eu/sup 3 +/ and Tb/sup 3 +/ has been studied. It has been shown as a result of a study of the excited states of orotic acid and its derivatives by a method based on the sensitized luminescence of the lanthanides that it is preferable to use the Tb/sup 3 +/ ion as an energy acceptor, since quenching of the luminescence by means of a charge-transfer process is observed in the complexes formed by the Eu/sup 3 +/ ion.

  1. Enrichment of the Amino Acid L-Isovaline by Aqueous Alteration on CI and CM Meteorite Parent Bodies

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel P.; Dworkin, Jason P.

    2009-01-01

    The distribution and enantiomeric composition of the 5-carbon (C(sub 5)) amino acids found in Cl-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/Nacetyl- l-cysteine derivatization. A large L-enantiomeric excess (ee) of the a-methyl amino acid isovaline was found in the CM meteorite Murchison (L(sub ee) = 18.5 +/- 2.6%) and the Cl meteorite Orguell (L(sub ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any Cl meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(sub 5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered Ct and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.

  2. Mycogenic Mn(II) oxidation promotes remediation of acid mine drainage and other anthropogenically impacted environments

    NASA Astrophysics Data System (ADS)

    Santelli, C. M.; Chaput, D.; Hansel, C. M.; Burgos, W. D.

    2014-12-01

    Manganese is a pollutant in worldwide environments contaminated with metals and organics, such as acid mine drainage (AMD), freshwater ponds, and agricultural waste storage sites. Microorganisms contribute to the removal of dissolved Mn compounds in the environment by promoting Mn(II) oxidation reactions. The oxidation of Mn(II) results in the precipitation of sparingly soluble Mn(IV) oxide minerals, effectively removing the metal from the aqueous milieu (e.g., groundwater or wastewater streams). In recent years, our research has identified a diversity of Mn(II)-oxidizing fungi inhabiting these polluted environments, however their overall contribution to the remediation process in situ remains poorly understood. Here we present results of culture-based and Next Generation Sequencing (NGS) studies in AMD treatment systems actively remediating Mn and other metals where we profile the bacterial, fungal, algal and archaeal communities to determine the overall community diversity and to establish the relative abundance of known Mn(II) oxidizers. A variety of treatment systems with varying Mn-removal efficiencies were sampled to understand the relationship between remediation efficiency and microbial community composition and activity. Targeted-amplicon sequencing of DNA and RNA of the 16S rRNA genes (bacteria and archaea), 23S rRNA genes (algae) and ITS region (fungi) was performed using both 454 pyrosequencing and Illumina platforms. Results showed that only the fungal taxonomic profiles significantly differed between sites that removed the majority of influent Mn and those that did not. Specifically, Ascomycota (which include known Mn(II) oxidizers isolated from these treatment systems) dominated greater efficiency systems whereas less efficient systems were dominated by Basidiomycota. Furthermore, known Mn(II) oxidizers accounted for only a minor proportion of bacterial sequences but a far greater proportion of fungal sequences. These culture-independent studies lend

  3. Effect of acid rain on the soil environment: a review

    SciTech Connect

    Rechcigl, J.E.; Sparks, D.L.

    1985-01-01

    This paper reviews the literature on acid rain, with emphasis on soils and leaching of soil elements. Several questions still exist concerning the effects of atmospheric acid deposition on soils: (1) does acid rain enhance mobilization of harmful heavy metals in soils which could leach into the groundwater; (2) does acid rain accelerate the kinetics of weathering of primary minerals and of secondary clay minerals in soils which would release large quantities of Al, Fe, and Si into the groundwater making it unfit for human consumption; and (3) do the beneficial effects of acid deposition outweigh the negative effects or vice versa. Literature pertaining to these questions is addressed in this review. 63 references.

  4. Long-term degradation study of hyaluronic acid in aqueous solutions without protection against microorganisms.

    PubMed

    Simulescu, Vasile; Kalina, Michal; Mondek, Jakub; Pekař, Miloslav

    2016-02-10

    The degradation of hyaluronan (HA) of different molecular weights (Mw 14.3, 267.2 and 1160.6 kDa, measured for fresh solutions, before degradation) was studied in aqueous solutions by SEC-MALLS determination of molecular mass, polydispersity and conformation parameters. The solutions were stored either at laboratory or refrigerator temperatures for two months. After this period the weight average molecular weight decreased by 90% for 14.3 kDa, 95% for 267.2 kDa and 71% for 1160.6 kDa hyaluronan (room temperature) or 5.6% for 14.3 kDa, 6.2% for 267.2 kDa and 7.7% for 1160.6 kDa hyaluronan (refrigerator temperature). The hyaluronan aqueous solutions studied did not contain sodium azide or other protectants against microorganisms, because the aim of our study was to assess the degradation in solutions to be used in medicine or cosmetics (without any compounds that are poisonous or toxic for the human body). The solvent used to prepare the samples was pure water. The polydispersity of all the samples remained unaltered during the entire degradation at both temperatures. This indicates a non-random mechanism of degradation. PMID:26686177

  5. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    PubMed

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively. PMID:25137539

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

    PubMed

    Garoma, Temesgen; Gurol, Mirat D

    2005-10-15

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

  7. Aqueous and surface chemistry of calcium-metal hydroxides in high pH environments

    SciTech Connect

    Cocke, D.L.; Mollah, M.Y.A.; Hess, T.R.; Lin, T.C.

    1997-08-01

    There is considerable interest in the chemistry associated with hazardous waste treatment by cement. The hydration of Portland cement is retarded in presence of zinc, cadmium and lead ions. Mixed hydroxides of calcium, zinc, cadmium and lead have been recently identified in the high pH environments of hydrating cement. FTIR, XRD, SEM, and SPM have been used to characterize these systems. A chemical equilibrium model of the early hydration of a zinc-doped cement/water system, Na-K-Ca-ZnH-SO{sub 4}-OH-Zn(OH){sub 2}-Zn(OH){sub 3}-Zn(OH){sub 4}-H{sub 2}O, has been developed to better understand the mechanism of the surface formation of calcium hydroxyzincate (CHZ). The model is based on Pitzer`s semi-empirical method for calculation of ion-activity coefficients at high ionic strength. The Pitzer parameters for Na{sup +}-Zn{sup 2+}, Na{sup +}-Zn{sup 2+}-SO{sub 4}{sup 2{minus}} and K{sup +}-Zn(OH){sub 4}{sup 2{minus}} have been evaluated, and the results successfully predict the equilibria (solubilities) of Na{sub 2}SO{sub 4}-ZnSO{sub 4}-H{sub 2}O, NaOH-Zn(OH){sub 2}-H{sub 2}O and KOH-ZnO-H{sub 2}O systems. The chemical model clearly demonstrates that the formation of CHZ on the calcium-silica-hydrate (C-S-H) surface is critically controlled by the Ca{sup 2+} ion concentration as well as pH of the pore water system. The results of this study suggest that the growth of CHZ is preceded by surface complex formation. Sequential charge control and sequential structure development have been used to discuss the surface selectivity of these compounds and their control of cement hydration.

  8. Fatigue Crack Propagation from Notched Specimens of 304 SS in elevated Temperature Aqueous Environment

    SciTech Connect

    Wire, G. L.; Mills, W. J.

    2002-08-01

    Fatigue crack propagation (FCP) rates for 304 stainless steel (304SS) were determined in 24 degree C and 288 degree C air and 288 degree C water using double-edged notch (DEN) specimens of 304 stainless steel (304 SS). Test performed at matched loading conditions in air and water at 288 degree C with 20-6- cc h[sub]2/kg h[sub]2O provided a direct comparison of the relative crack growth rates in air and water over a wide range of crack growth rates. The DEN crack extension ranged from short cracks (0.03-0.25 mm) to long cracks up to 4.06 mm, which are consistent with conventional deep crack tests. Crack growth rates of 304 SS in water were about 12 times the air rate. This 12X environmental enhancement persisted to crack extensions up to 4.06 mm, far outside the range associated with short crack effects. The large environmental degradation for 304 SS crack growth is consistent with the strong reduction of fatigue life in high hydrogen water. Further, very similar environmental effects w ere reported in fatigue crack growth tests in hydrogen water chemistry (HWC). Most literature data in high hydrogen water show only a mild environmental effect for 304 SS, of order 2.5 times air or less, but the tests were predominantly performed at high cyclic stress intensity or equivalently, high air rates. The environmental effect in low oxygen environments at low stress intensity depends strongly on both the stress ratio, R, and the load rise time, T[sub]r, as recently reported for austenitic stainless steel in BWR water. Fractography was performed for both tests in air and water. At 288 degree C in water, the fracture surfaces were crisply faceted with a crystallographic appearance, and showed striations under high magnification. The cleavage-like facets on the fracture surfaces suggest that hydrogen embrittlement is the primary cause of accelerated cracking.

  9. Extraction of electrolytes from aqueous solutions and their spectrophotometric determination by use of acid-base chromoionophores in lipophylic solvents.

    PubMed

    Barberi, Paola; Giannetto, Marco; Mori, Giovanni

    2004-04-01

    The formation of non-absorbing complexes in an organic phase has been exploited for the spectrophotometric determination of ionic analytes in aqueous solutions. The method is based on liquid-liquid extraction of aqueous solution with lipophylic organic phases containing an acid-base chromoionophore, a neutral lypophilic ligand (neutral carrier) selective to the analyte and a cationic (or anionic) exchanger. The method avoids all difficulties of the preparation of the very thin membranes used in optodes, so that it can advantageously be used for the study of the role physical-chemical parameters of the system in order to optimize them and to prepare, if necessary, an optimized optode. Two lipophylic derivatives of Nile Blue and 4',5-dibromofluorescein have been synthesized, in order to ensure their permanence within organic phase. Two different neutral carriers previously characterized by us as ionophores for liquid-membrane Ion Selective Electrodes have been employed. Three different ionic exchangers have been tested. Furthermore, a model allowing the interpolation of experimental data and the determination of the thermodynamic constant of the ionic-exchange equilibrium has been developed and applied. PMID:15242090

  10. Kinetic and thermodynamic characterization of C-N bond rotation by N-methylacetohydroxamic acid in aqueous media.

    PubMed

    Sippl, Stefanie P; White, Paul B; Fry, Charles G; Volk, Sarah E; Ye, Lingxiao; Schenck, Heather L

    2016-01-01

    Hydroxamic acids (HAs) perform tasks in medicine and industry that require bidentate metal binding. The two favored conformations of HAs are related by rotation around the C(=O)-N bond. The conformations are unequal in stability. Recently, we reported that the most stable conformation of a small secondary HA in water places the oxygen atoms anti to one another. The barrier to C-N bond rotation may therefore modulate metal binding by secondary HAs in aqueous media. We have now determined the activation barrier to C-N rotation from major to minor conformation of a small secondary HA in D2O to be 67.3 kJ/mol. The HA rotational barrier scales with solvent polarity, as is observed in amides, although the HA barrier is less than that of a comparable tertiary amide in aqueous solution. Successful design of new secondary HAs to perform specific tasks requires solid understanding of rules governing HA structural behavior. Results from this work provide a more complete foundation for HA design efforts. PMID:26477862

  11. Tandem bis-aza-Michael addition reaction of amines in aqueous medium promoted by polystyrenesulfonic Acid

    EPA Science Inventory

    An efficient and environmentally benign tandem bis-aza-Michael addition of amines catalyzed by polystyrene sulfonic acid (PSSA) is described. This operationally simple high yielding microwave assisted synthetic protocol proceeded in water in the absence of any organic solvent.

  12. Magnetically separable nanoferrite-anchored glutathione: Aqueous homocoupling of arylboronic acids under microwave irradiation

    EPA Science Inventory

    A highly active, stable and magnetically separable glutathione based organocatalyst provided good to excellent yields to symmetric biaryls in the homocoupling of arylboronic acids under microwave irradiation. Symmetrical biaryl motifs are present in a wide range of natural p...

  13. Spectrofluorimetric study of the interaction of ciprofloxacin with amino acids in aqueous solution following solvatochromic studies

    NASA Astrophysics Data System (ADS)

    Alizadeh, Kamal; Mobarrez, Mahsa; Ganjali, Mohammad Reza; Norouzi, Parviz; Chaichi, Mohammad Javad

    Complexation of a fluoroquinolone derivative (ciprofloxacin), L, and some amino acids has been studied using spectrofluorimetric method. Results indicated that ciprofloxacin have a greater tendency to form a 1:1 complex with aspartic acid and arginine than the other tested molecules. The fluorescence of ciprofloxacin exhibits quenching process while it has been titrated with these amino acids. Formation constant values (Kf) for complex formed between ciprofloxacin and amino acids were also calculated. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were studied too. Possible reasons for the observed stability sequence were discussed based on the structures proposed for the resulting complexes. Besides the solution studies, solvatochromic properties of the ciprofloxacin are discussed by studying its spectra in a selection of different solvents.

  14. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors

    PubMed Central

    Kawasaki, Shin-ichiro; Suzuki, Akira

    2013-01-01

    Summary The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd–Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  15. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors.

    PubMed

    Javaid, Rahat; Kawasaki, Shin-Ichiro; Suzuki, Akira; Suzuki, Toshishige M

    2013-01-01

    The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd-Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid. PMID:23843908

  16. Electrical conductivity measurements of aqueous boric acid at 25--350{degree}C at saturation vapor pressure. Final report

    SciTech Connect

    Ho, P.C.; Palmer, D.A.

    1995-09-01

    Electrical conductance measurements of aqueous boric acid solutions (15-110 g/kg-H{sub 2}O {equivalent_to} 0.251--1.815 mol/kg-H{sub 2}O) were measured over the temperature range 25 to 75 C at saturation vapor pressures in glass cells with parallel platinum electrodes. Sixteen series of measurements were made involving three samples of boric acid from different sources. Conductance measurements were also made at 15.5 and 30.5 g/kg-H{sub 2}O over the temperature range 100 to 350 C at 50 C intervals with a metallic cell fitted with concentric platinum electrodes. The specific conductances of H{sub 3}BO{sub 3} (aq)were calculated after correction for the conductance of the solvent (water) and are tabulated in this report. At the specific conditions requested in the project description, namely a concentration of 110 g/kg-H{sub 2}O and 65 C, the specific conductance of boric acid is 293.2 {+-} 1.8 microSiemens/cm based on duplicate measurements of four independent solutions. The results from these tests will be utilized by the Tokamak Physics Experimental Project (TPX).

  17. Self-consistent field theory investigation of the behavior of hyaluronic acid chains in aqueous salt solutions

    NASA Astrophysics Data System (ADS)

    Nogovitsin, E. A.; Budkov, Yu. A.

    2012-04-01

    In this work we continue to develop a field-theoretic methodology, which combines the technique of Gaussian equivalent representation for the calculation of functional integrals with the continuous Gaussian thread model of flexible polymers for solving statistical-mechanical problems of polyelectrolyte solutions. We present new analytic expressions for the osmotic pressure, the potential of mean force, and the monomer-monomer pair distribution function, and employ them to investigate the structural and thermodynamic quantities of the polyelectrolyte system. We demonstrate the applicability of the method for systems of polyelectrolyte chains in which the monomers interact via a Yukawa-type pair potential. As a specific example, the present work focuses on aqueous solutions of hyaluronic acid with added salts NaCl and CaCl2. Hyaluronic acid is a high molecular weight linear polysaccharide, which has a multitude of roles in biological tissues. We conclude that the effect of sodium chloride and calcium chloride on the osmotic properties of hyaluronic acid solutions can be accounted for by their contributions to the ionic strength. Nevertheless, the effects of coiling and self-association can be stimulated in solution by added salt.

  18. Acid dissociation mechanisms of Si(OH) 4 and Al(H 2O) 63+ in aqueous solution

    NASA Astrophysics Data System (ADS)

    Liu, Xiandong; Lu, Xiancai; Meijer, Evert Jan; Wang, Rucheng; Zhou, Huiqun

    2010-01-01

    Silicic acid and the hexa-aqua of Al 3+ are fundamental model aqueous species of chemical importance in nature. In order to investigate their hydroxyl dissociation mechanisms, Car-Parrinello molecular dynamics (CPMD) simulations were carried out, which allow treating the solutes and solvents on the same footing. The method of constraint was employed to trigger the reactions by taking coordination number as the reaction coordinate and the thermodynamic integration was used to obtain the free-energy profiles. The approximate transition states were located and the reactant and product states were also characterized. The free-energy changes of dissociation are found about 15.0 kcal/mol and 7.7 kcal/mol for silicic acid and Al-aqua, respectively. From the simulation results, the first p Kas were calculated by using two approaches, which are based on the pristine thermodynamic relation and the RDF (radial distribution function)-free energy relation, respectively. Because of more uncertainties involved in the RDF way, it is suggested that the pristine way should be favored, which shows an error margin of 1 p Ka unit. This study provides an encouraging basis for applying the present methodology to predict acidity constants of those groups that are difficult to measure experimentally.

  19. Acid in the environment: lessons learned and future prospects

    SciTech Connect

    Visgilio, Gerald R.; Whitelaw, Diana M.

    2007-07-01

    This book is the result of a conference held biannually at the Goodwin-Niering Center for Conservation Biology and Environmental Studies at Connecticut College. It uses an interdisciplinary approach to focus on important ecological impacts of acid deposition, the transboundary nature of the pollutants that cause acid rain, and domestic and international policies designed to reduce the emission of these pollutants. The book combines research findings and the policy analyses of experts from different academic disciplines with the positions advanced by representatives of various nongovernmental organizations (NGOs). The sixteen papers are arranged in four parts entitled: ecological impacts of acid deposition; acid emissions energy and policy; sulfur dioxide and the market; and lessons learned and future prospects.

  20. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.

    PubMed

    Qu, Yan; Zhang, Chaojie; Li, Fei; Bo, Xiaowen; Liu, Guangfu; Zhou, Qi

    2009-09-30

    Powdered activated carbon (PAC) was applied to remove perfluorooctanoic acid (PFOA) from the aqueous PFOA solution in this study. Contact time, adsorbent dose and temperature were analyzed as the effect factors in the adsorption reaction. The contact time of maximum PFOA uptake was around 1h while the sorption removal efficiency increased with the PAC concentrations. And the process of adsorption increased from 303 K to 313 K and then decreased from 313 K to 323 K. Among four applied models, the experimental isotherm data were discovered to follow Langmuir isotherm model more closely. Thermodynamically, adsorption was endothermic because enthalpy, entropy and Gibbs constants were 198.5 kJ/mol, 0.709 kJ/mol/K and negative, respectively, which also indicated that the adsorption process was spontaneous and feasible. From kinetic analysis, the adsorption was suggested to be pseudo-second-order model. The adsorption of PFOA on the PAC was mainly controlled by particle diffusion. PMID:19395160

  1. A mechanistic study of the photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid in aqueous solution.

    PubMed

    Yurkova, Maria P; Pozdnyakov, Ivan P; Plyusnin, Victor F; Grivin, Vycheslav P; Bazhin, Nikolay M; Kruppa, Alexandr I; Maksimova, Tatiana A

    2013-04-01

    Photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solution was investigated by stationary (254 nm) and nanosecond laser (266 nm) flash photolysis techniques. It was shown that in the primary photochemical step both photoionization (which generates a hydrated electron-radical cation pair) and heterolytic cleavage of a C-Cl bond takes place. The major products of substitution of one of the chlorine atoms in the 2-, 4- or 5-position by a hydroxyl group as well as the products of hydroxylation of the benzene ring in 3- and 6-positions were identified by HPLC and LC-MS methods. The complexation of 2,4,5-T with β- and γ-cyclodextrins (β(γ)CD) was investigated. The influence of such complexation on the quantum yield of herbicide photolysis and on the ratio of photodegradation products was determined. PMID:23085749

  2. Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

    NASA Astrophysics Data System (ADS)

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2009-04-01

    Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

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

    SciTech Connect

    Kritzer, P.; Boukis, N.; Dinjus, E.

    1998-12-31

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

  4. Corrosion processes of austenitic stainless steels and copper-based materials in gamma-irradiated aqueous environments

    SciTech Connect

    Glass, R.S.

    1985-09-01

    The US Department of Energy is evaluating a site located at Yucca Mountain in Nye County, Nevada, as a potential high-level nuclear waste repository. The rock at the proposed repository horizon (above the water table) is densely welded, devitrified tuff, and the fluid environment in the repository is expected to be primarily air-steam. A more severe environment would be present in the unlikely case of intrusion of vadose groundwater into the repository site. For this repository location, austenitic stainless steels and copper-based materials are under consideration for waste container fabrication. This study focuses on the effects of gamma irradiation on the electrochemical mechanisms of corrosion for the prospective waste container materials. The radiolytic production of such species as hydrogen peroxide and nitric acid are shown to exert an influence on corrosion mechanisms and kinetics.

  5. Photocatalytic decomposition of humic acids in anoxic aqueous solutions producing hydrogen, oxygen and light hydrocarbons.

    PubMed

    Klauson, Deniss; Budarnaja, Olga; Beltran, Ignacio Castellanos; Krichevskaya, Marina; Preis, Sergei

    2014-01-01

    Photocatalytic water splitting for hydrogen and oxygen production requires sacrificial electron donors, for example, organic compounds. Titanium dioxide catalysts doped with platinum, cobalt, tungsten, copper and iron were experimentally tested for the production of hydrogen, oxygen and low molecular weight hydrocarbons from aqueous solutions of humic substances (HS). Platinum-doped catalyst showed the best results in hydrogen generation, also producing methane, ethene and ethane, whereas the best oxygen production was exhibited by P25, followed by copper--and cobalt-containing photocatalysts. Iron-containing photocatalyst produced carbon monoxide as a major product. HS undergoing anoxic photocatalytic degradation produce hydrogen with minor hydrocarbons, and/or oxygen. It appears that better hydrogen yield is achieved when direct HS splitting takes place, as opposed to HS acting as electron donors for water splitting. PMID:25145176

  6. 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.

  7. Polarization Behavior of Water in Extreme Aqueous Environments: A molecular dynamics study based on the Gaussian Charge Polarizable Water Model.

    SciTech Connect

    Chialvo, Ariel A; Horita, Juske

    2010-01-01

    We study the polarization behavior of water under geologically-relevant extreme aqueous environments along four equidistant supercritical isotherms, 773 ! T (K) ! 1373, and over a wide pressure range, 0 < P(GPa) ! 30 , by isobaric-isothermal molecular dynamics simulations of the Gaussian Charge Polarizable (GCP ) water model, to unravel and discuss the underlying link between two precisely defined orientational order parameters and the magnitude of the average induced dipole moment of water. The predicted behavior indicates an isothermal linear dependence (a) between the magnitude of the average induced dipole moment ind and the average system density ! , (b) between the magnitude of the average induced dipole ind and that of the total dipole tot , resulting from (c) a compensating (inverse) dependence between the permanent-to-induced dipolar angle ! and the magnitude of the average induced dipole moment ind . Moreover, we interpret this behavior in terms of the evolution of the state dependent tetrahedral order parameter qT and the corresponding bond-order parameter Q6 , supplemented by the microstructural analysis based on the three site-site radial distribution functions of water and the distance-ranked nearest-neighbors distributions. Finally, we show that while water exhibits a dramatic microstructural transformation from an open four-coordinated hydrogen-bonded network at normal conditions to a quasi close-packed coordination, it still preserves a significant degree of hydrogen bonding.

  8. Occurrence of cyclophosphamide and ifosfamide in aqueous environment and their removal by biological and abiotic wastewater treatment processes.

    PubMed

    Česen, Marjeta; Kosjek, Tina; Laimou-Geraniou, Maria; Kompare, Boris; Širok, Brane; Lambropolou, Dimitra; Heath, Ester

    2015-09-15

    Cytostatic drug residues in the aqueous environment are of concern due to their possible adverse effects on non-target organisms. Here we report the occurrence and removal efficiency of cyclophosphamide (CP) and ifosfamide (IF) by biological and abiotic treatments including advanced oxidation processes (AOPs). Cyclophosphamide was detected in hospital wastewaters (14-22,000 ng L(-1)), wastewater treatment plant influents (19-27 ng L(-1)) and effluent (17 ng L(-1)), whereas IF was detected only in hospital wastewaters (48-6800 ng L(-1)). The highest removal efficiency during biological treatment (attached growth biomass in a flow through bioreactor) was 59 ± 15% and 35 ± 9.3% for CP and IF, respectively. Also reported are the removal efficiencies of both compounds from wastewater using hydrodynamic cavitation (HC), ozonation (O3) and/or UV, either individually or in combination with hydrogen peroxide (H2O2). Hydrodynamic cavitation did not remove CP and IF to any significant degree. The highest removal efficiencies: 99 ± 0.71% for CP and 94 ± 2.4% for IF, were achieved using UV/O3/H2O2 at 5 g L(-1) for 120 min. When combined with biological treatment, removal efficiencies were >99% for both compounds. This is the first report of combined biological and AOP treatment of CP and IF from wastewater with a removal efficiency >99%. PMID:25981944

  9. Protective or damage promoting effect of calcium carbonate layers on the surface of cement based materials in aqueous environments

    SciTech Connect

    Schwotzer, M.; Scherer, T.; Gerdes, A.

    2010-09-15

    Cement based materials permanently exposed to aggressive aqueous environments are subject to chemical changes affecting their durability. However, this holds also for tap water that is considered to be not aggressive to cementitious materials, although in that case a formation of covering layers of CaCO{sub 3} on the alkaline surfaces is commonly supposed to provide protection against reactive transport processes. Thus, investigations of the structural and chemical properties of the material/water interface were carried out in laboratory experiments and case studies to elucidate the consequences of surface reactions for the durability of cement based materials exposed to tap water. Focused Ion Beam investigations revealed that a protective effect of a CaCO{sub 3} covering layer depends on its structural properties, which are in turn affected by the hydro-chemical conditions during crystallization. Surface precipitation of CaCO{sub 3} can trigger further chemical degradation, if the required calcium is supplied by the pore solution of the material.

  10. A microfluidic device for the continuous culture and analysis of Caenorhabditis elegans in a toxic aqueous environment

    NASA Astrophysics Data System (ADS)

    Jung, Jaehoon; Nakajima, Masahiro; Tajima, Hirotaka; Huang, Qiang; Fukuda, Toshio

    2013-08-01

    The nematode Caenorhabditis elegans (C. elegans) receives attention as a bioindicator, and the C. elegans condition has been recently analyzed using microfluidic devices equipped with an imaging system. To establish a method without an imaging system, we have proposed a novel microfluidic device with which to analyze the condition of C. elegans from the capacitance change using a pair of micro-electrodes. The device was designed to culture C. elegans, to expose C. elegans to an external stimulus, such as a chemical or toxicant, and to measure the capacitance change which indicates the condition of C. elegans. In this study, to demonstrate the capability of our device in a toxic aqueous environment, the device was applied to examine the effect of cadmium on C. elegans. Thirty L4 larval stage C. elegans were divided into three groups. One group was a control group and the other groups were exposed to cadmium solutions with concentrations of 5% and 10% LC50 for 24 h. The capacitance change and the body volume of C. elegans as a reference were measured four times and we confirmed the correlation between them. It shows that our device can analyze the condition of C. elegans without an imaging system.

  11. Phase diagrams and water activities of aqueous ammonium salts of malonic acid.

    PubMed

    Beyer, Keith D; Richardson, Michael; Reusch, Breanna

    2011-04-14

    Malonic acid has been observed in the free troposphere and as a component of tropospheric aerosol, among other dicarboxylic acids. These aerosols can uptake ammonia, which partially or completely neutralizes the acids. Therefore, the impact of ammoniated dicarboxylic acids on the phases that can exist in aerosols at atmospheric temperatures needs investigation. To that end, the low temperature, solid/liquid phase diagrams of ammonium hydrogen malonate/water, ammonium malonate/water, and triammonium hydrogen malonate/water have been investigated with differential scanning calorimetry and infrared spectroscopy of thin films. Results show that the order of increasing solubility is triammonium hydrogen malonate, ammonium hydrogen malonate, malonic acid, and ammonium malonate. We have also determined a hydrate may form in the ammonium malonate system and decompose below 240 K. We report water activities at the ice melting points for each system up to the respective eutectic concentrations, and find for a given mole fraction of water, increasing ammonium content leads to decreasing water activity coefficients. PMID:21428389

  12. Historical usage of aqueous film forming foam: a case study of the widespread distribution of perfluoroalkyl acids from a military airport to groundwater, lakes, soils and fish.

    PubMed

    Filipovic, Marko; Woldegiorgis, Andreas; Norström, Karin; Bibi, Momina; Lindberg, Maria; Österås, Ann-Helen

    2015-06-01

    Historical usage of aqueous film forming foams (AFFFs) at military airports is a potential source of perfluoroalkyl acids (PFAAs) to the nearby environment. In this study, the distribution of perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS) and perfluorooctane sulfonate (PFOS) in soil, groundwater, surface water, tap water well, and fish muscle was investigated at a closed down military airfield (F18) and its surroundings in Stockholm, Sweden. The presence of PFOS at AFFF training sites was inventoried. One major finding of the study is that a former airfield, abandoned since 1994, may still be a point source of PFAAs to nearby recipients. PFOS and PFOA were ubiquitous in the soil samples at former AFFF training sites with concentrations ranging from 2.18 to 8520ngg(-1) dry weight and <0.12-287ngg(-1) dry weight respectively. The sum of PFAAs in the groundwater and surface waters ranged from 738 to 51000ngL(-1) and

  13. Rheology and interfacial properties of aqueous solutions of the diblock polyelectrolyte poly(styrene-block-acrylic acid)

    NASA Astrophysics Data System (ADS)

    Kimerling, Abigail

    In aqueous solutions diblock polyelectrolytes with amphiphilic character form aggregate structures, which affect physical properties such as viscosity, elasticity, surface tension, and film hydrophilicity. Potential applications for diblock polyelectrolyte solutions include coatings, inks, oil recovery agents, personal care products, and biomaterials. By varying the diblock polyelectrolyte and solution properties, the solutions can be tuned to meet the needs of particular applications. The research objective was to identify the influences of block length, pH, and ionic strength on the rheological and interfacial properties of poly(styrene- b-acrylic acid) (PS-PAA) solutions. Six polymers with varied PS and PAA block lengths were examined, all at 1.0 wt% in aqueous solutions. The hydrophobicity of the PS block causes the formation of spherical micelles in aqueous solutions. Increasing the solution pH ionizes the PAA block, which leads to an increase in micelle corona thickness due to repulsions between chains. Major trends observed in the rheological and interfacial properties can be understood in terms of expected changes in the micelle size and interfacial self-assembly with pH, ionic strength, and block length. Addition of NaOH was found to increase the solution pH and initially led to increases in solution viscosity, elasticity, surface tension, and film hydrophilicity. This effect was attributed to creation of larger micelles and greater inter-micellar repulsions as the PAA chain became more fully charged. However, when the concentration of NaOH exceeded a critical value, the solution viscosity, elasticity, and film hydrophilicity decreased. It is believed this was due to charge shielding by excess sodium ions, leading to shrinkage of the micelle corona and smaller micelles. Increasing the PS-PAA solution ionic strength by adding NaCl also provided charge shielding, as observed by decreases in solution viscosity and elasticity. Increasing the length of either

  14. Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton.

    PubMed

    Flores, Nelly; Sirés, Ignasi; Garrido, José Antonio; Centellas, Francesc; Rodríguez, Rosa María; Cabot, Pere Lluís; Brillas, Enric

    2016-12-01

    Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton's reaction between cathodically generated H2O2 and added catalytic Fe(2+). The substrate was very slowly removed by AO-H2O2, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with OH in the bulk. The AO-H2O2 process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC-MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization involving all the detected products is finally proposed. PMID:26691522

  15. Pervaporation of Water from Aqueous Sulfuric Acid at Elevated Temperatures Using Nafion® Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2009-01-01

    The concentration of sulfuric acid by pervaporation has been studied using Nafion-112® and Nafion-117® membranes, which have been characterized in terms of flux, permeability, and selectivity at 100 ºC and 120 ºC. Feed concentrations investigated ranged from 40 to over 80 weight percent. In general, water fluxes ranged from 100-8000 g/m2h, depending on feed acid concentration and separations factors as high as 104 were observed. Membrane stability was probed using Dynamic Mechanical Analysis that revealed some embrittlement of the membranes during use. Further studies showed that the embrittlement was due to an interaction with the acid and was not induced by the operating temperature.

  16. Thermodynamic and Ultrasonic Properties of Ascorbic Acid in Aqueous Protic Ionic Liquid Solutions

    PubMed Central

    Singh, Vickramjeet; Sharma, Gyanendra; Gardas, Ramesh L.

    2015-01-01

    In this work, we report the thermodynamic and ultrasonic properties of ascorbic acid (vitamin C) in water and in presence of newly synthesized ammonium based protic ionic liquid (diethylethanolammonium propionate) as a function of concentration and temperature. Apparent molar volume and apparent molar isentropic compression, which characterize the solvation state of ascorbic acid (AA) in presence of protic ionic liquid (PIL) has been determined from precise density and speed of sound measurements at temperatures (293.15 to 328.15) K with 5 K interval. The strength of molecular interactions prevailing in ternary solutions has been discussed on the basis of infinite dilution partial molar volume and partial molar isentropic compression, corresponding volume of transfer and interaction coefficients. Result has been discussed in terms of solute-solute and solute-solvent interactions occurring between ascorbic acid and PIL in ternary solutions (AA + water + PIL). PMID:26009887

  17. Chemisorption of Perfluorooctanoic Acid on Powdered Activated Carbon Initiated by Persulfate in Aqueous Solution.

    PubMed

    Sun, Bo; Ma, Jun; Sedlak, David L

    2016-07-19

    Perfluorooctanoic acid (PFOA) is a perfluorocarboxylic acid that is difficult to treat by most conventional methods. As a result, it is often removed from solution by adsorption on powdered activated carbon (PAC), followed by incineration of the spent carbon. To provide a new approach for treatment, PFOA was exposed to sulfate radicals (SO4(-•)) produced by thermolysis of persulfate (S2O8(2-)) in the presence of PAC. Under acidic conditions, thermal activation of persulfate resulted in transformation of PFOA to shorter-chain-length perfluorinated compounds, as previously reported. However, when thermolysis of persulfate occurred under circumneutral pH conditions in the presence of PAC, a new removal pathway for PFOA was observed. Under these conditions, the removal of PFOA was attributable to chemisorption, a process in which PAC catalyzed persulfate decomposition and reacted with the transformation products to produce covalently bound PFOA. At PAC concentrations between 200 and 1000 mg/L and an initial PFOA concentration of 0.5 μM, covalent bonding resulted in removal of 10-40% of the PFOA. Under these conditions, the process resulted in removal of more than half of a more hydrophilic perfluoroalkyl acid (i.e., perfluorobutanoic acid, PFBA), which was greater than the amount of PFBA removed by physical adsorption on PAC. Although the high reaction temperatures (i.e., 80 °C) and relatively high doses of PAC used in this study may be impractical for drinking water treatment, this process may be applied to the treatment of these recalcitrant compounds in industrial wastewater, reverse osmosis concentrate, and other waters that contain high concentrations of PFOA and other perfluorocarboxylic acids. PMID:27336204

  18. Interaction of some metals between marine-origin humic acids and aqueous solutions

    SciTech Connect

    Huljev, D.J.

    1986-08-01

    The interaction of metal ions (carrier-free form) in aquatic medium with humic acids is a complicated process depending on the properties of humic acids (elementary, chemical, and trace element composition), metals studied (valence, charge, chemical form, concentration), and medium used (pH, ionic strength). The use of radionuclides was found to be very suitable for a rapid and precise determination of the distribution coefficient K/sub d/ (ratio of the concentration of a certain trace metal association with a gram of humic acid over the concentration of the same trace metal per milliliter of solution) of the investigated system. Isolated humic acids from offshore sediments from the North Adriatic (Lim channel, near Rovinj, Yugoslavia) were characterized according to their elementary composition, the amount of products of hydrolysis, and the trace elements bound. All experiments were carried out between pH 3 and 5. It was found that conditions usually present at the site where humic acid interacts with metal ions (anaerobic conditions, H/sub 2/S) in brackish (21% S) and standard seawater (38% S) are determined in the pH range 3 to 5. The results of the pick-up (uptake) and replacement (release) experiments are presented as a distribution coefficient (K/sub d/), as a function of contact time. Processes of pick-up and replacement of a number of metals under various physicochemical conditions were investigated and special attention was paid to the influence of salinity. With the increase in NaCl concentration and pH in the system, the fixation of ruthenium, zinc, cobalt, and mercury by humic acids decreased.

  19. Acidic environments induce differentiation of Proteus mirabilis into swarmer morphotypes.

    PubMed

    Fujihara, Masatoshi; Obara, Hisato; Watanabe, Yusaku; Ono, Hisaya K; Sasaki, Jun; Goryo, Masanobu; Harasawa, Ryô

    2011-07-01

    Although swarmer morphotypes of Proteus mirabilis have long been considered to result from surfaced-induced differentiation, the present findings show that, in broth medium containing urea, acidic conditions transform some swimmer cells into elongated swarmer cells. This study has also demonstrates that P. mirabilis cells grown in acidic broth medium containing urea enhance virulence factors such as flagella production and cytotoxicity to human bladder carcinoma cell line T24, though no significant difference in urease activity under different pH conditions was found. Since there is little published data on the behavior of P. mirabilis at various hydrogen-ion concentrations, the present study may clarify aspects of cellular differentiation of P. mirabilis in patients at risk of struvite formation due to infection with urease-producing bacteria, as well as in some animals with acidic or alkaline urine. PMID:21707738

  20. Aqueous Alteration of Mars-Analog Rocks Under an Acidic Atmosphere

    NASA Technical Reports Server (NTRS)

    Bullock, M. A.; Moore, J. M.; Mellon, M. T.

    2001-01-01

    The wind-blown fines of Mars have high amounts of salts that are easily mobilized by water. We report on laboratory experiments that produce brines from the interaction of water with Mars-analog rocks and a simulated acidic Mars paleoatmosphere. Additional information is contained in the original extended abstract.

  1. Solute-enhanced production of gamma-valerolactone (GVL) from aqueous solutions of levulinic acid

    SciTech Connect

    Dumesic, James A; Wettstein, Stephanie G; Alonso, David Martin; Gurbuz, Elif Ispir

    2015-02-24

    A method to produce levulinic acid (LA) and gamma-valerolactone (GVL) from biomass-derived cellulose or lignocellulose by selective extraction of LA using GVL and optionally converting the LA so isolated into GVL, with no purifications steps required to yield the GVL.

  2. 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%.

  3. Interactions of aqueous amino acids and proteins with the (110) surface of ZnS in molecular dynamics simulations

    SciTech Connect

    Nawrocki, Grzegorz; Cieplak, Marek

    2014-03-07

    The growing usage of nanoparticles of zinc sulfide as quantum dots and biosensors calls for a theoretical assessment of interactions of ZnS with biomolecules. We employ the molecular-dynamics-based umbrella sampling method to determine potentials of mean force for 20 single amino acids near the ZnS (110) surface in aqueous solutions. We find that five amino acids do not bind at all and the binding energy of the remaining amino acids does not exceed 4.3 kJ/mol. Such energies are comparable to those found for ZnO (and to hydrogen bonds in proteins) but the nature of the specificity is different. Cysteine can bind with ZnS in a covalent way, e.g., by forming the disulfide bond with S in the solid. If this effect is included within a model incorporating the Morse potential, then the potential well becomes much deeper—the binding energy is close to 98 kJ/mol. We then consider tryptophan cage, a protein of 20 residues, and characterize its events of adsorption to ZnS. We demonstrate the relevance of interactions between the amino acids in the selection of optimal adsorbed conformations and recognize the key role of cysteine in generation of lasting adsorption. We show that ZnS is more hydrophobic than ZnO and that the density profile of water is quite different than that forming near ZnO—it has only a minor articulation into layers. Furthermore, the first layer of water is disordered and mobile.

  4. Interactions of aqueous amino acids and proteins with the (110) surface of ZnS in molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Nawrocki, Grzegorz; Cieplak, Marek

    2014-03-01

    The growing usage of nanoparticles of zinc sulfide as quantum dots and biosensors calls for a theoretical assessment of interactions of ZnS with biomolecules. We employ the molecular-dynamics-based umbrella sampling method to determine potentials of mean force for 20 single amino acids near the ZnS (110) surface in aqueous solutions. We find that five amino acids do not bind at all and the binding energy of the remaining amino acids does not exceed 4.3 kJ/mol. Such energies are comparable to those found for ZnO (and to hydrogen bonds in proteins) but the nature of the specificity is different. Cysteine can bind with ZnS in a covalent way, e.g., by forming the disulfide bond with S in the solid. If this effect is included within a model incorporating the Morse potential, then the potential well becomes much deeper—the binding energy is close to 98 kJ/mol. We then consider tryptophan cage, a protein of 20 residues, and characterize its events of adsorption to ZnS. We demonstrate the relevance of interactions between the amino acids in the selection of optimal adsorbed conformations and recognize the key role of cysteine in generation of lasting adsorption. We show that ZnS is more hydrophobic than ZnO and that the density profile of water is quite different than that forming near ZnO—it has only a minor articulation into layers. Furthermore, the first layer of water is disordered and mobile.

  5. Interactions of aqueous amino acids and proteins with the (110) surface of ZnS in molecular dynamics simulations.

    PubMed

    Nawrocki, Grzegorz; Cieplak, Marek

    2014-03-01

    The growing usage of nanoparticles of zinc sulfide as quantum dots and biosensors calls for a theoretical assessment of interactions of ZnS with biomolecules. We employ the molecular-dynamics-based umbrella sampling method to determine potentials of mean force for 20 single amino acids near the ZnS (110) surface in aqueous solutions. We find that five amino acids do not bind at all and the binding energy of the remaining amino acids does not exceed 4.3 kJ/mol. Such energies are comparable to those found for ZnO (and to hydrogen bonds in proteins) but the nature of the specificity is different. Cysteine can bind with ZnS in a covalent way, e.g., by forming the disulfide bond with S in the solid. If this effect is included within a model incorporating the Morse potential, then the potential well becomes much deeper--the binding energy is close to 98 kJ/mol. We then consider tryptophan cage, a protein of 20 residues, and characterize its events of adsorption to ZnS. We demonstrate the relevance of interactions between the amino acids in the selection of optimal adsorbed conformations and recognize the key role of cysteine in generation of lasting adsorption. We show that ZnS is more hydrophobic than ZnO and that the density profile of water is quite different than that forming near ZnO--it has only a minor articulation into layers. Furthermore, the first layer of water is disordered and mobile. PMID:24606380

  6. USEPA METHOD STUDY 38 - SW-846 METHOD 3010, ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS FOR TRACE METALS BY FLAME ATOMIC ABSORPTION SPECTROSCOPY

    EPA Science Inventory

    An interlaboratory collaborative study was conducted on SW-846 Method 3010, "Acid Digestion of Aqueous Samples and Extracts for Total Metals for Analysis by Flame Atomic Absorption Spectroscopy", to determine the mean recovery and precision for analyses of 21 trace metals in surf...

  7. Efficacy of chlorine, acidic electrolyzed water and aqueous chlorine dioxide solutions to decontaminate Escherichia coli O157:H7 from lettuce leaves

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study compared the efficacy of chlorine (20 – 200 ppm), acidic electrolyzed water (50 ppm chlorine, pH 2.6), acidified sodium chlorite (20 – 200 ppm chlorite ion concentration, Sanova), and aqueous chlorine dioxide (20 – 200 ppm chlorite ion concentration, TriNova) washes in reducing population...

  8. Production of fermentable sugars from corn fiber using soaking in aqueous ammonia (saa) pretreatment and fermentation to succinic acid by Escherichia coli afp184

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conversion of corn fiber (CF), a by-product from the corn-to-ethanol conversion process, into fermentable sugar and succinic acid was investigated using soaking in aqueous ammonia (SAA) pretreatment followed by biological conversions including enzymatic hydrolysis and fermentation using genetically ...

  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. IUPAC-NIST Solubility Data Series. 90. Hydroxybenzoic Acid Derivatives in Binary, Ternary, and Multicomponent Systems. Part I. Hydroxybenzoic Acids, Hydroxybenzoates, and Hydroxybenzoic Acid Salts in Water and Aqueous Systems

    NASA Astrophysics Data System (ADS)

    Goto, Rensuke; Fukuda, Hiroshi; Königsberger, Erich; Königsberger, Lan-Chi

    2011-03-01

    The solubility data for well-defined binary, ternary, and multicomponent systems of solid-liquid type are reviewed. One component, which is 2-, 3-, and 4-hydroxybenzoic acids, 4-hydroxybenzoate alkyl esters (parabens), or hydroxybenzoic acid salts, is in the solid state at room temperature and another component is liquid water, meaning that all of the systems are aqueous solutions. The ternary or multicomponent systems include organic substances of various classes (hydrocarbons of several structural types, halogenated hydrocarbons, alcohols, acids, ethers, esters, amides, and surfactants) or inorganic substances. Systems reported in the primary literature from 1898 through 2000 are compiled. For seven systems, sufficient binary data for hydroxybenzoic acids or parabens in water are available to allow critical evaluation. Almost all data are expressed as mass and mole fractions as well as the originally reported units, while some data are expressed as molar concentration.

  11. Eukaryotic Organisms in Extreme Acidic Environments, the Río Tinto Case

    NASA Astrophysics Data System (ADS)

    Angeles Aguilera, Angeles

    2013-07-01

    A major issue in microbial ecology is to identify the limits of life for growth and survival, and to understand the molecular mechanisms that define these limits. Thus, interest in the biodiversity and ecology of extreme environments has grown in recent years for several reasons. Some are basic and revolve around the idea that extreme environments are believed to reflect early Earth conditions. Others are related to the biotechnological potential of extremophiles. In this regard, the study of extremely acidic environments has become increasingly important since environmental acidity is often caused by microbial activity. Highly acidic environments are relatively scarce worldwide and are generally associated with volcanic activity or mining operations. For most acidic environments, low pH facilitates metal solubility, and therefore acidic waters tend to have high concentrations of heavy metals. However, highly acidic environments are usually inhabited by acidophilic and acidotolerant eukaryotic microorganisms such as algae, amoebas, ciliates, heliozoan and rotifers, not to mention filamentous fungi and yeasts. Here, we review the general trends concerning the diversity and ecophysiology of eukaryotic acidophilic microorganims, as well as summarize our latest results on this topic in one of the largest extreme acidic rivers, Río Tinto (SW, Spain).

  12. Acidity of the amidoxime functional group in aqueous solution: a combined experimental and computational study.

    PubMed

    Mehio, Nada; Lashely, Mark A; Nugent, Joseph W; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D; Bryantsev, Vyacheslav S

    2015-02-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pK(a) values that have been reported for the amidoxime functional group. To resolve this existing controversy we investigated the pK(a) values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pK(a) values of representative amidoximes, acetamidoxime, and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pK(a) values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance, with a root-mean-square deviation of 0.46 pK(a) units and 0.45 pK(a) units, respectively. Finally, we employ our two best methods to predict the pK(a) values of promising, uncharacterized amidoxime ligands, which provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents. PMID:25621618

  13. A combination of synchronous fluorescence spectroscopy with chemometric treatment and internal standards in non-aqueous potentiometric titrations of fulvic acids.

    PubMed

    Esteves da Silva, J C; Machado, A A

    1994-12-01

    The acid properties of a soil fulvic acid (sfua) were characterized by potentiometric titration with tetrabutylammonium hydroxide in two non-aqueous solvents with high acid-base resolution power N,N-dimethylformamide (DMF) and acetonitrile. Synchronous fluorescence spectroscopy (SyF) was also used to monitor directly the sfua status during the potentiometric titration in DMF. The potentiometric titration curves showed no clear end-point and the analysis of the sets of spectra obtained at increasing neutralization degree, with a self-modeling curve resolution method (SIMPLISMA), revealed the existence of two components with featureless concentration profiles. Internal standards (maleic, salicylic and p-hydroxylbenzoic acids) were used to determine the amounts of acid groups with different acid strengths in the two non-aqueous solvents. It was shown that the variations observed in the SyF spectra sets of the internal standards are not correlated with those observed in the sfua data. The splitting of the sfua groups in the non-aqueous titration curves seems to be forced artificially depending on the standards used. PMID:18966177

  14. Contact ion pair formation between hard acids and soft bases in aqueous solutions observed with 2DIR spectroscopy.

    PubMed

    Sun, Zheng; Zhang, Wenkai; Ji, Minbiao; Hartsock, Robert; Gaffney, Kelly J

    2013-12-12

    The interaction of charged species in aqueous solution has important implications for chemical, biological, and environmental processes. We have used 2DIR spectroscopy to study the equilibrium dynamics of thiocyanate chemical exchange between free ion (NCS(-)) and contact ion pair configurations (MNCS(+)), where M(2+) = Mg(2+) or Ca(2+). Detailed studies of the influence of anion concentration and anion speciation show that the chemical exchange observed with the 2DIR measurements results from NCS(-) exchanging with other anion species in the first solvation shell surrounding Mg(2+) or Ca(2+). The presence of chemical exchange in the 2DIR spectra provides an indirect, but robust, determinant of contact ion pair formation. We observe preferential contact ion pair formation between soft Lewis base anions and hard Lewis acid cations. This observation cannot be easily reconciled with Pearson's acid-base concept or Collins' Law of Matching Water Affinities. The anions that form contact ion pairs also correspond to the ions with an affinity for water and protein surfaces, so similar physical and chemical properties may control these distinct phenomena. PMID:23895531

  15. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework.

    PubMed

    Demir, Selvan; Brune, Nicholas K; Van Humbeck, Jeffrey F; Mason, Jarad A; Plakhova, Tatiana V; Wang, Shuao; Tian, Guoxin; Minasian, Stefan G; Tyliszczak, Tolek; Yaita, Tsuyoshi; Kobayashi, Tohru; Kalmykov, Stepan N; Shiwaku, Hideaki; Shuh, David K; Long, Jeffrey R

    2016-04-27

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr(2+), Fe(3+), Nd(3+), and Am(3+), from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  16. Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles.

    PubMed

    Callejas, Juan F; McEnaney, Joshua M; Read, Carlos G; Crompton, J Chance; Biacchi, Adam J; Popczun, Eric J; Gordon, Thomas R; Lewis, Nathan S; Schaak, Raymond E

    2014-11-25

    Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of -10 mA cm(-2), FeP nanoparticles deposited at a mass loading of ∼1 mg cm(-2) on Ti substrates exhibited overpotentials of -50 mV in 0.50 M H2SO4 and -102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO2 produced H2 at rates and amounts that begin to approach those of Pt/TiO2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically. PMID:25250976

  17. Solution properties and taste behavior of lactose monohydrate in aqueous ascorbic acid solutions at different temperatures: Volumetric and rheological approach.

    PubMed

    Sarkar, Abhijit; Sinha, Biswajit

    2016-11-15

    The densities and viscosities of lactose monohydrate in aqueous ascorbic acid solutions with several molal concentrations m=(0.00-0.08)molkg(-1) of ascorbic acid were determined at T=(298.15-318.15)K and pressure p=101kPa. Using experimental data apparent molar volume (ϕV), standard partial molar volume (ϕV(0)), the slope (SV(∗)), apparent specific volumes (ϕVsp), standard isobaric partial molar expansibility (ϕE(0)) and its temperature dependence [Formula: see text] the viscosity B-coefficient and solvation number (Sn) were determined. Viscosity B-coefficients were further employed to obtain the free energies of activation of viscous flow per mole of the solvents (Δμ1(0≠)) and of the solute (Δμ2(0≠)). Effects of molality, solute structure and temperature and taste behavior were analyzed in terms of solute-solute and solute-solvent interactions; results revealed that the solutions are characterized predominantly by solute-solvent interactions and lactose monohydrate behaves as a long-range structure maker. PMID:27283672

  18. Removal of Cu(II) and Ni(II) from aqueous solution by lignite-based humic acids

    SciTech Connect

    Arslan, G.; Cetin, S.; Pehlivan, E.

    2007-07-01

    The removal of Cu(II) and Ni(II) metal ions from an aqueous solution were investigated by using humic acids (HAs) in a batch arrangement. HAs were prepared by using alkaline extraction, following sedimentation and acidic precipitation from three Turkish lignites: Ilgin, Beysehir, and Ermenek. The interactions of Cu(II) and Ni(II) with solid HAs and influence of three parameters (initial metal concentration, solution pH and temperature) on the removal of metals were studied. Adsorption equilibrium was achieved in about 120 min for Cu(II) and Ni(II) ions. The sorption of Cu(II) and Ni(II) on the surface of HAs depended strongly on the pH, and increased with increasing pH and the initial concentration of metal. The sorption of Cu(II) was higher than that of Ni(II) for HAs. The equilibrium relationship between adsorbent and adsorbate is described by adsorption isotherms at a fixed temperature 35 {sup o}C, at pH about 4.0. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. Adsorption isotherms and kinetics data of Cu(II) and Ni(II) ions removed by HAs are presented and discussed.

  19. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

    PubMed Central

    2016-01-01

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  20. Study of the dose response of the system ferrous ammonium sulfate-sucrose-xylenol orange in acid aqueous solution

    NASA Astrophysics Data System (ADS)

    Juarez-Calderon, J. M.; Negron-Mendoza, A.; Ramos-Bernal, S.

    2014-11-01

    An aqueous solution of ammonium ferrous sulfate-sucrose-xylenol orange in sulfuric acid (FSX) is proposed as a dosimetric system for the processes of gamma irradiation in a range between 0.3 and 6 Gy. This system is based on the indirect oxidation of ferrous ion by an organic compound (sucrose) to ferric ion and on the formation of a color complex of Fe3+ in an acidic medium with xylenol orange (a dye). After gamma radiation, an observable change occurs in the color of the system. Irradiation was executed at three different temperatures (13 °C, 22 °C, and 40 °C). A spectrometric readout method at 585 nm was employed to evaluate the system's dose response. In all of the cases analyzed, the responses had a linear behavior, and a slight effect of irradiation temperature was observed. Post-irradiation response was also evaluated and showed the stability of the solutions 24 h after the irradiation. The results obtained suggest that FSX might be used as a dosimeter for low doses of gamma irradiation because it provides a stable signal, good reproducibility, and an accessible technique for analysis.

  1. How Does the C-Halogen Bond Break in the Photosubstitution Reaction of 3-Fluorobenzophenone in Acidic Aqueous Solutions?

    PubMed

    Huang, Jinqing; Ma, Jiani; Li, Mingde; Liu, Mingyue; Zhang, Xiting; Phillips, David Lee

    2015-10-01

    The efficient photosubstitution reaction of m-fluorobenzophenone and the related photohydration reactions were systematically investigated in acidic aqueous solutions. The mechanisms and intermediates were directly characterized by femtosecond transient absorption spectroscopy and nanosecond time-resolved resonance Raman spectroscopy, which is supported by density functional theory calculations. This photosubstitution was found to be a two-step process, based on the observation of a meta-hydration intermediate. The protonation of the ketone was confirmed as a crucial precursor step for further photochemical reactions as indicated by the observation of the absorption spectrum of an excited triplet protonated species. More interestingly, the efficient photosubstitution reaction could selectively occur under specific conditions. Control experiments on a series of halogen-substituted benzophenones were conducted to study the influence of the solution acidity, substituent positions, and the kind of substituted halogens on the efficiency in forming the corresponding hydroxyl photosubstitution product. Some practical conditions in predicting the efficiency of the photosubstitution reaction of interest are summarized, and they were successfully used to predict when the photosubstitution reaction takes place for some other halogen-substituted benzophenone derivatives. The driving force of this photosubstitution reaction may provide insights into several possible applications which are also briefly discussed. PMID:26322959

  2. Temperature-Induced Aggregate Transitions in Mixtures of Cationic Ammonium Gemini Surfactant with Anionic Glutamic Acid Surfactant in Aqueous Solution.

    PubMed

    Ji, Xiuling; Tian, Maozhang; Wang, Yilin

    2016-02-01

    The aggregation behaviors of the mixtures of cationic gemini surfactant 1,4-bis(dodecyl-N,N-dimethylammonium bromide)-2,3-butanediol (C12C4(OH)2C12Br2) and anionic amino acid surfactant N-dodecanoylglutamic acid (C12Glu) in aqueous solution of pH = 10.0 have been studied. The mixture forms spherical micelles, vesicles, and wormlike micelles at 25 °C by changing mixing ratios and/or total surfactant concentration. Then these aggregates undergo a series of transitions upon increasing the temperature. Smaller spherical micelles transfer into larger vesicles, vesicles transfer into solid spherical aggregates and then into larger irregular aggregates, and entangled wormlike micelles transfer into branched wormlike micelles. Moreover, the larger irregular aggregates and branched micelles finally lead to precipitation and clouding phenomenon, respectively. All these transitions are thermally reversible, and the transition temperatures can be tuned by varying the mixing ratios and/or total concentration. These temperature-dependent aggregate transitions can be elucidated on the basis of the temperature-induced variations in the dehydration, electrostatic interaction, and hydrogen bonds of the headgroup area and in the hydrophobic interaction between the hydrocarbon chains. The results suggest that the surfactants carrying multiple binding sites will greatly improve the regulation ability and temperature sensitivity. PMID:26750978

  3. Effect of abiotic factors on the mercury reduction process by humic acids in aqueous systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mercury (Hg) in the environment can have serious toxic effects on a variety of living organisms, and is a pollutant of concern worldwide. The reduction of mercury from the toxic Hg2+ form to Hg0 is especially important. One pathway for this reduction to occur is through an abiotic process with humic...

  4. Electrochemical degradation of trichloroacetic acid in aqueous media: influence of the electrode material.

    PubMed

    Esclapez, M D; Díez-García, M I; Sàez, V; Bonete, P; González-García, José

    2013-01-01

    The electrochemical degradation of trichloroacetic acid (TCAA) in water has been analysed through voltammetric studies with a rotating disc electrode and controlled-potential bulk electrolyses. The influence of the mass-transport conditions and initial concentration of TCAA for titanium, stainless steel and carbon electrodes has been studied. It is shown that the electrochemical reduction of TCAA takes place prior to the massive hydrogen evolution in the potential window for all electrode materials studied. The current efficiency is high (> 18%) compared with those normally reported in the literature, and the fractional conversion is above 50% for all the electrodes studied. Only dichloroacetic acid (DCAA) and chloride anions were routinely detected as reduction products for any of the electrodes, and reasonable values of mass balance error were obtained. Of the three materials studied, the titanium cathode gave the best results. PMID:23530352

  5. A novel, stable, aqueous glucagon formulation using ferulic acid as an excipient.

    PubMed

    Bakhtiani, Parkash A; Caputo, Nicholas; Castle, Jessica R; El Youssef, Joseph; Carroll, Julie M; David, Larry L; Roberts, Charles T; Ward, W Kenneth

    2015-01-01

    Commercial glucagon is unstable due to aggregation and degradation. In closed-loop studies, it must be reconstituted frequently. For use in a portable pump for 3 days, a more stable preparation is required. At alkaline pH, curcumin inhibited glucagon aggregation. However, curcumin is not sufficiently stable for long-term use. Here, we evaluated ferulic acid, a stable breakdown product of curcumin, for its ability to stabilize glucagon. Ferulic acid-formulated glucagon (FAFG), composed of ferulic acid, glucagon, L-methionine, polysorbate-80, and human serum albumin in glycine buffer at pH 9, was aged for 7 days at 37°C. Glucagon aggregation was assessed by transmission electron microscopy (TEM) and degradation by high-performance liquid chromatography (HPLC). A cell-based protein kinase A (PKA) assay was used to assess in vitro bioactivity. Pharmacodynamics (PD) of unaged FAFG, 7-day aged FAFG, and unaged synthetic glucagon was determined in octreotide-treated swine. No fibrils were observed in TEM images of fresh or aged FAFG. Aged FAFG was 94% intact based on HPLC analysis and there was no loss of bioactivity. In the PD swine analysis, the rise over baseline of glucose with unaged FAFG, aged FAFG, and synthetic native glucagon (unmodified human sequence) was similar. After 7 days of aging at 37°C, an alkaline ferulic acid formulation of glucagon exhibited significantly less aggregation and degradation than that seen with native glucagon and was bioactive in vitro and in vivo. Thus, this formulation may be stable for 3-7 days in a portable pump for bihormonal closed-loop treatment of T1D. PMID:25253164

  6. Kinetic measurements of the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Schöne, L.; Herrmann, H.

    2014-05-01

    Free radical reactions are an important degradation process for organic compounds within the aqueous atmospheric environment. Nevertheless, non-radical oxidants such as hydrogen peroxide and ozone also contribute to the degradation and conversion of these substances (Tilgner and Herrmann, 2010). In this work, kinetic investigations of non-radical reactions were conducted using UV / Vis spectroscopy (dual-beam spectrophotometer and stopped flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics to reactions of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acid as well as methacrolein (MACR) and methyl vinyl ketone (MVK) with H2O2 and ozone at 298 K. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M-1 s-1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH • ~109 M-1 s-1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated first-order conversion rate constants change the picture towards H2O2 reactions becoming more important, especially when compared to the nitrate radical. For some reactions mechanistic suggestions are also given.

  7. Kinetic measurements on the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solution

    NASA Astrophysics Data System (ADS)

    Schöne, L.; Herrmann, H.

    2013-10-01

    Within the aqueous atmospheric environment free radical reactions are an important degradation process for organic compounds. Nevertheless, non-radical oxidants like hydrogen peroxide and ozone also contribute to the degradation and conversion of this substance group (Tilgner und Herrmann, 2010). In this work kinetic investigations of non-radical reactions were conducted using UV/Vis spectroscopy (dual-beam spectrophotometer and Stopped Flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acids as well as methacrolein (MACR) and methyl vinyl ketone (MVK) towards H2O2 and ozone. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M-1 s-1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH· ~ 109 M-1 s-1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated turnovers change the picture to more important H2O2 reactions especially when compared to the nitrate radical. For some reactions also mechanistic suggestions are given.

  8. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    SciTech Connect

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.

  9. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    DOE PAGESBeta

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopicmore » titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.« less

  10. Cross Dimerization of Amyloid-β and αSynuclein Proteins in Aqueous Environment: A Molecular Dynamics Simulations Study

    PubMed Central

    Jose, Jaya C.; Chatterjee, Prathit; Sengupta, Neelanjana

    2014-01-01

    Self-assembly of the intrinsically unstructured proteins, amyloid beta (Aβ) and alpha synclein (αSyn), are associated with Alzheimer’s Disease, and Parkinson’s and Lewy Body Diseases, respectively. Importantly, pathological overlaps between these neurodegenerative diseases, and the possibilities of interactions between Aβ and αSyn in biological milieu emerge from several recent clinical reports and in vitro studies. Nevertheless, there are very few molecular level studies that have probed the nature of spontaneous interactions between these two sequentially dissimilar proteins and key characteristics of the resulting cross complexes. In this study, we have used atomistic molecular dynamics simulations to probe the possibility of cross dimerization between αSyn1–95 and Aβ1–42, and thereby gain insights into their plausible early assembly pathways in aqueous environment. Our analyses indicate a strong probability of association between the two sequences, with inter-protein attractive electrostatic interactions playing dominant roles. Principal component analysis revealed significant heterogeneity in the strength and nature of the associations in the key interaction modes. In most, the interactions of repeating Lys residues, mainly in the imperfect repeats ‘KTKEGV’ present in αSyn1–95 were found to be essential for cross interactions and formation of inter-protein salt bridges. Additionally, a hydrophobicity driven interaction mode devoid of salt bridges, where the non-amyloid component (NAC) region of αSyn1–95 came in contact with the hydrophobic core of Aβ1–42 was observed. The existence of such hetero complexes, and therefore hetero assembly pathways may lead to polymorphic aggregates with variations in pathological attributes. Our results provide a perspective on development of therapeutic strategies for preventing pathogenic interactions between these proteins. PMID:25210774

  11. Hyaluronic acid-coated niosomes facilitate tacrolimus ocular delivery: Mucoadhesion, precorneal retention, aqueous humor pharmacokinetics, and transcorneal permeability.

    PubMed

    Zeng, Weidong; Li, Qi; Wan, Tao; Liu, Cui; Pan, Wenhui; Wu, Zushuai; Zhang, Guoguang; Pan, Jingtong; Qin, Mengyao; Lin, Yuanyuan; Wu, Chuanbin; Xu, Yuehong

    2016-05-01

    Tacrolimus (FK506) was used to prevent corneal allograft rejection in patients who were resistant to steroids and cyclosporine. However, the formulation for FK506 ocular delivery remained a challenge due to the drug's high hydrophobicity, high molecular weight, and eye's physiological and anatomical constraints. The aim of this project is to develop an ocular delivery system for FK506 based on a combined strategy of niosomes and mucoadhesive hyaluronic acid (HA), i.e., FK506HA-coated niosomes, which exploits virtues of both niosomes and HA to synergistically improve ophthalmic bioavailability. The FK506HA-coated niosomes were characterized with particle size, zeta potential, and rheology behavior. Mucoadhesion of FK506HA-coated niosomes to mucin was investigated through surface plasmon resonance in comparison with non-coated niosomes and HA solution. The results showed that niosomes possessed adhesion to mucin, and HA coating enhanced the adhesion. The in vivo precorneal retention was evaluated in rabbit, and the results showed that HA-coated niosomes prolonged the residence of FK506 significantly in comparison with non-coated niosomes or suspension. Aqueous humor pharmacokinetics test showed that area under curve of HA-coated niosomes was 2.3-fold and 1.2-fold as that of suspension and non-coated niosomes, respectively. Moreover, the synergetic corneal permeability enhancement of the hybrid delivery system on FK506 was visualized and confirmed by confocal laser scanning microscope. Overall, the results indicated that the hybrid system facilitated FK506 ocular delivery on mucoadhesion, precorneal retention, aqueous humor pharmacokinetics and transcorneal permeability. Therefore, HA-coated niosomes may be a promising approach for ocular targeting delivery of FK506. PMID:26820107

  12. Mineral-microorganism interactions in Acid Mine Drainage environments: preliminary results

    NASA Astrophysics Data System (ADS)

    Carbone, Cristina; Zotti, Mirca; Pozzolini, Marina; Giovine, Marco; Di Piazza, Simone; Mariotti, Mauro; Lucchetti, Gabriella

    2014-05-01

    Minerals play a key role in controlling the mobility and distribution of metals and metalloids of environmental concern in supergenic environments. These are involved in a variety of processes, spanning the alteration of primary minerals to the formation of secondary authigenic phases and can represent a source or a trap for Potentially Ecotoxic Elements (PTEs). Soil, sediments, and waters heavily polluted with PTEs through AMD processes are a reservoir of a unusual bacteria and fungi well adapted to these toxic environments. Classical studies of biotic weathering have mainly focused on water-mineral interaction and on the ability of microorganism to influence the soil solution chemical composition. In this work, we analyzed two different representative ochreous and greenish-blue AMD colloidal precipitates in order to i) characterize the biota population present in these colloidal minerals and ii) verify the bioaccumulation of PTEs into the fungi and the potential impact of bacteria in the geochemistry of the system. The samples are composed by nanocrystalline goethite which contains high amounts of Fe, Cu, Zn, Pb, and Ni and woodwardite that is characterized by Cu, Zn, Ni, Y, and Ce. These precipitates were examined in order to evaluate the presence of fungal strains and to extract bacteria DNA. The preliminary results of fungi characterization show an interesting and selected mycobiota able to survive under unfavourable environmental conditions. A significant number of fungal strains was isolated in pure culture. Most of them belong to the genus Mucor and Penicillium. It is worth noting the presence of Trametes versicolor, a macrofungal lignicolous species already known for heavy metal biosorption capability from aqueous solution (Gülay et al 2003). The same colloidal precipitates have been processed to extract bacteria DNA, using a specific procedure developed for DNA extraction from sediments. The results gave a good yield of nucleic acids and the positive PCR

  13. Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass.

    PubMed

    Steimer, Sarah S; Berkemeier, Thomas; Gilgen, Anina; Krieger, Ulrich K; Peter, Thomas; Shiraiwa, Manabu; Ammann, Markus

    2015-12-14

    Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) × 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O3 uptake at very low humidity suggests contribution of a self-reaction of O3 on the surface. PMID:26536455

  14. Cassava starch maltodextrinization/monomerization through thermopressurized aqueous phosphoric acid hydrolysis.

    PubMed

    Fontana, J D; Passos, M; Baron, M; Mendes, S V; Ramos, L P

    2001-01-01

    Kinetic conditions were established for the depolymerization of cassava starch for the production of maltodextrins and glucose syrups. Thin-layer chromatography and high-performance liquid chromatography analyses corroborated that the proper H3PO4 strength and thermopressurization range (e.g., 142-170 degrees C; 2.8-6.8 atm) can be successfully explored for such hydrolytic purposes of native starch granules. Because phosphoric acid can be advantageously maintained in the hydrolysate and generates, after controlled neutralization with ammonia, the strategic nutrient triplet for industrial fermentations (C, P, N), this pretreatment strategy can be easily recognized as a recommended technology for hydrolysis and upgrading of starch and other plant polysaccharides. Compared to the classic catalysts, the mandatory desalting step (chloride removal by expensive anion-exchange resin or sulfate precipitation as the calcium-insoluble salt) can be avoided. Furthermore, properly diluted phosphoric acid is well known as an allowable additive in several popular soft drinks such as colas since its acidic feeling in the mouth is compatible and synergistic with both natural and artificial sweeteners. Glycosyrups from phosphorolyzed cassava starch have also been upgraded to high-value single-cell protein such as the pigmented yeast biomass of Xanthophyllomyces dendrorhous (Phaffia rhodozyma), whose astaxanthin (diketo-dihydroxy-beta-carotene) content may reach 0.5-1.0 mg/g of dry yeast cell. This can be used as an ideal complement for animal feeding as well as a natural staining for both fish farming (meat) and poultry (eggs). PMID:11963875

  15. Synthesis of high intrinsic loss power aqueous ferrofluids of iron oxide nanoparticles by citric acid-assisted hydrothermal-reduction route

    SciTech Connect

    Behdadfar, Behshid; Kermanpur, Ahmad; Sadeghi-Aliabadi, Hojjat; Morales, Maria del Puerto; Mozaffari, Morteza

    2012-03-15

    Monodispersed aqueous ferrofluids of iron oxide nanoparticle were synthesized by hydrothermal-reduction route. They were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy and dynamic light scattering. The results showed that certain concentrations of citric acid (CA) are required to obtain only magnetic iron oxides with mean particle sizes around 8 nm. CA acts as a modulator and reducing agent in iron oxide formation which controls nanoparticle size. The XRD, magnetic and heating measurements showed that the temperature and time of hydrothermal reaction can affect the magnetic properties of obtained ferrofluids. The synthesized ferrofluids were stable at pH 7. Their mean hydrodynamic size was around 80 nm with polydispersity index (PDI) of 0.158. The calculated intrinsic loss power (ILP) was 9.4 nHm{sup 2}/kg. So this clean and cheap route is an efficient way to synthesize high ILP aqueous ferrofluids applicable in magnetic hyperthermia. - Graphical abstract: Monodispersed aqueous ferrofluids of iron oxide nanoparticles were synthesized by hydrothermal-reduction method with citric acid as reductant which is an efficient way to synthesize aqueous ferrofluids applicable in magnetic hyperthermia. Highlights: Black-Right-Pointing-Pointer Aqueous iron oxide ferrofluids were synthesized by hydrothermal-reduction route. Black-Right-Pointing-Pointer Citric acid acted as reducing agent and surfactant in the route. Black-Right-Pointing-Pointer This is a facile, low energy and environmental friendly route. Black-Right-Pointing-Pointer The aqueous iron oxide ferrofluids were monodispersed and stable at pH of 7. Black-Right-Pointing-Pointer The calculated intrinsic loss power of the synthesized ferrofluids was very high.

  16. REDUCTION OF PLUTONIUM VALUES IN AN ACIDIC AQUEOUS SOLUTION WITH FORMALDEHYDE

    DOEpatents

    Olson, C.M.

    1959-06-01

    A method is given for reducing Pu to the tetravalent state and lowering the high acidity of dissolver solutions containing U and Pu. Formaldehyde is added to the HNO/sub 3/ solution of U and Pu to effect a formaldehyde to HNO/sub 3/ molar ratio of 0.375:1 to 1.5:1. The Pu can then be removed from the solution by carrier precipitation using BiPO/sub 4/ or by ion exchange. (T.R.H.)

  17. Genotype x environment interactions in eggplant for fruit phenolic acid content

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Eggplant fruit are a rich source of phenolic acids that contribute to fruit nutritive value and influence culinary quality. We evaluated the influence of production environment on eggplant fruit phenolic acid content. Ten Solanum melongena accessions including five F1 hybrid cultivars, three open-...

  18. The effect of alloy composition on the mechanism of stress corrosion cracking of titanium alloys in aqueous environments

    NASA Technical Reports Server (NTRS)

    Williams, D. N.

    1971-01-01

    Emphasis has been placed on determining the interrelations among the composition, phase structure, deformation, and fracture properties of the alpha phase in susceptible alpha-beta alloys. The program is divided into two parts: (1) evaluation of the aqueous stress corrosion susceptibility of a series of alloys that contain various alpha-soluble elements; and (2) investigations of the metallurgical aspects of the mechanism of aqueous stress corrosion cracking.

  19. Transport phenomena accompanying redox switching in polythionine films immersed in aqueous acetic acid solutions

    SciTech Connect

    Bruckenstein, S.; Wilde, C.P. ); Hillman, A.R. )

    1990-08-09

    The transport of neutral molecules in electroactive polymer films is a problem of considerable importance and is addressed here for thin (ca. 10 nm thick) polythionine films. In weak acid media, pH < pK{sub HA}, both solvent and undissociated weak acid are present in the polymer. Raising the pH above pK{sub HA} progressively removes HA. Using the quartz crystal microbalance, we determined the film weight changes accompanying the redox switching process. At all pH's studied, a mass decrease accompanies reduction. The magnitude of this change is consistent with the expulsion of one water molecule per redox site where, at low pH, HA within the film acts as the sole source of counterion, A{sup {minus}}. At higher pH, counterions must increasingly be supplied by the bathing solution, with the result that the mass change becomes less negative. These results are interpreted from a purely thermodynamic viewpoint, and then we discuss a coordination model as a relevant, special case.

  20. Kinetics and mechanism of the oxidation of bromide by periodate in aqueous acidic solution.

    PubMed

    Szél, Viktor; Csekő, György; Horváth, Attila K

    2014-11-13

    The periodate–bromide reaction has been studied spectrophotometrically mainly in excess of bromide ion, monitoring the formation of the total amount of bromine at 450 nm at acidic buffered conditions and at a constant ionic strength in the presence of a phosphoric acid/dihydrogen phosphate buffer. The stoichiometry of the reaction was established to be strictly IO4(–) + 2Br(–) + 2H(+) → Br2 + IO3(–) + H2O. The formal kinetic order of the reactants was found to be perfectly one and two in the cases of periodate and bromide, respectively, but that of the hydrogen ion lies between one and two. We have also provided experimental evidence that dihydrogen phosphate accelerates the formation of bromine, suggesting the appearance of strong buffer assistance. On the basis of the experiments, a simple two-step kinetic model is proposed involving BrIO3 as a key intermediate that perfectly explains all of the experimental findings. Furthermore, we have also shown that in huge excess of bromide, the apparent rate coefficient obtained from the individual curve fitting method of the absorbance–time series is necessarily independent of the initial periodate concentration that may falsely be interpreted as the rate of bromine formation is also independent of the concentration of periodate. PMID:25365468

  1. Halocarbons in the environment: Estimates of thermodynamic properties for aqueous chloroethylene species and their stabilities in natural settings

    SciTech Connect

    Haas, J.R.; Shock, E.L.

    1999-10-01

    Standard partial molal thermodynamic parameters for the aqueous chlorinated-ethylene species, perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), cis-1,2-dichloroethylene (cis-1,2-DCE), trans-1,2-dichloroethylene (trans-1,2-DCE), and vinyl chloride (VC) have been estimated by using experimental gas-solubility data and correlation algorithms. The provided thermodynamic values may be used to calculate properties of reactions involving the aqueous chloroethylene species at a wide range of temperatures and pressures. Estimated values for the chloroethylenes were used, along with published values for minerals, gases, aqueous ions, and aqueous neutral organic species, to calculate the stability of chloroethylene species in equilibrium with the minerals magnetite, hematite, pyrite, and pyrrhotite in the subsurface. Estimated values for the aqueous chloroethylenes were also used to calculate reduction potentials for microbially-mediated reductive dechlorination half-reactions at elevated temperatures. Calculations indicate that all aqueous chloroethylene species are energetically favored to decompose to ethylene(aq) under a wide range of conditions in the subsurface, by both abiotic and biotic pathways. Anaerobic microbially mediated degradation is especially favored under conditions at least sufficiently reducing to promote sulfate-reduction, but not under conditions sufficient for microbial denitrification, pyrolusite reduction, or ferric-iron reduction.

  2. Halocarbons in the environment: estimates of thermodynamic properties for aqueous chloroethylene species and their stabilities in natural settings

    NASA Astrophysics Data System (ADS)

    Haas, Johnson R.; Shock, Everett L.

    1999-10-01

    Standard partial molal thermodynamic parameters for the aqueous chlorinated-ethylene species, perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), cis-1,2-dichloroethylene (cis-1,2-DCE), trans-1,2-dichloroethylene (trans-1,2,-DCE), and vinyl chloride (VC) have been estimated by using experimental gas-solubility data and correlation algorithms. The provided thermodynamic values may be used to calculate properties of reactions involving the aqueous chloroethylene species at a wide range of temperatures and pressures. Estimated values for the chloroethylenes were used, along with published values for minerals, gases, aqueous ions, and aqueous neutral organic species, to calculate the stability of chloroethylene species in equilibrium with the minerals magnetite, hematite, pyrite, and pyrrhotite in the subsurface. Estimated values for the aqueous chloroethylenes were also used to calculate reduction potentials for microbially-mediated reductive dechlorination half-reactions at elevated temperatures. Calculations indicate that all aqueous chloroethylene species are energetically favored to decompose to ethylene(aq) under a wide range of conditions in the subsurface, by both abiotic and biotic pathways. Anaerobic microbially mediated degradation is especially favored under conditions at least sufficiently reducing to promote sulfate-reduction, but not under conditions sufficient for microbial denitrification, pyrolusite reduction, or ferric-iron reduction.

  3. The dissolution behavior of scorodite in acidic environments

    NASA Astrophysics Data System (ADS)

    Pande, Preeti

    2001-11-01

    The safe disposal of arsenic-containing waste has been a difficult problem for the mining and metallurgical industry. One of the solutions to the arsenic problem is the precipitation of scorodite, an arsenic-containing mineral. Scorodite is reported to be relatively stable over a wide range of pH, and therefore may be a preferred disposal option. The effect of organic complexing agents on scorodite stability, however, is largely unknown. The present study is a phenomenological investigation into the dissolution kinetics of scorodite in the presence of oxalic acid under varying conditions of pH, oxalic acid concentration and temperature. The effect of scorodite particle size was also investigated. The morphological changes accompanying the dissolution process were examined by SEM and TEM analyses. Dissolution curves were divided into a linear induction period and a post-induction period. Activation energies were determined. Complete dissolution data were fit to the Prout-Tompkins/Austin-Rickett model. Dissolution data are indicative of auto-accelerated processes. The rapid increase in dissolution rate following the induction period is believed to be associated with an increase in the effective surface area. Pitting was observed on the surface of scorodite in the early stages of dissolution. In the later stages of dissolution, these pits were observed to grow and coalesce, in many cases resulting in the formation of dissolution holes.

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

    PubMed Central

    2015-01-01

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

  5. Bacteria and Archaea in acidic environments and a key to morphological identification

    USGS Publications Warehouse

    Robbins, E.I.

    2000-01-01

    Natural and anthropogenic acidic environments are dominated by bacteria and Archaea. As many as 86 genera or species have been identified or isolated from pH <4.5 environments. This paper reviews the worldwide literature and provide tables of morphological characteristics, habitat information and a key for light microscope identification for the non-microbiologist.

  6. Surface modification of activated carbon for enhanced adsorption of perfluoroalkyl acids from aqueous solutions.

    PubMed

    Zhi, Yue; Liu, Jinxia

    2016-02-01

    The objective of the research was to examine the effect of increasing carbon surface basicity on uptake of perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) by activated carbon. Granular activated carbons made from coal, coconut shell, wood, and phenolic-polymer-based activated carbon fibers were modified through high-temperature and ammonia gas treatments to facilitate systematical evaluation of the impact of basicity of different origins. Comparison of adsorption isotherms and adsorption distribution coefficients showed that the ammonia gas treatment was more effective than the high-temperature treatment in enhancing surface basicity. The resultant higher point of zero charges and total basicity (measured by total HCl uptake) correlated with improved adsorption affinity for PFOS and PFOA. The effectiveness of surface modification to enhance adsorption varied with carbon raw material. Wood-based carbons and activated carbon fibers showed enhancement by one to three orders of magnitudes while other materials could experience reduction in adsorption towards either PFOS or PFOA. PMID:26469934

  7. Factor analysis for isolation of the Raman spectra of aqueous sulfuric acid components

    SciTech Connect

    Malinowski, E.R.; Cox, R.A.; Haldna, U.L.

    1984-04-01

    The Raman spectra of 16 sulfuric acid/water mixtures over the entire mole fraction range were studied by various factor analysis techniques. Abstract factor analysis showed that three factors account for 98.69% of the variation in the data with a real error of 13%. Key-set factor analysis, was used to identify three spectral wavenumbers unique to each component. Spectral-isolation factor analysis, based on the key wavenumbers, revealed the spectra of each unknown component. Target factor analysis, based on the isolated spectra, yielded the relative amounts of the three spectral components. The concentration profiles obtained from the factor loadings, as well as the isolated spectra, were used to identify the chemical species.

  8. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    PubMed

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process. PMID:26398038

  9. Enhanced removal of 8-quinolinecarboxylic acid in an activated carbon cloth by electroadsorption in aqueous solution.

    PubMed

    López-Bernabeu, S; Ruiz-Rosas, R; Quijada, C; Montilla, F; Morallón, E

    2016-02-01

    The effect of the electrochemical treatment (potentiostatic treatment in a filter-press electrochemical cell) on the adsorption capacity of an activated carbon cloth (ACC) was analyzed in relation with the removal of 8-quinolinecarboxylic acid pollutant from water. The adsorption capacity of an ACC is quantitatively improved in the presence of an electric field (electroadsorption process) reaching values of 96% in comparison to 55% in absence of applied potential. In addition, the cathodic treatment results in higher removal efficiencies than the anodic treatment. The enhanced adsorption capacity has been proved to be irreversible, since the removed compound remains adsorbed after switching the applied potential. The kinetics of the adsorption processes is also improved by the presence of an applied potential. PMID:26433936

  10. Dissolution kinetics of kaolinite in acidic aqueous solutions at 25 C

    SciTech Connect

    Wieland, E.; Stumm, W. Swiss Federal Inst. of Tech., Zuerich )

    1992-09-01

    The dissolution of kaolinite is interpreted in terms of the surface complexation model. Acid/base properties of the terminal OH groups and ion exchange reactions occurring at the kaolinite surface have been investigated. A three-site model incorporating solid-solution equilibria at aluminol groups of the edge and gibbsite surfaces and at negatively charged XO groups of the siloxane surface account for the protonation of kaolinite platelets in acidic solutions. The dissolution kinetics of kaolinite at 25 C has been studied as a function of solution pH. The dissolution of kaolinite is nonstoichiometric in the pH range 2-6.5 with a preferential release of silicon. Stoichiometry of the dissolution reaction is achieved, however, in the presence of oxalate as Al-complexing ligand. The detachment of aluminium from the lattice structure of the kaolinite surface and its readsorption on distinct surface sites occur simultaneously during the dissolution process causing the experimentally observed nonstoichiometry. The proton-promoted dissolution of kaolinite occurs at the edge surface (pH < 6.5) and the gibbsite surface (pH < 4). The pH-dependence of the dissolution rate R[sub H](Si) reflects sequential protonation of terminal OH groups on both surfaces. The dissolution reaction can be interpreted as a coupled release of Al and Si with the detachment of the Al center from the surface lattice structure as the rate-limiting step. The aluminium:proton stoichiometry of the activated complex is 1:3 at the gibbsite surface and 1:1 at the edge surface.

  11. EFFECT OF AN ACID RAIN ENVIRONMENT ON LIMESTONE SURFACES.

    USGS Publications Warehouse

    Mossotti, Victor G.; Lindsay, James R.; Hochella, Michael F., Jr.

    1987-01-01

    Salem limestone samples were exposed to weathering for 1 y in several urban and one rural environments. Samples exposed in the rural location were chemically indistinguishable from the freshly quarried limestone, whereas all samples collected from urban exposure sites developed gypsum stains on the ground-facing surfaces where the stones were not washed by precipitation. The gas-solid reaction of SO//2 with calcite was selected for detailed consideration. It appears from the model that under arid conditions, the quantity of stain deposited on an unwashed surface is independent of atmospheric SO//2 concentration once the surface has been saturated with gypsum. Under wet conditions, surface sulfation and weight loss are probably dominated by mechanisms involving wet stone. However, if the rain events are frequent and delimited by periods of dryness, the quantity of gypsum produced by a gas-solid reaction mechanism should correlate with both the frequency of rain events and the atmospheric SO//2 level.

  12. Sequence dependent N-terminal rearrangement and degradation of peptide nucleic acid (PNA) in aqueous solution

    NASA Technical Reports Server (NTRS)

    Eriksson, M.; Christensen, L.; Schmidt, J.; Haaima, G.; Orgel, L.; Nielsen, P. E.

    1998-01-01

    The stability of the PNA (peptide nucleic acid) thymine monomer inverted question markN-[2-(thymin-1-ylacetyl)]-N-(2-aminoaminoethyl)glycine inverted question mark and those of various PNA oligomers (5-8-mers) have been measured at room temperature (20 degrees C) as a function of pH. The thymine monomer undergoes N-acyl transfer rearrangement with a half-life of 34 days at pH 11 as analyzed by 1H NMR; and two reactions, the N-acyl transfer and a sequential degradation, are found by HPLC analysis to occur at measurable rates for the oligomers at pH 9 or above. Dependent on the amino-terminal sequence, half-lives of 350 h to 163 days were found at pH 9. At pH 12 the half-lives ranged from 1.5 h to 21 days. The results are discussed in terms of PNA as a gene therapeutic drug as well as a possible prebiotic genetic material.

  13. Synthesis and Evaluation of Molecularly Imprinted Silica Gel for 2-Hydroxybenzoic Acid in Aqueous Solution

    PubMed Central

    Abdul Raof, Siti Farhana; Mohamad, Sharifah; Abas, Mhd Radzi

    2013-01-01

    A molecularly imprinted silica gel sorbent for selective removal of 2-Hydroxybenzoic acid (2-HA) was prepared by a surface imprinting technique with a sol-gel process. The 2-HA molecularly imprinted silica gel (2-HA-MISG) sorbent was evaluated by various parameters, including the influence of pH, static, kinetic adsorption and selectivity experiments. The optimum adsorption capacity to the 2-HA appeared to be around pH 2 by the polymer. Morevoer, the imprinted sorbent displayed fast uptake kinetics, obtained within 20 min. The adsorption capacity of the 2-HA-MISG (76.2 mg g−1) was higher than that of the non-imprinted silica gel (NISG) (42.58 mg g−1). This indicates that the 2-HA-MISG offers a higher affinity for 2-HA than the NISG. The polymer displays good selectivity and exhibits good reusability. Experimental results show the potential of molecularly imprinted silica sorbent for selective removal of 2-HA. PMID:23493059

  14. Effect of acid hydrolysis on regenerated kenaf core membrane produced using aqueous alkaline-urea systems.

    PubMed

    Padzil, Farah Nadia Mohammad; Zakaria, Sarani; Chia, Chin Hua; Jaafar, Sharifah Nabihah Syed; Kaco, Hatika; Gan, Sinyee; Ng, Peivun

    2015-06-25

    Bleached kenaf core pulps (BKC) were hydrolyzed in H2SO4 (0.5M) at different time (0min to 90min) at room temperature. After the hydrolysis process, the viscosity average molecular weight (Mŋ) for BKC sample has reduced from 14.5×10(4) to 2.55×10(4). The hydrolyzed BKC was then dissolved in NaOH:urea:water and in LiOH:urea:water mixed solvent at the ratio of 7:12:81 and 4.6:15:80.4, respectively. The increased in hydrolysis time has decreased Mŋ of cellulose leading to easy dissolution process. Higher porosity and transparency with lower crystallinity index (CrI) of regenerated membrane produced can be achieved as the Mŋ reduced. The properties of membrane were observed through FESEM, UV-vis spectrophotometer and XRD. This study has proven that acid hydrolysis has reduced the Mŋ of cellulose, thus, enhanced the properties of regenerated membrane produced with assisted by alkaline/urea system. PMID:25839807

  15. Adsorption of 2,4-Dichlorophenoxyacetic Acid from an Aqueous Solution on Fly Ash.

    PubMed

    Kuśmierek, Krzysztof; Świątkowski, Andrzej

    2016-03-01

    The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on fly ash was studied. The effects of adsorbent dose, contact time, pH, ionic strength, and temperature on the adsorption were investigated. Adsorption kinetic data were analyzed using pseudo-first and pseudo-second order models, and results showed that adsorption kinetics were better represented by the pseudo-second order model. Adsorption isotherms of 2,4-D on fly ash were analyzed using the Freundlich and Langmuir models. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicated that the adsorption process was spontaneous and endothermic. The negative values of ΔG° and the positive value of ΔH° indicate the spontaneous nature of 2,4-D adsorption on fly ash, and that the adsorption process was endothermic. Results showed that fly ash is an efficient, low-cost adsorbent for removal of 2,4-D from water. PMID:26931534

  16. The initiation of material corrosion in semicritical and supercritical aqueous hydrochloric acid solutions

    SciTech Connect

    Boukis, N.; Kritzer, P.; Schacht, M.; Dinjus, E.

    1999-11-01

    In recent years, a lot of work has been performed to interpret corrosion during the process of supercritical water oxidation (SCWO). For a better understanding of the corrosion mechanisms, the initiation processes of corrosion have to be known. The corrosion resistance of two alumina ceramics and sapphire in hydrochloric acid (HCl) solutions was investigated at T = 240 C -- 500 C and p = 27 MPa. For the alumina ceramics, intergranular corrosion and dissolution of the grains were identified as corrosion mechanisms. The corrosion experiments with the nickel-base alloy 625 (UNS N06625) and its main constituents nickel, chromium, and molybdenum were performed in oxygenated HCl solutions at T = 350 C and p = 24 MPa. Nickel and molybdenum showed severe weight loss after only 5 h of reaction. The attack on chromium started with grain boundary etching and proceeded via the formation of thick, spalling oxide layers on the surface. Initial corrosion phenomena observed on alloy 625 were intergranular attack and pit formation. At longer reaction times, a complete surface attack was observed.

  17. Adsorption removal of acid black 1 from aqueous solution using ordered mesoporous carbon

    NASA Astrophysics Data System (ADS)

    Peng, Xiaoming; Hu, Xijun; Fu, Dafang; Lam, Frank L. Y.

    2014-03-01

    A novel ordered mesoporous carbon CMK-3 and synthetic CMK-3 containing nitrogen functional groups by ammonia-treated were applied for acid black 1(AB1) dye adsorption. The ammonia-treated(chemical vapor deposition method) before and after CMK-3 were characterized by using a Micrometitics ASAP 2020 surface area analyzer (ASAP 2020), Fourier transform infrared spectrophotometer (FT-IR), X-ray Photoelectron Spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM) and equilibrium studies. This result indicates that the prepared CMK-3 and modified CMK-3 were almost uniform, as rope-like domains and their uniform mesopore with diameter centered at 3.2 nm and 3.7 nm. The FIIR analysis depicted that the presence of a variety of new basic functional groups on the modified CMK-3 surface. Several effect variables of pH, dye concentration and temperature were studied. The pseudo second-order model showed the fitter well to agree with the kinetic data. The experimental data were analyzed by the Langmuir and Freundlich models, with the latter found to closely the isotherm model. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The results show that CMK-3 using ammonia gas modified by thermal treatment system is an effective method to improvement capacity as it shows the highest adsorption capacity of AB1, as compared to the unmodified CMK-3 and the bamboo-based carbon, respectively.

  18. Kinetics and thermodynamic studies for removal of acid blue 129 from aqueous solution by almond shell

    PubMed Central

    2014-01-01

    Efficiency and performance of Almond shell (AS) adsorbent for the removal and recovery of Acid Blue 129 (AB129) from wastewater is presented in this report. The influence of variables including pH, initial dye concentration, adsorbent dosage, particle size, contact time and temperature on the dye removal have been investigated in batch method by one at a time optimization method. The experimental equilibrium data were tested by four widely used isotherm models namely, Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich (D–R). It was found that adsorption of AB129 on AS well with the Langmuir isotherm model, implying monolayer coverage of dye molecules onto the surface of the adsorbent. More than 98% removal efficiency was obtained within 14 min at adsorbent dose of 0.4 g for initial dye concentration of 40 mg/L at pH 2. Kinetics of the adsorption process was tested by pseudo-first-order and pseudo-second-order kinetics, and intraparticle diffusion mechanism. Pseudo-second-order kinetic model provided a better correlation for the experimental data studied in comparison to the pseudo-first-order model. Calculation of various thermodynamic parameters such as, Gibb’s free energy, entropy and enthalpy of the on-going adsorption process indicate feasibility and endothermic nature of AB129 adsorption on all adsorbents. This work can be used in design of adsorption columns for dyes removal. PMID:24620822

  19. Transport of trivalent and hexavalent chromium through different ion-selective membranes in acidic aqueous media

    SciTech Connect

    Costa, R.F.D.; Rodrigues, M.A.S.; Ferreira, J.Z.

    1998-06-01

    The aim of this work was to evaluate the transport of trivalent and hexavalent chromium through anion- and cation-selective membranes using two- and three-compartment electrodialysis cells. Tests were done with acidic solutions of trivalent chromium ions, Cr{sup 3+}, and hexavalent chromium ions, Cr{sub 2}O{sub 7}{sup 2{minus}}. In each situation the transport of metallic ions through the membrane was evaluated. In the tests with trivalent chromium, Nafion 417 and Selemion CMT cation-selective membranes were used, and in the tests with hexavalent chromium, Selemion AMT membrane was used. The influence of SO{sub 4}{sup 2{minus}} ions and of the concentration of H{sup +} ions in the solutions was also analyzed. Results showed the oxidation of the Cr{sup 3+} ion at the anode and the reduction of the Cr{sub 2}O{sub 7}{sup 2{minus}} ion at the cathode. The maximum yield in the process was reached when hexavalent chromium solutions were used in the absence of sulfate ions and a Selemion AMT membrane in a three-compartment cell.

  20. Effects of toxic work environments on sperm quality and ascorbic acid levels

    SciTech Connect

    Dawson, E.B.; Harris, W.A.; Powell, L.C. )

    1990-02-26

    Surveys have shown that toxic work environments lower sperm quality, and controlled studies indicate that ascorbic acid supplementation improves sperm viability and agglutination. The sperm quality of 50 subjects each from: (1) office workers, (2) a lead smelter, (3) petroleum refineries, and (4) a herbicide plant were compared with serum and semen ascorbic acid levels. The sperm characteristics studied were: count as million/ml and as percent; viability, motility, clumping, and abnormal morphology. The serum ascorbic acid levels were directly proportional to sperm viability and inversely correlated to clumping of all groups. Moreover, serum ascorbic acid levels were also inversely correlated to twin tail and amorphous forms of abnormal sperm morphology. The results of the study indicate that toxic environments depress sperm quality and suggest that ascorbic acid supplementation will improve sperm quality and fertility.