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Sample records for 236pu tracer anion

  1. Adsorption behaviour of PuF6 on UO2F2 by the use of 236Pu

    NASA Astrophysics Data System (ADS)

    Sato, Nobuaki; Matsuda, Minoru; Mitsugashira, Toshiaki; Kirishima, Akira

    2010-03-01

    To know the behavior of plutonium in the fluoride volatility process (FLUOREX PROCESS) for the spent nuclear fuel, both UO2 and PuO2 are fluorinated by fluorine forming volatile UF6 and PuF6, respectively. Then PuF6 is separated and recovered from UF6 by using adsorption materials such as uranyl fluoride UO2F2. In this paper, adsorption behavior of PuF6on UO2F2 was examined by the use of 236Pu tracer. First, the stability of UO2F2 in F2atmosphere was analyzed by TG-DTA method showing that uranium volatilized completely over 350 °C by the formation of UF6 and the adsorption of plutonium by UO2F2 should be done at temperatures lower than 250 °C. The behavior of PtF6 as a chemical analogue of PuF6 was also conducted for comparison and it showed that the deposition of PtF4 on UO2F2 at 200 °C. When the 236Pu doped U3O8 was reacted with 10%F2-He gas, the PuF6 vaporized at ca. 600 °C. Then adsorption of 236Pu on UO2F2 was observed by α ray measurement. The adsorption mechanism of Pu on UO2F2 was discussed with experimental data and thermodynamic consideration.

  2. The Concentration of (236)Pu Daughters in Plutonium for Application to MOX Production from Plutonium from Dismantled US Nuclear Weapons

    SciTech Connect

    Sampson, T.E.; Cremers, T.L.

    2001-05-01

    The isotope {sup 236}Pu in the weapons-grade plutonium to be used in the US MOX (mixed-oxide) plant is of concern because the daughter products of {sup 236}Pu are sources of high-energy gamma rays. The {sup 208}Tl daughter of {sup 236}Pu emits intense, high-energy gamma rays that are important for radiation exposure calculations for plant design. It is generally thought that the concentrations of {sup 236}Pu and its daughters are well below 10{sup {minus}10}, but these concentrations are generally below the detection limits of most analytical techniques. One technique that can be used to determine the concentration {sup 208}Tl is the direct measurement of the intensity of the {sup 208}Tl gamma rays in the gamma-ray spectrum from plutonium. Thallium-208 will be in equilibrium with {sup 228}Th, and may very well be in equilibrium with {sup 232}U for most aged plutonium samples. We have used the FRAM isotopic analysis software to analyze dozens of archived high-resolution gamma ray spectra from various samples of US and foreign plutonium. We are able to quantify the ratio of minor isotopes with measurable gamma-ray emissions to the major isotope of plutonium and hence, through the measurement of the plutonium isotopic distribution of the sample, to elemental plutonium itself. Excluding items packaged in fluoropolymer vials, all samples analyzed with {sup 240}Pu < 9% gave {sup 228}Th/Pu ratios < 3.4 e-012 and all samples of US-produced plutonium, including {sup 240}Pu values up to 16.4%, gave {sup 228}Th/Pu ratios < 9.4 e-012. None of these values is significant from a radiation dose standpoint.

  3. A highly resolved anion-exchange chromatographic method for determination of saccharidic tracers for biomass combustion and primary bio-particles in atmospheric aerosol

    NASA Astrophysics Data System (ADS)

    Iinuma, Yoshiteru; Engling, Guenter; Puxbaum, Hans; Herrmann, Hartmut

    An improved high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD) method is developed and validated for simultaneous determination of atmospherically relevant sugar alcohols, monosaccharides, and monosaccharide anhydrides. The improved method enables the separation of levoglucosan and arabitol which were not or insufficiently separated by the previous HPAEC-PAD methods. Reproducibility of the method was tested for both standard solutions and atmospheric aerosol samples. The peak area relative standard deviation (RSD%) of standard solutions were found to be lower than 1.5% for consecutive analyses ( n = 3) and lower than 4% for day to day variation ( n = 9). The peak area RSD% of atmospheric samples with typical European wintertime monosaccharide concentrations ( n = 9) was found to be similar to that of standard solutions. Limits of detection ranged from 0.002 mg L -1 for inositol to 0.08 mg L -1 for fructose. The developed method offers a simple, reliable and cost effective determination of atmospheric tracers for biomass combustion and for selected bio-aerosol components at sub-nanogram per cubic-meter-air concentration levels for routine analysis.

  4. Tracer Technique

    NASA Astrophysics Data System (ADS)

    Haba, H.; Motomura, S.; Kamino, S.; Enomoto, S.

    In radioactive tracer technique, radioactive nuclides are used to follow the behavior of elements or chemical species in chemical and other processes. This is realized by means of radioactivity measurement. In 1913, Hevesy and Paneth succeeded in determining the extremely low solubility of lead salts by using naturally occurring 210Pb as a radioactive tracer. As various radioactive nuclides became artificially available, this technique has been widely employed in studies of chemical equilibrium and reactions as well as in chemical analysis. It is also an essential technique in biochemical, biological, medical, geological, and environmental studies. Medical diagnosis and industrial process control are the fields of its most important practical application. In this chapter, fundamental ideas concerning radioactive tracers will be described followed by their application with typical examples. Detailed description on their application to life sciences and medicine is given in Vol. 4.

  5. INL Tracer Interpretation

    Energy Science and Technology Software Center (ESTSC)

    2007-03-27

    This spreadsheet application is for tracer test analysis. The analyses are based on the first temporal moment of a tracer. The governing equations are briefly discussed, and the individual steps required of the user are outlined. A series of Excel macros written in Visual Basic calculate mean residence time, swept pore volume, and flow-storage geometry from a tracer history.

  6. Anion exchange membrane

    DOEpatents

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  7. Anions in Cometary Comae

    NASA Technical Reports Server (NTRS)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  8. Biological tracer method

    DOEpatents

    Strong-Gunderson, Janet M.; Palumbo, Anthony V.

    1998-01-01

    The present invention is a biological tracer method for characterizing the movement of a material through a medium, comprising the steps of: introducing a biological tracer comprising a microorganism having ice nucleating activity into a medium; collecting at least one sample of the medium from a point removed from the introduction point; and analyzing the sample for the presence of the biological tracer. The present invention is also a method for using a biological tracer as a label for material identification by introducing a biological tracer having ice nucleating activity into a material, collecting a sample of a portion of the labelled material and analyzing the sample for the presence of the biological tracer.

  9. Biological tracer method

    DOEpatents

    Strong-Gunderson, J.M.; Palumbo, A.V.

    1998-09-15

    The present invention is a biological tracer method for characterizing the movement of a material through a medium, comprising the steps of: introducing a biological tracer comprising a microorganism having ice nucleating activity into a medium; collecting at least one sample of the medium from a point removed from the introduction point; and analyzing the sample for the presence of the biological tracer. The present invention is also a method for using a biological tracer as a label for material identification by introducing a biological tracer having ice nucleating activity into a material, collecting a sample of a portion of the labelled material and analyzing the sample for the presence of the biological tracer. 2 figs.

  10. Anion solvation in alcohols

    SciTech Connect

    Jonah, C.D.; Xujia, Zhang; Lin, Yi

    1996-03-01

    Anion solvation is measured in alcohols using pump-probe pulse radiolysis and the activation energy of solvation is determined. Solvation of an anion appears to be different than excited state solvation. The continuum dielectric model does not appear to explain the results.

  11. Tracer attenuation in groundwater

    NASA Astrophysics Data System (ADS)

    Cvetkovic, Vladimir

    2011-12-01

    The self-purifying capacity of aquifers strongly depends on the attenuation of waterborne contaminants, i.e., irreversible loss of contaminant mass on a given scale as a result of coupled transport and transformation processes. A general formulation of tracer attenuation in groundwater is presented. Basic sensitivities of attenuation to macrodispersion and retention are illustrated for a few typical retention mechanisms. Tracer recovery is suggested as an experimental proxy for attenuation. Unique experimental data of tracer recovery in crystalline rock compare favorably with the theoretical model that is based on diffusion-controlled retention. Non-Fickian hydrodynamic transport has potentially a large impact on field-scale attenuation of dissolved contaminants.

  12. Perfluorocarbon tracer technology

    SciTech Connect

    Dietz, R.N.

    1986-01-01

    Perfluorocarbon tracer technology developments at Brookhaven is described, including the latest identified as well as available PFTs and air sampling and analysis tools, to demonstrate their utility in a number of different atmospheric tracer experiments as well as in other applications, and to provide food-for-thought on new ways in which the PFTs can be applied in other research objectives. All of the important tools are described, but emphasis is given to the latest developments in the technology.

  13. Anion-π Enzymes

    PubMed Central

    2016-01-01

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anion-π catalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anion-π catalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pKa of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pKa of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  14. Anion-π Enzymes.

    PubMed

    Cotelle, Yoann; Lebrun, Vincent; Sakai, Naomi; Ward, Thomas R; Matile, Stefan

    2016-06-22

    In this report, we introduce artificial enzymes that operate with anion-π interactions, an interaction that is essentially new to nature. The possibility to stabilize anionic intermediates and transition states on an π-acidic surface has been recently demonstrated, using the addition of malonate half thioesters to enolate acceptors as a biologically relevant example. The best chiral anion-π catalysts operate with an addition/decarboxylation ratio of 4:1, but without any stereoselectivity. To catalyze this important but intrinsically disfavored reaction stereoselectively, a series of anion-π catalysts was equipped with biotin and screened against a collection of streptavidin mutants. With the best hit, the S112Y mutant, the reaction occurred with 95% ee and complete suppression of the intrinsically favored side product from decarboxylation. This performance of anion-π enzymes rivals, if not exceeds, that of the best conventional organocatalysts. Inhibition of the S112Y mutant by nitrate but not by bulky anions supports that contributions from anion-π interactions exist and matter, also within proteins. In agreement with docking results, K121 is shown to be essential, presumably to lower the pK a of the tertiary amine catalyst to operate at the optimum pH around 3, that is below the pK a of the substrate. Most importantly, increasing enantioselectivity with different mutants always coincides with increasing rates and conversion, i.e., selective transition-state stabilization. PMID:27413782

  15. Intrinsic anion oxidation potentials.

    PubMed

    Johansson, Patrik

    2006-11-01

    Anions of lithium battery salts have been investigated by electronic structure calculations with the objective to find a computational measure to correlate with the observed (in)stability of nonaqueous lithium battery electrolytes vs oxidation often encountered in practice. Accurate prediction of intrinsic anion oxidation potentials is here made possible by computing the vertical free energy difference between anion and neutral radical (Delta Gv) and further strengthened by an empirical correction using only the anion volume as a parameter. The 6-311+G(2df,p) basis set, the VSXC functional, and the C-PCM SCRF algorithm were used. The Delta Gv calculations can be performed using any standard computational chemistry software. PMID:17078600

  16. Anion exchange polymer electrolytes

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik

    2015-06-02

    Anion exchange polymer electrolytes that include guanidinium functionalized polymers may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  17. Anion-π catalysis.

    PubMed

    Zhao, Yingjie; Beuchat, César; Domoto, Yuya; Gajewy, Jadwiga; Wilson, Adam; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2014-02-01

    The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol(-1) are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 10(5) M(-1). Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the

  18. Halogen bonding anion recognition.

    PubMed

    Brown, Asha; Beer, Paul D

    2016-07-01

    A halogen bond is an attractive non-covalent interaction between an electrophilic region in a covalently bonded halogen atom and a Lewis base. While these interactions have long been exploited as a tool in crystal engineering their powerful ability to direct supramolecular self-assembly and molecular recognition processes in solution has, until recently, been overlooked. During the last decade however an ever-increasing number of studies on solution-phase halogen-bond-mediated anion recognition processes has emerged. This Feature Article summarises advancements which have been made thus far in this rapidly developing research area. We survey the use of iodoperfluoroarene, haloimidazolium and halotriazole/triazolium halogen-bond-donor motifs in anion receptor design, before providing an account of our research into the application of mechanically interlocked rotaxane and catenane frameworks as halogen bonding anion host systems. PMID:27273600

  19. Vanadogermanate cluster anions.

    PubMed

    Whitfield, T; Wang, X; Jacobson, A J

    2003-06-16

    Three novel vanadogermanate cluster anions have been synthesized by hydrothermal reactions. The cluster anions are derived from the (V(18)O(42)) Keggin cluster shell by substitution of V=O(2+) "caps" by Ge(2)O(OH)(2)(4+) species. In Cs(8)[Ge(4)V(16)O(42)(OH)(4)].4.7H(2)O, 1, (monoclinic, space group C2/c (No. 15), Z = 8, a = 44.513(2) A, b = 12.7632(7) A, c = 22.923(1) A, beta = 101.376(1) degrees ) and (pipH(2))(4)(pipH)(4)[Ge(8)V(14)O(50).(H(2)O)] (pip = C(4)N(2)H(10)), 2 (tetragonal, space group P4(2)/nnm (No. 134), Z = 2, a = 14.9950(7) A, c = 18.408(1) A), two and four VO(2+) caps are replaced, respectively, and each cluster anion encapsulates a water molecule. In K(5)H(8)Ge(8)V(12)SO(52).10H(2)O, 3, (tetragonal, space group I4/m (No. 87), Z = 2, a = 15.573(1) A, c = 10.963(1) A), four VO(2+) caps are replaced by Ge(2)O(OH)(2)(4+) species, and an additional two are omitted. The cluster ion in 3 contains a sulfate anion disordered over two positions. The cluster anions are analogous to the vanadoarsenate anions [V(18)(-)(n)()As(2)(n)()O(42)(X)](m)(-) (X = SO(3), SO(4), Cl; n = 3, 4) previously reported. PMID:12793808

  20. ION CHROMATOGRAPHY OF ANIONS

    EPA Science Inventory

    A Dionex Model 10 Ion Chromatograph was evaluated for the measurement of anionic species in water. The theoretical effect of hydrogen ion activity (pH) on the elution time of phosphate and arsenate was tested and empirical selectivity coefficients were determined for the major pr...

  1. Tracer for circulation determinations

    SciTech Connect

    Moore, H.; Santos, S.; Wysong, R. D.

    1985-03-19

    An improved tracer particle is described comprising an ion exchange core having a polymer coating thereon, the coated ion exchange core having a reaction site capable of reacting with a compound containing an oxirane group, said coated ion exchange core having been treated with a compound containing an oxirane group to react with said coated ion exchange core causing an increase in mass of the tracer particle. Preferably, the ion exchange core is labelled with a radionuclide. These particles have improved characteristics including improved stability against leaching and improved handling properties. Such particles are useful in circulatory determinations involving the injection of the particles as a suspension in a physiologically acceptable carrier or medium into the circulatory system of animals.

  2. Tracers and Tracer Testing: Design, Implementation, Tracer Selection, and Interpretation Methods

    SciTech Connect

    G. Michael Shook; Shannon L.; Allan Wylie

    2004-01-01

    Conducting a successful tracer test requires adhering to a set of steps. The steps include identifying appropriate and achievable test goals, identifying tracers with the appropriate properties, and implementing the test as designed. When these steps are taken correctly, a host of tracer test analysis methods are available to the practitioner. This report discusses the individual steps required for a successful tracer test and presents methods for analysis. The report is an overview of tracer technology; the Suggested Reading section offers references to the specifics of test design and interpretation.

  3. Tracer tomography (in) rocks!

    NASA Astrophysics Data System (ADS)

    Somogyvári, Márk; Jalali, Mohammadreza; Jimenez Parras, Santos; Bayer, Peter

    2016-04-01

    Physical behavior of fractured aquifers is rigorously controlled by the presence of interconnected conductive fractures, as they represent the main pathways for flow and transport. Ideally, they are simulated as a discrete fracture network (DFN) in a model to capture the role of fracture system geometry, i.e. fracture length, height, and width (aperture/transmissivity). Such network may be constrained by prior geological information or direct data resources such as field mapping, borehole logging and geophysics. With the many geometric features, however, calibration of a DFN to measured data is challenging. This is especially the case when spatial properties of a fracture network need to be calibrated to flow and transport data. One way to increase the insight in a fractured rock is by combining the information from multiple field tests. In this study, a tomographic configuration that combines multiple tracer tests is suggested. These tests are conducted from a borehole with different injection levels that act as sources. In a downgradient borehole, the tracer is recorded at different levels or receivers, in order to maximize insight in the spatial heterogeneity of the rock. As tracer here we chose heat, and temperature breakthrough curves are recorded. The recorded tracer data is inverted using a novel stochastic trans-dimensional Markov Chain Monte Carlo procedure. An initial DFN solution is generated and sequentially modified given available geological information, such as expected fracture density, orientation, length distribution, spacing and persistency. During this sequential modification, the DFN evolves in a trans-dimensional inversion space through adding and/or deleting fracture segments. This stochastic inversion algorithm requires a large number of thousands of model runs to converge, and thus using a fast and robust forward model is essential to keep the calculation efficient. To reach this goal, an upwind coupled finite difference method is employed

  4. Simultaneous analyses and applications of multiple fluorobenzoate and halide tracers in hydrologic studies

    NASA Astrophysics Data System (ADS)

    Hu, Qinhong; Moran, Jean E.

    2005-09-01

    An analytical method that employs ion chromatography has been developed to exploit the use of fluorobenzoic acids (FBAs) and halides more fully as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g. nitrate and sulphate). The usefulness of this analytical method is demonstrated in both field and laboratory tracer experiments. The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the USA - mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need - reveal several insights about tracer transport behaviour: (1) bromide and FBAs are not always transported conservatively; (2) the delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy; (3) use of iodine as a hydrologic tracer should take into account the different sorption behaviours of iodide and iodate and the possible conversion of iodine's initial chemical form; (4) the transport behaviour of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large-scale field tracer experiments.

  5. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  6. Studies of oxide anions

    NASA Astrophysics Data System (ADS)

    Castleman, A. W., Jr.

    1991-06-01

    Several metal and metal oxide anion sources were used to investigate the formation and reactivity of species of relevance to the AFGL program. A new class of reactions were identified between anions of the form H(x)M(y)O(z) for several metals including M=W, Ta, Ti, Mo, and HCl. The reactions have analogy to acid-base reactions. In another series of experiments, reactions of Al(n)(-), and these clusters bound with V and or Nb, with O2 were investigated. It was found that the Jellium model, though by no means a compendious concept, provides a good guide to the electronic structure of clusters and their general patterns of reactivity.

  7. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-01-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  8. Anion permselective membrane

    NASA Astrophysics Data System (ADS)

    Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

    1984-07-01

    Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

  9. Stratospheric Tracer Spectra.

    NASA Astrophysics Data System (ADS)

    Haynes, P. H.; Vanneste, J.

    2004-01-01

    The combined effects of advection and diffusion on the equilibrium spatial structure of a tracer whose spatial variation is maintained by a large-scale forcing are considered. Motivated by the lower stratosphere, the flow is taken to be large-scale, time-dependent, and purely horizontal but varying in the vertical, with the vertical shear much larger than horizontal velocity gradients. As a result, the ratio α between horizontal and vertical tracer scales is large. (For the lower stratospheric surf zone α has been shown to be about 250.) The diffusion parameterizes the mixing effects of small-scale processes.The three space dimensions and the large range between the forcing scale and the diffusive scale mean that direct numerical simulation would be prohibitively expensive for this problem. Instead, an ensemble approach is used that takes advantage of the separation between the large scale of the flow and the small scale of the tracer distribution. This approach, which has previously been used in theoretical investigations of two-dimensional flows, provides an efficient technique to derive statistical properties of the tracer distributions such as horizontal-wavenumber spectrum.First, the authors consider random-strain models in which the velocity gradient experienced by a fluid parcel is modeled by a random process. The results show the expected k-1 Batchelor spectrum at large scales, with a deviation from this form at a scale that is larger by a factor α than the diffusive scale found in the absence of vertical shear. This effect may be crudely captured by replacing the diffusivity κ by an “=uivalent diffusivity” α2κ, but the diffusive dissipation is then substantially overestimated, and the spectrum at large k is too steep. This may be attributed to the failure of the equivalent diffusivity to capture the variability of the vertical shear.The technique is then applied to lower-stratospheric velocity fields. For realistic values of the diffusivity κ

  10. Analysis of radiolabelled thiocyanate tracer in oil field brines

    NASA Astrophysics Data System (ADS)

    Bjørnstad, T.; Brendsdal, E.; Michelsen, O. B.; Rogde, S. A.

    1990-12-01

    Thiocyanate (SCN -) labelled with 14C or 35S is applicable for the tracing of the water flow in water-driven oil production. This work describes two improved methods for increasing the concentration of S 14CN - with sample sizes up to 1000 ml of sampled brine. The radioactivity detection is carried out by low-background liquid scintillation counting using standard-size counting vials of 20 ml. The first method is based on solvent extraction: two extraction/strip steps reduce the volume by the required factor of 100 down to 10 ml. The extraction agent is 0.5M tri-isooctylamine (TiOA) in Solvesso-150 and the stripping agent is 5M NH 3. A chemical yield of 70-75%, a somewhat unfavourable quenching factor and a moderate reproducibility lead to a detection limit LD of 0.04 Bq/1. The second method is based on anion exchange. 1000 ml tracer-containing brine may be loaded onto 6.1 ml of the anion-exchange resin AG1-x8 before significant breakthrough of the tracer. More than 98.4% is absorbed. By elution with 2.8M sodiumperchlorate, more than 99.5% of the absorbed tracer is concentrated in a sharp elution peak of 10 ml. With a total chemical yield of 98%, a lower quenching factor and higher reproducibility than for the solvent extraction method, an LD-value of 0.005 Bq/1 is obtained.

  11. Tracer testing for reservoir description

    SciTech Connect

    Brigham, W.E.; Abbaszadeh-Dehghani, M.

    1987-05-01

    When a reservoir is studied in detail for an EOR project, well-to-well tracers should be used as a tool to help understand the reservoir in a quantitative way. Tracers complement the more traditional reservoir evaluation tools. This paper discusses the concepts underlying tracer testing, the analysis methods used to produce quantitative results, and the meaning of these results in terms of conceptual picture of the reservoir. Some of the limitations of these analysis methods are discussed, along with ongoing research on tracer flow.

  12. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1980-01-01

    The efforts on the synthesis of polymer anion redox membranes were mainly concentrated in two areas, membrane development and membrane fabrication. Membrane development covered the preparation and evaluation of experimental membranes systems with improved resistance stability and/or lower permeability. Membrane fabrication covered the laboratory scale production of prime candidate membranes in quantities of up to two hundred and sizes up to 18 inches x 18 inches (46 cm x 46 cm). These small (10 in x 11 in) and medium sized membranes were mainly for assembly into multicell units. Improvements in processing procedures and techniques for preparing such membrane sets lifted yields to over 90 percent.

  13. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Hodgdon, R. B.; Waite, W. A.

    1982-01-01

    The synthesis and fabrication of polymeric anion permselective membranes for redox systems are discussed. Variations of the prime candidate anion membrane formulation to achieve better resistance and/or lower permeability were explored. Processing parameters were evaluated to lower cost and fabricate larger sizes. The processing techniques to produce more membranes per batch were successfully integrated with the fabrication of larger membranes. Membranes of about 107 cm x 51 cm were made in excellent yield. Several measurements were made on the larger sample membranes. Among the data developed were water transport and transference numbers for these prime candidate membranes at 20 C. Other work done on this system included characterization of a number of specimens of candidate membranes which had been returned after service lives of up to sixteen months. Work with new polymer constituents, with new N.P.'s, catalysts and backing fabrics is discussed. Some work was also done to evaluate other proportions of the ingredients of the prime candidate system. The adoption of a flow selectivity test at elevated temperature was explored.

  14. Pseudorotation in fullerene anions

    NASA Astrophysics Data System (ADS)

    Dunn, Janette L.; Hands, Ian D.; Bates, Colin A.

    2007-07-01

    Jahn-Teller (JT) problems are often characterised by an adiabatic potential energy surface (APES) containing either a set of isoenergetic wells or a trough of equivalent-energy points, which may be warped by higher-order coupling terms or anisotropic effects. In all three cases, the JT effect will be dynamic. Either tunnelling between the wells or rotation (of a distortion) around the trough will restore the original symmetry of the system. This motion is referred to as pseudorotation. It should be possible to observe a JT system in a distorted geometry if measurements are made on a sufficiently short timescale. In various cubic systems, this timescale has been calculated to be the order of picoseconds. Such timescales are accessible using modern methods of ultrafast spectroscopy. Measurements of pseudorotation rates can lead to important information on the strength and nature of the JT coupling present. We will present analytical calculations that allow the rate of pseudorotation to be determined in terms of the vibronic coupling parameters. We will show how these results can be applied to E ⊗ e systems and then to the more complicated system applicable to C60- anions. This is of particular interest because of the high icosahedral symmetry of fullerene ions and also because of the many potential uses of materials containing these ions. We conclude by outlining experiments that should be capable of measuring pseudorotation in C 60 anions.

  15. Dynamic chemistry of anion recognition

    SciTech Connect

    Custelcean, Radu

    2012-01-01

    In the past 40 years, anion recognition by synthetic receptors has grown into a rich and vibrant research topic, developing into a distinct branch of Supramolecular Chemistry. Traditional anion receptors comprise organic scaffolds functionalized with complementary binding groups that are assembled by multistep organic synthesis. Recently, a new approach to anion receptors has emerged, in which the host is dynamically self-assembled in the presence of the anionic guest, via reversible bond formation between functional building units. While coordination bonds were initially employed for the self-assembly of the anion hosts, more recent studies demonstrated that reversible covalent bonds can serve the same purpose. In both cases, due to their labile connections, the molecular constituents have the ability to assemble, dissociate, and recombine continuously, thereby creating a dynamic combinatorial library (DCL) of receptors. The anionic guests, through specific molecular recognition, may then amplify (express) the formation of a particular structure among all possible combinations (real or virtual) by shifting the equilibria involved towards the most optimal receptor. This approach is not limited to solution self-assembly, but is equally applicable to crystallization, where the fittest anion-binding crystal may be selected. Finally, the pros and cons of employing dynamic combinatorial chemistry (DCC) vs molecular design for developing anion receptors, and the implications of both approaches to selective anion separations, will be discussed.

  16. Simultaneous Analyses and Applications of Multiple Fluorobenzoate and Halide Tracers in Hydrologic Studies

    SciTech Connect

    Hu, Q; Moran, J E

    2004-01-22

    An analytical method that employs ion chromatography has been developed to more fully exploit the use of fluorobenzoic acids (FBAs) and halides as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g., nitrate and sulfate). The usefulness of this ion chromatographic (IC) analytical method is demonstrated in both field and laboratory tracer experiments. Field experiments in unsaturated tuff featuring fractures or a fault show that this efficient and cost-effective method helps achieve the objectives of tracer studies that use multiple FBAs and/or diffusivity tracers (simultaneous use of one or more FBA and halide). The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the United States--mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need--reveal several insights about tracer transport behavior: (1) Bromide and FBAs are not always transported conservatively. (2) The delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy. (3) Any use of iodine as a hydrologic tracer should take into account the different sorption behaviors of iodide and iodate and the possible conversion of iodine's initial chemical form. (4) The transport behavior of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large-scale field tracer experiments.

  17. Organic Anion Transporting Polypeptides

    PubMed Central

    Stieger, Bruno; Hagenbuch, Bruno

    2013-01-01

    Organic anion transporting polypeptides or OATPs are central transporters in the disposition of drugs and other xenobiotics. In addition, they mediate transport of a wide variety of endogenous substrates. The critical role of OATPs in drug disposition has spurred research both in academia and in the pharmaceutical industry. Translational aspects with clinical questions are the focus in academia, while the pharmaceutical industry tries to define and understand the role these transporters play in pharmacotherapy. The present overview summarizes our knowledge on the interaction of food constituents with OATPs, and on the OATP transport mechanisms. Further, it gives an update on the available information on the structure-function relationship of the OATPs, and finally, covers the transcriptional and posttranscriptional regulation of OATPs. PMID:24745984

  18. Anion permselective membrane

    NASA Technical Reports Server (NTRS)

    Alexander, S.; Hodgdon, R. B.

    1977-01-01

    The objective of NAS 3-20108 was the development and evaluation of improved anion selective membranes useful as efficient separators in a redox power storage cell system being constructed. The program was divided into three parts, (a) optimization of the selected candidate membrane systems, (b) investigation of alternative membrane/polymer systems, and (c) characterization of candidate membranes. The major synthesis effort was aimed at improving and optimizing as far as possible each candidate system with respect to three critical membrane properties essential for good redox cell performance. Substantial improvements were made in 5 candidate membrane systems. The critical synthesis variables of cross-link density, monomer ratio, and solvent composition were examined over a wide range. In addition, eight alternative polymer systems were investigated, two of which attained candidate status. Three other alternatives showed potential but required further research and development. Each candidate system was optimized for selectivity.

  19. Tracer dating and ocean ventilation

    SciTech Connect

    Thiele, G.; Sarmiento, J.L. )

    1990-06-15

    The interpretation of transient tracer observations depends on difficult to obtain information on the evolution in time of the tracer boundary conditions and interior distributions. Recent studies have attempted to circumvent this problem by making use of a derived quantity, age, based on the simultaneous distribution of two complementary tracers, such as tritium and its daughter, helium 3. The age is defined with reference to the surface such that the boundary condition takes on a constant value of zero. The authors use a two-dimensional model to explore the circumstances under which such a combination of conservation equations for two complementary tracers can lead to a cancellation of the time derivative terms. An interesting aspect of this approach is that mixing can serve as a source or sink of tracer based age. The authors define an idealized ventilation age tracer that is conservative with respect to mixing, and they explore how its behavior compares with that of the tracer-based ages over a range of advective and diffusive parameters.

  20. Tracer airflow measurement system (TRAMS)

    DOEpatents

    Wang, Duo

    2007-04-24

    A method and apparatus for measuring fluid flow in a duct is disclosed. The invention uses a novel high velocity tracer injector system, an optional insertable folding mixing fan for homogenizing the tracer within the duct bulk fluid flow, and a perforated hose sampling system. A preferred embodiment uses CO.sub.2 as a tracer gas for measuring air flow in commercial and/or residential ducts. In extant commercial buildings, ducts not readily accessible by hanging ceilings may be drilled with readily plugged small diameter holes to allow for injection, optional mixing where desired using a novel insertable foldable mixing fan, and sampling hose.

  1. Chemical Modeling of Cometary Anions

    NASA Astrophysics Data System (ADS)

    Cordiner, Martin; Charnley, S. B.

    2009-09-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of 1P/Halley. The anions O-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not previously been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydrodynamical model of Rodgers & Charnley (2002), we investigate the role of the hydrocarbon and nitrile anions Cn-, CnH- and CnN- in the coma. We calculate the effects of these anions on the charge balance and examine their impact on cometary coma chemistry. References: Chaizy, P. et al. 1991, Nature, 349, 393 Rodgers, S.D. & Charnley, S.B. 2002, MNRAS, 330, 660

  2. Glomerular anionic site distribution in nonproteinuric rats. A computer-assisted morphometric analysis.

    PubMed

    Pilia, P A; Swain, R P; Williams, A V; Loadholt, C B; Ainsworth, S K

    1985-12-01

    The cationic ultrastructural tracer polyethyleneimine (PEI: pI approximately equal to 11.0), binds electrophysically to uniformly spaced discrete electron-dense anionic sites present in the laminae rarae of the rat glomerular basement membrane (GBM), mesangial reflections of the GBM, Bowman's capsule, and tubular basement membranes when administered intravenously. Computer-assisted morphometric analysis of glomerular anionic sites reveals that the maximum concentration of stainable lamina rara externa (lre) sites (21/10,000 A GBM) occurs 60 minutes after PEI injection with a site-site interspacing of 460 A. Lamina rara interna (lri) sites similarly demonstrate a maximum concentration (20/10,000 A GBM) at 60 minutes with a periodicity of 497 A. The concentration and distribution of anionic sites within the lri was irregular in pattern and markedly decreased in number, while the lre possesses an electrical field that is highly regular at all time intervals analyzed (15, 30, 60, 120, 180, 240, and 300 minutes). Immersion and perfusion of renal tissue with PEI reveals additional heavy staining of the epithelial and endothelial cell sialoprotein coatings. PEI appears to bind to glomerular anionic sites reversibly: ie, between 60 and 180 minutes the concentration of stained sites decreases. At 300 minutes, the interspacing once again approaches the 60-minute concentration. This suggests a dynamic turnover or dissociation followed by a reassociation of glomerular negatively charged PEI binding sites. In contrast, morphometric analysis of anionic sites stained with lysozyme and protamine sulfate reveals interspacings of 642 A and 585 A, respectively; in addition, these tracers produce major glomerular ultrastructural alterations and induce transient proteinuria. PEI does not induce proteinuria in rats, nor does it produce glomerular morphologic alterations when ten times the tracer dosage is administered intravenously. These findings indicate that the choice of

  3. Redesigning TRACER trial after TRITON.

    PubMed

    Serebruany, Victor L

    2015-10-15

    Designing of smart clinical trials is critical for regulatory approval and future drug utilization. Importantly, trial design should be reconsidered if the interim analyses suggest unexpected harm, or conflicting results were yielded from the other trials within the same therapeutic area. With regard to antiplatelet agents, the perfect example is redesigning of the ongoing PRoFESS trial by eliminating aspirin from clopidogrel arm after the earlier MATCH trial results became available. The goal was to aseess the unchanged TRACER trial design in light of the evidence yielded from the earlier completed TRITON trial. TRACER was designed as a triple versus dual antiplatelet trial in NSTEMI patients with no previous long-term outcome data supporting such aggressive strategy. TRITON data represented dual versus dual antiplatelet therapy, and became available before TRACER enrollment starts revealing prasugrel front-loaded early vascular benefit predominantly in STEMI patients with the growing over time bleeding and cancer risks. Moreover, large prasugrel NSTEMI TRITON cohort exhibited trend towards excess mortality in experimental arm warning against aggressive TRACER design. The long-term TRITON results in general, and especially in the NSTEMI patients challenge unchanged TRACER trial design. Applying dual, rather than triple antiplatelet therapy protocol modification should be considered in TRACER to minimize bleeding, cancer, and non-cardiovascular death risks. PMID:26126053

  4. Tracer Verification of Trajectory Models.

    NASA Astrophysics Data System (ADS)

    Haagenson, Philip L.; Kuo, Ying-Hwa; Syumanich, Marina; Seaman, Nelson L.

    1987-03-01

    Perfluorocarbon tracer data collected during the Cross Appalachian Tracer Experiment (CAPTEX '83) are used to determine the accuracy of three trajectory models: an isentropic, an isobaric, and a dimensional sigma model. The root-mean-square separation between model trajectories and trajectories derived from the surface tracer concentration is used to evaluate the models and assess the validity of isobaric, isentropic, isosigma, and mean transport vector assumptions. The root-mean-square data suggest that wind flow corresponding approximately to the low to middle boundary layer is the most appropriate for simulating the transport of boundary layer pollutants, and that the isentropic and isosigma transport assumptions are more realistic than the isobaric assumption, The results also indicate that synoptic type and the diurnal variation of mixing and wind shell within the boundary layer can affect the magnitude of root-mean-square separation between tracer trajectory and transport model trajectories. The uncertainty of the trajectory error suggested by the root-mean- square separation is approximately 50 km. Comparison of the tracer study with a theoretical study suggests that surface tracer data are useful for quantifying the magnitude of error in trajectory model calculations of boundary layer transport.

  5. Identification and characterization of conservative organic tracers for use as hydrologic tracers for the Yucca Mountain site characterization study. Progress report, October 1, 1994--December 31, 1994

    SciTech Connect

    Stetzenbach, K.; Farnham, I.

    1994-12-31

    The bromide anion has been used extensively as a tracer for mapping the flow of groundwater. It has proven to be both a safe and reliable groundwater tracer. The goal in this study is to find several tracing compounds with characteristics similar to the bromide anion to be used in multiple well tracing tests. Four groups of fluorinated organic acids were selected as candidates for groundwater tracers. These groups include fluorinated benzoic acids (FBA), fluorinated salicylic acids (FSA), fluorinated toluic acids (FTA), and fluorinated cinnamic acids (FCA). These compounds have been shown to move readily with the flow of water and do not adsorb to soil. They are also non-toxic. In this study, the retention of the fluorinated organic acids on to a soil column is compared to that of the bromide ion. The time required for the elution of each analyte from the soil column is measured using a UV-Vis detector. The soils consist of the light, medium, and dark tuffs used in the batch study. The work performed during this quarter consists of the continuation of the batch studies for the fluorinated benzoic acids and column studies for several potential tracer compounds.

  6. Anion Transport with Chalcogen Bonds.

    PubMed

    Benz, Sebastian; Macchione, Mariano; Verolet, Quentin; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-07-27

    In this report, we introduce synthetic anion transporters that operate with chalcogen bonds. Electron-deficient dithieno[3,2-b;2',3'-d]thiophenes (DTTs) are identified as ideal to bind anions in the focal point of the σ holes on the cofacial endocyclic sulfur atoms. Anion binding in solution and anion transport across lipid bilayers are found to increase with the depth of the σ holes of the DTT anionophores. These results introduce DTTs and related architectures as a privileged motif to engineer chalcogen bonds into functional systems, complementary in scope to classics such as 2,2'-bipyrroles or 2,2'-bipyridines that operate with hydrogen bonds and lone pairs, respectively. PMID:27433964

  7. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  8. Bound anionic states of adenine

    SciTech Connect

    Haranczyk, Maciej; Gutowski, Maciej S; Li, Xiang; Bowen, Kit H

    2007-03-20

    Anionic states of nucleic acid bases are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated nucleic acid base parent anions probed only dipole-bound states, which are not present in condensed phase environments, but did not observe valence anionic states, which for purine bases, are thought to be adiabatically unbound. Contrary to this expectation, we have demonstrated that some thus far ignored tautomers of adenine, which result from enamine-imine transformations, support valence anionic states with electron vertical detachment energies as large as 2.2 eV, and at least one of these anionic tautomers is adiabatically bound. Moreover, we predict that the new anionic tautomers should also dominate in solutions and should be characterized by larger values of electron vertical detachment energy than the canonical valence anion. All of the new-found anionic tautomers might be formed in the course of dissociative electron attachment followed by a hydrogen atom attachment to a carbon atom, and they might affect the structure and properties of DNA and RNA exposed to low-energy electrons. The discovery of these valence anionic states of adenine was facilitated by the development of: (i) a new experimental method for preparing parent anions of nucleic acid bases for photoelectron experiments, and (ii) a new combinatorial/ quantum chemical approach for identification of the most stable tautomers of organic molecules. The computational portion of this work was supported by the: (i) Polish State Committee for Scientific Research (KBN) Grants: DS/8000-4-0140-7 (M.G.) and N204 127 31/2963 (M.H.), (ii) European Social Funds (EFS) ZPORR/2.22/II/2.6/ARP/U/2/05 (M.H.), and (iii) US DOE Office of Biological and Environmental Research, Low Dose Radiation Research Program (M.G.). M.H. holds the Foundation for Polish Science (FNP) award for young scientists. The calculations were performed at the Academic

  9. Ambident reactivities of pyridone anions.

    PubMed

    Breugst, Martin; Mayr, Herbert

    2010-11-01

    The kinetics of the reactions of the ambident 2- and 4-pyridone anions with benzhydrylium ions (diarylcarbenium ions) and structurally related Michael acceptors have been studied in DMSO, CH(3)CN, and water. No significant changes of the rate constants were found when the counterion was varied (Li(+), K(+), NBu(4)(+)) or the solvent was changed from DMSO to CH(3)CN, whereas a large decrease of nucleophilicity was observed in aqueous solution. The second-order rate constants (log k(2)) correlated linearly with the electrophilicity parameters E of the electrophiles according to the correlation log k(2) = s(N + E) (Angew. Chem., Int. Ed. Engl. 1994, 33, 938-957), allowing us to determine the nucleophilicity parameters N and s for the pyridone anions. The reactions of the 2- and 4-pyridone anions with stabilized amino-substituted benzhydrylium ions and Michael acceptors are reversible and yield the thermodynamically more stable N-substituted pyridones exclusively. In contrast, highly reactive benzhydrylium ions (4,4'-dimethylbenzhydrylium ion), which react with diffusion control, give mixtures arising from N- and O-attack with the 2-pyridone anion and only O-substituted products with the 4-pyridone anion. For some reactions, rate and equilibrium constants were determined in DMSO, which showed that the 2-pyridone anion is a 2-4 times stronger nucleophile, but a 100 times stronger Lewis base than the 4-pyridone anion. Quantum chemical calculations at MP2/6-311+G(2d,p) level of theory showed that N-attack is thermodynamically favored over O-attack, but the attack at oxygen is intrinsically favored. Marcus theory was employed to develop a consistent scheme which rationalizes the manifold of regioselectivities previously reported for the reactions of these anions with electrophiles. In particular, Kornblum's rationalization of the silver ion effect, one of the main pillars of the hard and soft acid/base concept of ambident reactivity, has been revised. Ag(+) does not

  10. Hydrogen in anion vacancies of semiconductors

    SciTech Connect

    Du, Mao-Hua; Singh, David J

    2009-01-01

    Density functional calculations show that, depending on the anion size, hydrogen in anion vacancies of various II-VI semiconductors can be either two-fold or four-fold coordinated, and has either amphoteric or shallow donor character. In general, the multi-coordination of hydrogen in an anion vacancy is the indication of an anionic H, H { ion, in the relatively ionic environment. In more covalent semiconductors, H would form a single cation-H bond in the anion vacancy.

  11. Results of Chemical Analyses for Alcove 8/Niche 3 Tracer Studies

    SciTech Connect

    Daniels, Jeanette

    2006-02-23

    This is the final report detailing the analyses performed under ORD-FY04-011 "Chemical Analyses for Alcove 8/Niche 3 Tracer Studies." The work was performed under the University and Community College System of Nevada (UCCSN) and the Department of Energy (DOE) Cooperative Agreement Number DE-FC28-04RW12232. This task provided method development and analytical support for the Alcove 8/Niche 3 Tracer Studies in the Exploratory Studies Facility (ESF). Concentrations of tracers, as well as major anions and cations, were reported for samples provided by Lawrence Berkeley National Laboratory (LBNL) and the US Geological Survey (USGS). Samples were analyzed using High Performance Liquid Chromatography (HPLC) and Ion Chromatography (IC). Samples were analyzed and controlled according to Implementing Procedures (IP's) written and approved in accordance with the Office of Civilian Radioactive Waste Management (OCRWM) approved Nevada System of Higher Education (NSHE) Quality Assurance Program.

  12. Pu Anion Exchange Process Intensification

    SciTech Connect

    Taylor-Pashow, K.

    2015-10-08

    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  13. Tracer-monitored flow titrations.

    PubMed

    Sasaki, Milton K; Rocha, Diogo L; Rocha, Fábio R P; Zagatto, Elias A G

    2016-01-01

    The feasibility of implementing tracer-monitored titrations in a flow system is demonstrated. A dye tracer is used to estimate the instant sample and titrant volumetric fractions without the need for volume, mass or peak width measurements. The approach was applied to spectrophotometric flow titrations involving variations of sample and titrant flow-rates (i.e. triangle programmed technique) or concentration gradients established along the sample zone (i.e. flow injection system). Both strategies required simultaneous monitoring of two absorbing species, namely the titration indicator and the dye tracer. Mixing conditions were improved by placing a chamber with mechanical stirring in the analytical path aiming at to minimize diffusional effects. Unlike most of flow-based titrations, the innovation is considered as a true titration, as it does not require a calibration curve thus complying with IUPAC definition. As an application, acidity evaluation in vinegars involving titration with sodium hydroxide was selected. Phenolphthalein and brilliant blue FCF were used as indicator and dye tracer, respectively. Effects of sample volume, titrand/titrant concentrations and flow rates were investigated aiming at improved accuracy and precision. Results were reliable and in agreement with those obtained by a reference titration procedure. PMID:26703261

  14. Mobility of Metal Tracers in Unsaturated Tuffs of Busted Butte, Nevada

    SciTech Connect

    A.R. Groffman; H.J. Turin; J. Roach; C.L. Jones; W.E. Soll

    2003-09-20

    A complex tracer mixture was injected continuously for over two years into a 10 m x 10 m x 7 m block of unsaturated tuff as part of the Busted Butte unsaturated-zone tracer test at Yucca Mountain. The test was designed to measure tracer transport within the Topopah Springs and Calico Hills tuffs, units that occur between the potential high-level nuclear waste repository at Yucca Mountain and the water table below. The mixture included nonreactive (Br, I, and fluorinated benzoic acids (FBAs)) and reactive tracers (Li, Ce, Sm, Ni, Co, and Mn). Bromide, I, FBAs, and Li were detected during the test on absorbent pads emplaced in a series of solute collection boreholes located beneath the injectors but the more strongly sorbing metals did not reach the collection boreholes during this period. To determine the distribution and mobility of these metals, tracer constituents were extracted from tuff samples collected during overcoring and mineback of the test block. Tracers were extracted from the tuff samples by leaching with a 5% nitric acid solution for metals and a bicarbonate-carbonate buffer for anions. Results from the overcore sample suite show that metals have migrated through the tuff in the region adjacent to and immediately below the tracer injectors. Consistent with laboratory sorption measurements and observed breakthrough in the collection boreholes, rock analyses showed that Li is the most mobile of the metals. Co and Ni behave similarly, traveling tens of cm from the injection sites, while Sm and Ce moved far less, possibly due to precipitation reactions in addition to sorption. Determination of Mn transport is complicated by high background concentrations in the tuff; additional background samples are currently being evaluated. As expected, the rock analyses show that the nonreactive tracers Br and FBAs have moved beyond the overcore region, corroborating results from collection boreholes.

  15. Anion binding in biological systems

    NASA Astrophysics Data System (ADS)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  16. Hydrograph separation using hydrochemical tracers in the Makanya catchment, Tanzania

    NASA Astrophysics Data System (ADS)

    Mul, Marloes L.; Mutiibwa, Robert K.; Uhlenbrook, Stefan; Savenije, Hubert H. G.

    Hydrochemical tracers were used to separate and quantify different runoff components in the semi-arid Makanya catchment in the South Pare Mountains of Tanzania. One flood event was investigated during the rainy season of October-December 2005 and analysed for electrical conductivity, dissolved silica and major anions and cations. The event on 9 November 2005 showed two peaks, each originating from one of two sub-catchments, upper-Vudee and Ndolwa, each with a distinct water quality signature. Hydrograph separation indicated that the two peaks in the hydrograph originated from a delay in response between the two catchments. The hydrograph separation indicated that, for this event, over 95% of the discharge could be attributed to sub-surface runoff, while the remainder was due to faster surface runoff processes. The dominance of sub-surface processes was also indicated by the lack of suspended sediments in the samples, which is a clear indication that no surface runoff took place.

  17. Multiple-tracer gas analyzer

    SciTech Connect

    Uhl, J.E.

    1982-01-01

    A multi-gas tracer system has been designed, built, and used on an explosively fractured oil shale rubble bed. This paper deals exclusively with the hardware, software, and overall operation of the tracer system. This system is a field portable, self-contained unit, which utilizes a mass spectrometer for gas analysis. The unit has a 20 channel sample port capability and is controlled by a desk top computer. The system is configured to provide a dynamic sensitivity range of up to six orders of magnitude. A roots blower is manifolded to the unit to provide continuous flow in all sample lines. The continuous flow process allows representative samples as well as decreasing the time between each measurement. Typical multiplex cycle time to evaluate four unique gases is approximately 12 seconds.

  18. Comparative mobility of sulfonamides and bromide tracer in three soils

    USGS Publications Warehouse

    Kurwadkar, S.T.; Adams, C.D.; Meyer, M.T.; Kolpin, D.W.

    2011-01-01

    In animal agriculture, sulfonamides are one of the routinely used groups of antimicrobials for therapeutic and sub-therapeutic purposes. It is observed that, the animals when administered the antimicrobials, often do not completely metabolize them; and excrete the partially metabolized forms into the environment. Due to the continued use of antimicrobials and disposal of untreated waste, widespread occurrence of partially metabolized antimicrobials in aquatic and terrestrial environments has been reported in various scientific journals. In this research, the mobility of two sulfonamides - sulfamethazine (SMN), sulfathiazole (STZ) and a conservative bromide tracer was investigated in three soils collected from regions in the United States with large number of concentrated animal-feed operations. Results of a series of column studies indicate that the mobility of these two sulfonamides was dependent on pH, soil charge density, and contact time. At low pH and high charge density, substantial retention of sulfonamides was observed in all three soils investigated, due to the increased fraction of cationic and neutral forms of the sulfonamides. Conversely, enhanced mobility was observed at high pH, where the sulfonamides are predominantly in the anionic form. The results indicate that when both SMN and STZ are predominantly in anionic forms, their mobility approximates the mobility of a conservative bromide tracer. This observation is consistent for the mobility of both SMN and STZ individually, and also in the presence of several other antimicrobials in all three soils investigated. Higher contact time indicates lower mobility due to increased interaction with soil material. ?? 2011.

  19. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, Gordon D.; Marsh, S. Fredric; Bartsch, Richard A.

    1997-01-01

    Anion exchange resins including at least two positively charged sites and a ell-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  20. Ion exchange polymers for anion separations

    DOEpatents

    Jarvinen, G.D.; Marsh, S.F.; Bartsch, R.A.

    1997-09-23

    Anion exchange resins including at least two positively charged sites and a well-defined spacing between the positive sites are provided together with a process of removing anions or anionic metal complexes from aqueous solutions by use of such resins. The resins can be substituted poly(vinylpyridine) and substituted polystyrene.

  1. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  2. Anion Solvation in Carbonate Electrolytes

    SciTech Connect

    Zhang, Zhengcheng

    2015-11-16

    With the correlation between Li+ solvation and interphasial chemistry on anodes firmly established in Li-ion batteries, the effect of cation–solvent interaction has gone beyond bulk thermodynamic and transport properties and become an essential element that determines the reversibility of electrochemistry and kinetics of Li-ion intercalation chemistries. As of now, most studies are dedicated to the solvation of Li+, and the solvation of anions in carbonate-based electrolytes and its possible effect on the electrochemical stability of such electrolytes remains little understood. As a mirror effort to prior Li+ solvation studies, this work focuses on the interactions between carbonate-based solvents and two anions (hexafluorophosphate, PF6–, and tetrafluoroborate, BF4–) that are most frequently used in Li-ion batteries. The possible correlation between such interaction and the interphasial chemistry on cathode surface is also explored.

  3. Aza compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  4. Aza compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  5. Transient Anion States of Biomolecules

    NASA Astrophysics Data System (ADS)

    Varella, Marcio

    2012-10-01

    Much of the interest on electron interactions with biomolecules is related to radiation damage [Gohlke and Illenberger, Europhys. News 33, 207 (2002)]. The high energy photons employed in radiology and radiotherapy generate a large number of fast electrons in living cells. These electrons thermalize in a picosecond scale, eventually forming dissociative matestable anions with water and biomolecules. In this work, we employ the parallel version of Schwinger Multichannel Method with Pseudopotentials [Bettega et al., Phys. Rev. A 47, 1111 (1993); Santos et al., J. Phys. Chem. 136, 084307 (2012)] to investigate transient anion states of protein and nucleic acid precursors. We address glycine in both neutral and zwitterionic forms, as well as glycine-water clusters and disulfide bonds. The interest on the two forms of glycine (and other amino acids) relies on the fact that only the neutral form is stable in the gas phase, while the zwitterion is more stable in solution, pointing out limitations of standard gas-phase studies. Electron attachment to disulfide bonds also has potential impact on protein stability. Finally we address transient anion states of substituted uracil molecules in the gas phase. [4pt] In collaboration with M. H. F. Bettega, S. d'A. Sanchez, R. F. da Costa, M. A. P. Lima, J. S. dos Santos, and F. Kossoski.

  6. Petroleum characterization by perfluorocarbon tracers

    SciTech Connect

    Senum, G.I.; Fajer, R.W. ); Harris, B.R. Jr. ); DeRose, W.E. ); Ottaviani, W.L. )

    1992-02-01

    Perfluorocarbon tracers (PFTs), a class of six compounds, were used to help characterize the Shallow Oil Zone (SOZ) reservoir at the Naval Petroleum Reserve in California (NPRC) at Elk Hills. The SOZ reservoir is undergoing a pilot gas injection program to assess the technical feasibility and economic viability of injecting gas into the SOZ for improved oil recovery. PFTs were utilized in the pilot gas injection to qualitatively assess the extent of the pilot gas injection so as to determine the degree of gas containment within the SOZ reservoir.

  7. Effects of submesoscale turbulence on ocean tracers

    NASA Astrophysics Data System (ADS)

    Smith, Katherine M.; Hamlington, Peter E.; Fox-Kemper, Baylor

    2016-01-01

    Ocean tracers such as carbon dioxide, nutrients, plankton, and oil advect, diffuse, and react primarily in the oceanic mixed layer where air-sea gas exchange occurs and light is plentiful for photosynthesis. There can be substantial heterogeneity in the spatial distributions of these tracers due to turbulent stirring, particularly in the submesoscale range where partly geostrophic fronts and eddies and small-scale three-dimensional turbulence are simultaneously active. In this study, a large eddy simulation spanning horizontal scales from 20 km down to 5 m is used to examine the effects of multiscale turbulent mixing on nonreactive passive ocean tracers from interior and sea-surface sources. The simulation includes the effects of both wave-driven Langmuir turbulence and submesoscale eddies, and tracers with different initial and boundary conditions are examined in order to understand the respective impacts of small-scale and submesoscale motions on tracer transport. Tracer properties are characterized using spatial fields and statistics, multiscale fluxes, and spectra, and the results detail how tracer mixing depends on air-sea tracer flux rate, tracer release depth, and flow regime. Although vertical fluxes of buoyancy by submesoscale eddies compete with mixing by Langmuir turbulence, vertical fluxes of tracers are often dominated by Langmuir turbulence, particularly for tracers that are released near the mixed-layer base or that dissolve rapidly through the surface, even in regions with pronounced submesoscale activity. Early in the evolution of some tracers, negative eddy diffusivities occur co-located with regions of negative potential vorticity, suggesting that symmetric instabilities or other submesoscale phenomenon may act to oppose turbulent mixing.

  8. TRACER-TEST PLANNING USING THE EFFICIENT HYDROLOGIC TRACER-TEST DESIGN (EHTD) PROGRAM 2003

    EPA Science Inventory

    Hydrological tracer testing is the most reliable diagnostic technique available for establishing flow trajectories and hydrologic connections and for determining basic hydraulic and geometric parameters necessary for establishing operative solute-transport processes. Tracer-test ...

  9. TRACER-TEST PLANNING USING THE EFFICIENT HYDROLOGIC TRACER-TEST DESIGN (EHTD) PROGRAM 2005

    EPA Science Inventory

    Hydrological tracer testing is the most reliable diagnostic technique available for establishing flow trajectories and hydrologic connections and for determining basic hydraulic and geometric parameters necessary for establishing operative solute-transport processes. Tracer-test ...

  10. Balloon tracer for atmospheric pollutants

    SciTech Connect

    Lichfield, E.W.; Ivey, M.D.; Zak, B.D.; Church, H.W.

    1985-01-01

    An operational prototype of the Balloon Tracer was developed and described. This prototype was designed to be capable of meeting all of the desired specifications for the Balloon Tracer. Its buoyancy adjustment subsystem is shown. Three Gilian instrument pumps operating in parallel provide a flow of about 12 litres per minute, depending upon backpressure. The miniature Klippard mechanical valves are actuated by a servo mechanism which only requires power when the state of the valves is being changed. The balloon itself for the operational prototype is just under 3 meters in diameter. A block diagram of the operational prototype payload measures ambient pressure, temperature, and humidity obtained from AIR which outputs its data in ASCII format. The vertical anemometer, which has a measured starting speed of under 2 cm/s, makes use of a Gill styrofoam propeller and a Spaulding Instruments rotation sendor. The command decoder is built around a chip developed originally for remote control television tuners. The command receiver operating on 13.8035 MHz was developed and built by Hock Engineering. The Argos transmitter is a Telonics platform transmitter terminal. The heart of the control system is an Intel 8052AH BASIC microcomputer with both random access and read only memory.

  11. Tracers of Past Ocean Circulation

    NASA Astrophysics Data System (ADS)

    Lynch-Stieglitz, J.

    2003-12-01

    Information about how the ocean circulated during the past is useful in understanding changes in ocean and atmospheric chemistry, changes in the fluxes of heat and freshwater between the ocean and atmosphere, and changes in global wind patterns. The circulation of surface waters in the ocean leaves an imprint on sea surface temperature, and is also inextricably linked to the patterns of oceanic productivity. Much valuable information about past ocean circulation has been inferred from reconstructions of surface ocean temperature and productivity, which are covered in separate chapters. Here the focus is on the geochemical tracers that are used to infer the flow patterns and mixing of subsurface water masses.Several decades ago it was realized that chemistry of the shells of benthic foraminifera (carbon isotope and Cd/Ca ratios) carried an imprint of the nutrient content of deep-water masses (Shackleton, 1977; Broecker, 1982; Boyle, 1981). This led rapidly to the recognition that the water masses in the Atlantic Ocean were arrayed differently during the last glacial maximum than they are today, and the hypothesis that the glacial arrangement reflected a diminished contribution of low-nutrient North Atlantic deep water (NADW) ( Curry and Lohmann, 1982; Boyle and Keigwin, 1982). More detailed spatial reconstructions indicated a shallow nutrient-depleted water mass overlying a more nutrient-rich water mass in the glacial Atlantic. These findings spurred advances not only in geochemistry but in oceanography and climatology, as workers in these fields attempted to simulate the inferred glacial circulation patterns and assess the vulnerability of the modern ocean circulation to changes such as observed for the last ice age.While the nutrient distributions in the glacial Atlantic Ocean were consistent with a diminished flow of NADW, they also could have reflected an increase in inflow from the South Atlantic and/or a shallower yet undiminished deep-water mass. Clearly

  12. Tracers for Characterizing Enhanced Geothermal Systems

    SciTech Connect

    Karen Wright; George Redden; Carl D. Palmer; Harry Rollins; Mark Stone; Mason Harrup; Laurence C. Hull

    2010-02-01

    Information about the times of thermal breakthrough and subsequent rates of thermal drawdown in enhanced geothermal systems (EGS) is necessary for reservoir management, designing fracture stimulation and well drilling programs, and forecasting economic return. Thermal breakthrough in heterogeneous porous media can be estimated using conservative tracers and assumptions about heat transfer rates; however, tracers that undergo temperature-dependent changes can provide more detailed information about the thermal profile along the flow path through the reservoir. To be effectively applied, the thermal reaction rates of such temperature sensitive traces must be well characterized for the range of conditions that exist in geothermal systems. Reactive tracers proposed in the literature include benzoic and carboxylic acids (Adams) and organic esters and amides (Robinson et al.); however, the practical temperature range over which these tracers can be applied (100-275°C) is somewhat limited. Further, for organic esters and amides, little is known about their sorption to the reservoir matrix and how such reactions impact data interpretation. Another approach involves tracers where the reference condition is internal to the tracer itself. Two examples are: 1) racemization of polymeric amino acids, and 2) mineral thermoluminescence. In these cases internal ratios of states are measured rather than extents of degradation and mass loss. Racemization of poly-L-lactic acid (for example) is temperature sensitive and therefore can be used as a temperature-recording tracer depending on the rates of racemization and stability of the amino acids. Heat-induced quenching of thermoluminescence of pre-irradiated LiF can also be used. To protect the tracers from alterations (extraneous reactions, dissolution) in geothermal environments we are encapsulating the tracers in core-shell colloidal structures that will subsequently be tested for their ability to be transported and to protect the

  13. USING TRACERS TO DESCRIBE NAPL HETEROGENEITY

    EPA Science Inventory

    Tracers are frequently used to estimate both the average travel time for water flow through the tracer swept volume and NAPL saturation. The same data can be used to develop a statistical distribution describing the hydraulic conductivity in the sept volume and a possible distri...

  14. Mobile Measurement of an Atmospheric Tracer

    SciTech Connect

    Milham, R.C.

    2001-03-09

    This paper describes a mobile analyzer for sulfur hexafluoride, an atmospheric tracer. A commercial instrument is used on-board a moving vehicle to measure tracer concentrations in the parts per trillion (ppt) range. This instrument provides rapid, in-the-field data at minimum cost.

  15. CROSS-APPALACHIAN TRACER EXPERIMENT (CAPTEX '83)

    EPA Science Inventory

    Scientists in the United States and Canada have collaborated on the Cross-Appalachian Tracer Experiment (CAPTEX '83) using the perfluorocarbon tracer to simulate the long-range transport of pollutants in the atmosphere. The experiments, conducted in September and October of 1983 ...

  16. Adsorption affinity of anions on metal oxyhydroxides

    NASA Astrophysics Data System (ADS)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.

    2013-03-01

    The dependences of anion (phosphate, carbonate, sulfate, chromate, oxalate, tartrate, and citrate) adsorption affinity anions from geometric characteristics, acid-base properties, and complex forming ability are generalized. It is shown that adsorption depends on the nature of both the anions and the ionic medium and adsorbent. It is established that anions are generally grouped into the following series of adsorption affinity reduction: PO{4/3-}, CO{3/2-} > C2O{4/2-}, C(OH)(CH2)2(COO){3/3-}, (CHOH)2(COO){2/2-} > CrO{4/2-} ≫ SO{4/2-}.

  17. Modeling of solute transport in snow using conservative tracers and artificial rain-on-snow experiments

    NASA Astrophysics Data System (ADS)

    Lee, Jeonghoon; Feng, Xiahong; Posmentier, Eric S.; Faiia, Anthony M.; Osterhuber, Randall; Kirchner, James W.

    2008-02-01

    We report a study of solute transport in snow, using artificial rain-on-snow experiments with conservative anions (F-, Br-, and SO42-). The tracers were mixed into tap water and sprayed onto the snow surface from two water supply tanks. The water flux out of the base of the snowpack was recorded, and discharge samples were collected and analyzed for the three tracers. The chemical concentration of tracers in the discharge was negatively associated with the water flux. The objectives of the experiment were to test whether the mobile-immobile model (MIM) with variable mobile-immobile water exchange coefficient can simulate both positive and negative concentration-discharge relationships in this and previous tracer experiments. By simulating our experimental data, we confirm that it is necessary for the exchange coefficient to increase with water velocity. In addition, we use the model to show that with a diurnal variation of clean water flux, a negative concentration-discharge relationship occurs when solutes are evenly distributed in the mobile and immobile fluids, while a positive relationship occurs when the solutes were present only in the immobile fluid near the surface. This result may help in explaining the complicated concentration-discharge relationships observed in catchments.

  18. Analysis of colloid and tracer breakthrough curves

    NASA Astrophysics Data System (ADS)

    Grindrod, Peter; Edwards, Mark S.; Higgo, Jenny J. W.; Williams, Geoffrey M.

    1996-02-01

    We consider the dispersion and elution of colloids and dissolved nonsorbing tracers within saturated heterogeneous porous media. Since flow path geometry in natural systems is often ill-characterized macroscopic (mean) flow rates and dispersion tensors are utilized in order to account for the sub-model scale microscopic fluctuations in media structure (and the consequent hydrodynamic profile). Even for tracer migration and dispersal this issue is far from settled. Here we consider how colloid and tracer migration phenomena can be treated consistently. Theoretical calculations for model flow geometries yield two quantitative predictions for the transport of free (not yet captured) colloids with reference to a non-sorbing dissolved tracer within the same medium: the average migration velocity of the free colloids is higher than that of the tracer; and that the ratio of the equivalent hydrodynamic dispersion rates of colloids and tracer is dependent only upon properties of the colloids and the porous medium, it is independent of pathlengths and fluid flux, once length scales are large enough. The first of these is well known, since even in simple flow paths free colloids must stay more centre stream. The second, if validated suggests how solute and colloid dispersion may be dealt with consistently in macroscopic migration models. This is crucial since dispersion is usually ill-characterized and unaddressed by the experimental literature. In this paper we present evidence based upon an existing Drigg field injection test for the validity of these predictions. We show that starting from experimental data the fitted dispersion rates of both colloids and non-sorbing tracers increase with the measured elution rates (obeying slightly different rules for tracers and colloids); and that the ratio of colloid and nonsorbing tracer elution rates, and the ratio of colloid and nonsorbing tracer dispersion rates may be dependent upon properties of the colloids and the medium (not

  19. Tripodal Receptors for Cation and Anion Sensors

    PubMed Central

    Kuswandi, Bambang; Nuriman; Verboom, Willem; Reinhoudt, David N.

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selective recognition and sensing of cations and anions. Examples on the relationship between structure and selectivity towards cations and anions are described. Furthermore, their applications as potentiometric ion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  20. Wanted: Scalable Tracers for Diffusion Measurements

    PubMed Central

    2015-01-01

    Scalable tracers are potentially a useful tool to examine diffusion mechanisms and to predict diffusion coefficients, particularly for hindered diffusion in complex, heterogeneous, or crowded systems. Scalable tracers are defined as a series of tracers varying in size but with the same shape, structure, surface chemistry, deformability, and diffusion mechanism. Both chemical homology and constant dynamics are required. In particular, branching must not vary with size, and there must be no transition between ordinary diffusion and reptation. Measurements using scalable tracers yield the mean diffusion coefficient as a function of size alone; measurements using nonscalable tracers yield the variation due to differences in the other properties. Candidate scalable tracers are discussed for two-dimensional (2D) diffusion in membranes and three-dimensional diffusion in aqueous solutions. Correlations to predict the mean diffusion coefficient of globular biomolecules from molecular mass are reviewed briefly. Specific suggestions for the 3D case include the use of synthetic dendrimers or random hyperbranched polymers instead of dextran and the use of core–shell quantum dots. Another useful tool would be a series of scalable tracers varying in deformability alone, prepared by varying the density of crosslinking in a polymer to make say “reinforced Ficoll” or “reinforced hyperbranched polyglycerol.” PMID:25319586

  1. Tracer motion in an active dumbbell fluid

    NASA Astrophysics Data System (ADS)

    Suma, Antonio; Cugliandolo, Leticia F.; Gonnella, Giuseppe

    2016-05-01

    The diffusion properties of spherical tracers coupled through a repulsive potential to a system of active dumbbells are analyzed. We model the dumbbells’ dynamics with Langevin equations and the activity with a self-propulsive force of constant magnitude directed along the main axis of the molecules. Two types of tracers are considered. Thermal tracers are coupled to the same bath as the dumbbells while athermal tracers are not; both interact repulsively with the dumbbells. We focus our attention on the intruders’ mean square displacement and how it compares to the one of the dumbbells. We show that the dynamics of thermal intruders, with mass similar to the one of the dumbbells, display the typical four time-lag regimes of the dumbbells’ mean square displacement. The thermal tracers’ late-time diffusion coefficient depends on their mass very weakly and it is close to the one of the dumbbells at low Péclet only. Athermal tracers only have ballistic and late-time diffusive regimes. The late time diffusion coefficients of athermal tracers and dumbbells have similar values at high Péclet number when their masses are of the same order, while at low Péclet number this coefficient gets close to the one of the dumbbells only when the tracers are several order of magnitude heavier than the dumbbells. We propose a generalization of the Enskog law for dilute hard disks, that describes the athermal tracers’ mean square displacement in the form of a scaling law in terms of their mass.

  2. Tracer design for magnetic particle imaging (invited)

    PubMed Central

    Ferguson, R. Matthew; Khandhar, Amit P.; Krishnan, Kannan M.

    2012-01-01

    Magnetic particle imaging (MPI) uses safe iron oxide nanoparticle tracers to offer fundamentally new capabilities for medical imaging, in applications as vascular imaging and ultra-sensitive cancer therapeutics. MPI is perhaps the first medical imaging platform to intrinsically exploit nanoscale material properties. MPI tracers contain magnetic nanoparticles whose tunable, size-dependent magnetic properties can be optimized by selecting a particular particle size and narrow size-distribution. In this paper we present experimental MPI measurements acquired using a homemade MPI magnetometer: a zero-dimensional MPI imaging system designed to characterize tracer performance by measuring the derivative of the time-varying tracer magnetization, M’(H(t)), at a driving frequency of 25 kHz. We show that MPI performance is optimized by selecting phase-pure magnetite tracers of a particular size and narrow size distribution; in this work, tracers with 20 nm median diameter, log-normal distribution shape parameter, σv, equal to 0.26, and hydrodynamic diameter equal to 30 nm showed the best performance. Furthermore, these optimized MPI tracers show 4 × greater signal intensity (measured at the third harmonic) and 20% better spatial resolution compared with commercial nanoparticles developed for MRI. PMID:22434939

  3. Using Tracer Technology to Characterize Contaminated Pipelines

    SciTech Connect

    Maresca, Joseph, W., Jr., Ph.D.; Bratton, Wesley, L., Ph.D., P.E.; Dickerson, Wilhelmina; Hales, Rochelle

    2005-12-30

    The Pipeline Characterization Using Tracers (PCUT) technique uses conservative and partitioning, reactive or other interactive tracers to remotely determine the amount of contaminant within a run of piping or ductwork. The PCUT system was motivated by a method that has been successfully used to characterize subsurface soil contaminants and is similar in operation to that of a gas chromatography column. By injecting a ?slug? of both conservative and partitioning tracers at one end (or section) of the piping and measuring the time history of the concentration of the tracers at the other end (or another section) of the pipe, the presence, location, and amount of contaminant within the pipe or duct can be determined. The tracers are transported along the pipe or duct by a gas flow field, typically air or nitrogen, which has a velocity that is slow enough so that the partitioning tracer has time to interact with the contaminant before the tracer slug completely passes over the contaminate region. PCUT not only identifies the presence of contamination, it also can locate the contamination along the pipeline and quantify the amount of residual. PCUT can be used in support of deactivation and decommissioning (D&D) of piping and ducts that may have been contaminated with hazardous chemicals such as chlorinated solvents, petroleum products, radioactive materials, or heavy metals, such as mercury.

  4. Gels based on anion recognition between triurea receptor and phosphate anion.

    PubMed

    Yang, Cuiling; Wu, Biao; Chen, Yongming; Zhang, Ke

    2015-04-01

    Anion recognition between the triurea receptor and phosphate anion is demonstrated as the cross-linkage to build supramolecular polymer gels for the first time. A novel multi-block copolymer (3) is designed to have functional triurea groups as cross-linking units along the polymer main chain. By virtue of anion coordination between the triurea receptor and phosphate anion with a binding mode of 2:1, supramolecular polymer gels are then prepared based on anion recognition using 3 as the building block. PMID:25694389

  5. Counterintuitive interaction of anions with benzene derivatives

    NASA Astrophysics Data System (ADS)

    Quiñonero, David; Garau, Carolina; Frontera, Antonio; Ballester, Pau; Costa, Antonio; Deyà, Pere M.

    2002-06-01

    Ab initio calculations were carried out on complexes between 1,3,5-trinitrobenzene (TNB) and anions, where the anion is positioned over the ring along the C3 axis. This study combines crystallographic and computational evidences to demonstrate an attractive interaction between the anion and the π-cloud of TNB. This interaction is rationalized based on the important role of the quadrupole moment of TNB and the anion-induced polarization. In addition, this study has been extended to 1,3,5-trifluorobenzene (TFB), which possesses a very small quadrupole moment. As a result, minimum energy complexes have been found between TFB and both anions and cations due to the stabilization obtained from the ion-induced polarization.

  6. Creating molecular macrocycles for anion recognition

    PubMed Central

    2016-01-01

    Summary The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures. PMID:27340452

  7. Picosecond dynamics of benzophenone anion solvation

    SciTech Connect

    Lin, Y.; Jonah, C.D. )

    1993-01-14

    The dynamics of benzophenone anion solvation in alcohols are studied by pulse-radiolysis techniques. The solvation process is characterized by the blue shift of the transient absorption spectrum of the anion and is faster for the smaller alcohols. The anion is solvated more slowly than the electron in the same solvent, but the solvation times of both are similar to [tau][sub 2], the solvent dielectric relaxation time. The familiar phenomenological two-state model of solvation was found to be inappropriate for describing the anion solvation process. A multistate process appears to be a more appropriate description. The authors modeled the kinetics of the spectral relaxation. In most cases, nearly quantitative agreement between the calculated and observed spectra is achieved. The characteristic relaxation times for the alcohol solvents around the anions were also reproduced. 50 refs., 8 figs., 3 tabs.

  8. Covalent Polymers Containing Discrete Heterocyclic Anion Receptors

    PubMed Central

    Rambo, Brett M.; Silver, Eric S.; Bielawski, Christopher W.; Sessler, Jonathan L.

    2010-01-01

    This chapter covers recent advances in the development of polymeric materials containing discrete heterocyclic anion receptors, and focuses on advances in anion binding and chemosensor chemistry. The development of polymers specific for anionic species is a relatively new and flourishing area of materials chemistry. The incorporation of heterocyclic receptors capable of complexing anions through non-covalent interactions (e.g., hydrogen bonding and electrostatic interactions) provides a route to not only sensitive but also selective polymer materials. Furthermore, these systems have been utilized in the development of polymers capable of extracting anionic species from aqueous environments. These latter materials may lead to advances in water purification and treatment of diseases resulting from surplus ions. PMID:20871791

  9. Dual-tracer receptor concentration imaging using tracers with different tissue delivery kinetics

    NASA Astrophysics Data System (ADS)

    Tichauer, Kenneth M.; Diop, Mamadou; Elliott, Jonathan T.; Samkoe, Kimberley S.; Hasan, Tayyaba; St. Lawrence, Keith; Pogue, Brian W.

    2014-03-01

    Simultaneous dynamic fluorescent imaging of a suitable untargeted tracer in conjunction with any molecular targeted fluorescent agent has been shown to be a powerful approach for quantifying cancer-specific cell surface receptors in vivo in the presence of non-specific uptake and tracer delivery variability. The identification of a "suitable" untargeted tracer (i.e., one having equivalent plasma and tissue delivery pharmacokinetics to the targeted tracer) for every targeted tracer, however, may not always be feasible or could require extensive testing. This work presents a "deconvolution" approach capable of correcting for plasma and tissue-delivery pharmacokinetic differences between tracers by quantifying dynamic differences in targeted and untargeted tracer uptake in a receptor-free tissue (one devoid of targeted molecular species) and correcting uptake in all other tissues accordingly. This deconvolution correction approach is evaluated in theoretical models and explored in an in vivo mouse xenograft model of human glioma. In the animal experiments, epidermal growth factor receptor (EGFR: a receptor known to be overexpressed in the investigated glioma cell line) was targeted using a fluorescent tracer with very different plasma pharmacokinetics than a second untargeted fluorescent tracer. Without correcting for these differences, the dual-tracer approach yielded substantially higher estimations of EGFR concentration in all tissues than expected; however, deconvolution correction was able to produce estimates that matched ex vivo validation.

  10. Anion conductance selectivity mechanism of the CFTR chloride channel.

    PubMed

    Linsdell, Paul

    2016-04-01

    All ion channels are able to discriminate between substrate ions to some extent, a process that involves specific interactions between permeant anions and the so-called selectivity filter within the channel pore. In the cystic fibrosis transmembrane conductance regulator (CFTR) anion-selective channel, both anion relative permeability and anion relative conductance are dependent on anion free energy of hydration--anions that are relatively easily dehydrated tend to show both high permeability and low conductance. In the present work, patch clamp recording was used to investigate the relative conductance of different anions in CFTR, and the effect of mutations within the channel pore. In constitutively-active E1371Q-CFTR channels, the anion conductance sequence was Cl(-) > NO3(-) > Br(-) > formate > SCN(-) > I(-). A mutation that disrupts anion binding in the inner vestibule of the pore (K95Q) disrupted anion conductance selectivity, such that anions with different permeabilities showed almost indistinguishable conductances. Conversely, a mutation at the putative narrowest pore region that is known to disrupt anion permeability selectivity (F337A) had minimal effects on anion relative conductance. Ion competition experiments confirmed that relatively tight binding of permeant anions resulted in relatively low conductance. These results suggest that the relative affinity of ion binding in the inner vestibule of the pore controls the relative conductance of different permeant anions in CFTR, and that the pore has two physically distinct anion selectivity filters that act in series to control anion conductance selectivity and anion permeability selectivity respectively. PMID:26779604

  11. Ketoprofen as a photoinitiator for anionic polymerization.

    PubMed

    Wang, Yu-Hsuan; Wan, Peter

    2015-06-01

    A new photoinitiating system for anionic polymerization of acrylates based on the efficient photodecarboxylation of Ketoprofen (1) and the related derivatives 3 and 4 that generate the corresponding carbanion intermediates is presented. Carbanion intermediates are confirmed by deuterium incorporation in the trapped Michael adducts and by spectroscopic detection using laser flash photolysis (LFP). This novel anionic initiating system features excitation in the near UV and visible regions, potential characteristics of photocontrolled living polymerization, and metal-free photoinitiators generated from photoexcitation, different from typical anionic polymerization where the polymerizations are initiated by heat and strong base containing alkali metals. PMID:25917384

  12. Photoelectron spectroscopy of nitromethane anion clusters

    NASA Astrophysics Data System (ADS)

    Pruitt, Carrie Jo M.; Albury, Rachael M.; Goebbert, Daniel J.

    2016-08-01

    Nitromethane anion and nitromethane dimer, trimer, and hydrated cluster anions were studied by photoelectron spectroscopy. Vertical detachment energies, estimated electron affinities, and solvation energies were obtained from the photoelectron spectra. Cluster structures were investigated using theoretical calculations. Predicted detachment energies agreed with experiment. Calculations show water binds to nitromethane anion through two hydrogen bonds. The dimer has a non-linear structure with a single ionic Csbnd H⋯O hydrogen bond. The trimer has two different solvent interactions, but both involve the weak Csbnd H⋯O hydrogen bond.

  13. Analysis of tracer and thermal transients during reinjection

    SciTech Connect

    Kocabas, I.

    1989-10-01

    This work studied tracer and thermal transients during reinjection in geothermal reserviors and developed a new technique which combines the results from interwell tracer tests and thermal injection-backflow tests to estimate the thermal breakthrough times. Tracer tests are essential to determine the degree of connectivity between the injection wells and the producing wells. To analyze the tracer return profiles quantitatively, we employed three mathematical models namely, the convection-dispersion (CD) model, matrix diffusion (MD) model, and the Avodnin (AD) model, which were developed to study tracer and heat transport in a single vertical fracture. We considered three types of tracer tests namely, interwell tracer tests without recirculation, interwell tracer tests with recirculation, and injection-backflow tracer tests. To estimate the model parameters, we used a nonlinear regression program to match tracer return profiles to the solutions.

  14. Transient tracer applications in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Stöven, T.; Tanhua, T.; Hoppema, M.

    2014-10-01

    Transient tracers can be used to constrain the Inverse-Gaussian transit time distribution (IG-TTD) and thus provide information about ocean ventilation. Individual transient tracers have different time and application ranges which are defined by their atmospheric history (chronological transient tracers) or their decay rate (radioactive transient tracers). The classification ranges from tracers for highly ventilated water masses, e.g. sulfur hexafluoride (SF6), the decay of Tritium (δ3H) and to some extent also dichlorodifluoromethane (CFC-12) to tracers for less ventilated deep ocean basins, e.g. CFC-12, Argon-39 (39Ar) and radiocarbon (14C). The IG-TTD can be empirically constrained by using transient tracer couples with sufficiently different input functions. Each tracer couple has specific characteristics which influence the application limit of the IG-TTD. Here we provide an overview of commonly used transient tracer couples and their validity areas within the IG-TTD by using the concept of tracer age differences (TAD). New measured CFC-12 and SF6 data from a section along 10° E in the Southern Ocean in 2012 are presented. These are combined with a similar data set of 1998 along 6° E in the Southern Ocean as well as with 39Ar data from the early 1980s in the western Atlantic Ocean and the Weddell Sea for investigating the application limit of the IG-TTD and to analyze changes in ventilation in the Southern Ocean. We found that the IG-TTD can be constrained south to 46° S which corresponds to the Subantarctic Front (SAF) denoting the application limit. The constrained IG-TTD north of the SAF shows a slight increase in mean ages between 1998 and 2012 in the upper 1200 m between 42-46° S. The absence of SF6 inhibits ventilation analyses below this depth. The time lag analysis between the 1998 and 2012 data shows an increase in ventilation down to 1000 m and a steady ventilation between 2000 m-bottom south of the SAF between 51-55° S.

  15. EVALUATION OF LEAKAGE FROM FUME HOODS USING TRACER GAS, TRACER NANOPARTICLES AND NANOPOWDER HANDLING TEST METHODOLOGIES

    PubMed Central

    Dunn, Kevin H.; Tsai, Candace Su-Jung; Woskie, Susan R.; Bennett, James S.; Garcia, Alberto; Ellenbecker, Michael J.

    2015-01-01

    The most commonly reported control used to minimize workplace exposures to nanomaterials is the chemical fume hood. Studies have shown, however, that significant releases of nanoparticles can occur when materials are handled inside fume hoods. This study evaluated the performance of a new commercially available nano fume hood using three different test protocols. Tracer gas, tracer nanoparticle, and nanopowder handling protocols were used to evaluate the hood. A static test procedure using tracer gas (sulfur hexafluoride) and nanoparticles as well as an active test using an operator handling nanoalumina were conducted. A commercially available particle generator was used to produce sodium chloride tracer nanoparticles. Containment effectiveness was evaluated by sampling both in the breathing zone (BZ) of a mannequin and operator as well as across the hood opening. These containment tests were conducted across a range of hood face velocities (60, 80, and 100 feet/minute) and with the room ventilation system turned off and on. For the tracer gas and tracer nanoparticle tests, leakage was much more prominent on the left side of the hood (closest to the room supply air diffuser) although some leakage was noted on the right side and in the BZ sample locations. During the tracer gas and tracer nanoparticle tests, leakage was primarily noted when the room air conditioner was on for both the low and medium hood exhaust air flows. When the room air conditioner was turned off, the static tracer gas tests showed good containment across most test conditions. The tracer gas and nanoparticle test results were well correlated showing hood leakage under the same conditions and at the same sample locations. The impact of a room air conditioner was demonstrated with containment being adversely impacted during the use of room air ventilation. The tracer nanoparticle approach is a simple method requiring minimal setup and instrumentation. However, the method requires the reduction in

  16. Kinetics and mechanism of exogenous anion exchange in FeFbpA-NTA: significance of periplasmic anion lability and anion binding activity of ferric binding protein A.

    PubMed

    Heymann, Jared J; Gabricević, Mario; Mietzner, Timothy A; Crumbliss, Alvin L

    2010-02-01

    The bacterial transferrin ferric binding protein A (FbpA) requires an exogenous anion to facilitate iron sequestration, and subsequently to shuttle the metal across the periplasm to the cytoplasmic membrane. In the diverse conditions of the periplasm, numerous anions are known to be present. Prior in vitro experiments have demonstrated the ability of multiple anions to fulfill the synergistic iron-binding requirement, and the identity of the bound anion has been shown to modulate important physicochemical properties of iron-bound FbpA (FeFbpA). Here we address the kinetics and mechanism of anion exchange for the FeFbpA-nitrilotriacetate (NTA) assembly with several biologically relevant anions (citrate, oxalate, phosphate, and pyrophosphate), with nonphysiologic NTA serving as a representative synergistic anion/chelator. The kinetic data are consistent with an anion-exchange process that occurs in multiple steps, dependent on the identity of both the entering anion and the leaving anion. The exchange mechanism may proceed either as a direct substitution or through an intermediate FeFbpA-X* assembly based on anion (X) identity. Our kinetic results further develop an understanding of exogenous anion lability in the periplasm, as well as address the final step of the iron-free FbpA (apo-FbpA)/Fe(3+) sequestration mechanism. Our results highlight the kinetic significance of the FbpA anion binding site, demonstrating a correlation between apo-FbpA/anion affinity and the FeFbpA rate of anion exchange, further supporting the requirement of an exogenous anion to complete tight sequestration of iron by FbpA, and developing a mechanism for anion exchange within FeFbpA that is dependent on the identity of both the entering anion and the leaving anion. PMID:19813031

  17. Molecular physiology of EAAT anion channels.

    PubMed

    Fahlke, Christoph; Kortzak, Daniel; Machtens, Jan-Philipp

    2016-03-01

    Glutamate is the major excitatory neurotransmitter in the mammalian central nervous system. After release from presynaptic nerve terminals, glutamate is quickly removed from the synaptic cleft by a family of five glutamate transporters, the so-called excitatory amino acid transporters (EAAT1-5). EAATs are prototypic members of the growing number of dual-function transport proteins: they are not only glutamate transporters, but also anion channels. Whereas the mechanisms underlying secondary active glutamate transport are well understood at the functional and at the structural level, mechanisms and cellular roles of EAAT anion conduction have remained elusive for many years. Recently, molecular dynamics simulations combined with simulation-guided mutagenesis and experimental analysis identified a novel anion-conducting conformation, which accounts for all experimental data on EAAT anion currents reported so far. We here review recent findings on how EAATs accommodate a transporter and a channel in one single protein. PMID:26687113

  18. Tracer-based prediction of thermal reservoir lifetime: scope, limitations, and the role of thermosensitive tracers

    NASA Astrophysics Data System (ADS)

    Ghergut, I.; Behrens, H.; Karmakar, S.; Licha, T.; Nottebohm, M.; Sauter, M.

    2012-04-01

    Thermal-lifetime prediction is a traditional endeavour of inter-well tracer tests conducted in geothermal reservoirs. Early tracer test signals (detectable within the first few years of operation) are expected to correlate with late-time production temperature evolutions ('thermal breakthrough', supposed to not occur before some decades of operation) of a geothermal reservoir. Whenever a geothermal reservoir can be described as a single-fracture system, its thermal lifetime will, ideally, be determined by two parameters (say, fracture aperture and porosity), whose inversion from conservative-tracer test signals is straightforward and non-ambiguous (provided that the tracer tests, and their interpretation, are performed in accordance to the rules of the art). However, as soon as only 'few more' fractures are considered, this clear-cut correlation is broken. A given geothermal reservoir can simultaneously feature a single-fracture behaviour, in terms of heat transport, and a multiple-fracture behaviour, in terms of solute tracer transport (or vice-versa), whose effective values of fracture apertures, spacings, and porosities are essentially uncorrelated between heat and solute tracers. Solute transport parameters derived from conservative-tracer tests will no longer characterize the heat transport processes (and thus temperature evolutions) taking place in the same reservoir. Parameters determining its thermal lifetime will remain 'invisible' to conservative tracers in inter-well tests. We demonstrate this issue at the example of a five-fracture system, representing a deep-geothermal reservoir, with well-doublet placement inducing fluid flow 'obliquely' to the fractures. Thermal breakthrough in this system is found to strongly depend on fracture apertures, whereas conservative-solute tracer signals from inter-well tests in the same system do not show a clear-cut correlation with fracture apertures. Only by using thermosensitive substances as tracers, a reliable

  19. A new class of organocatalysts: sulfenate anions.

    PubMed

    Zhang, Mengnan; Jia, Tiezheng; Yin, Haolin; Carroll, Patrick J; Schelter, Eric J; Walsh, Patrick J

    2014-09-26

    Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate-catalyzed (1-10 mol%) coupling of benzyl halides in the presence of base to generate trans-stilbenes in good to excellent yields (up to 99%). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst. PMID:25111259

  20. Vertical diffusivities of active and passive tracers

    NASA Astrophysics Data System (ADS)

    Canuto, V. M.; Cheng, Y.; Howard, A. M.

    The climate models that include a carbon-cycle need the vertical diffusivity of a passive tracer. Since an expression for the latter is not available, it has been common practice to identify it with that of salt. The identification is questionable since T, S are active, not passive tracers. We present the first derivation of the diffusivity of a passive tracer in terms of Ri (Richardson number) and R ρ (density ratio, ratio of salinity over temperature z-gradients). The following results have emerged: The passive tracer diffusivity is an algebraic function of Ri, R ρ. In doubly stable regimes (DS, ∂ T/∂z > 0, ∂S/∂ z < 0), the passive scalar diffusivity is nearly the same as that of salt/heat for any values of R ρ < 0 and Ri > 0. In DC regimes (diffusive convection, ∂ T/∂ z < 0, ∂ S/∂ z < 0, R ρ > 1), the passive scalar diffusivity is larger than that of salt. At Ri = O(1), it can be more than twice as large. In SF regimes (salt fingers, ∂ T/∂ z > 0, ∂ S/∂ z > 0, R ρ < 1), the passive scalar diffusivity is smaller than that of salt. At Ri = O(1), it can be less than half of it. The passive tracer diffusivity predicted at the location of NATRE (North Atlantic Tracer Release Experiment) is discussed. Perhaps the most relevant conclusion is that the common identification of the tracer diffusivity with that of salt is valid only in DS regimes. In the Southern Ocean, where there is the largest CO 2 absorption, the dominant regime is diffusive convection discussed in (c) above.

  1. Vertical Diffusivities of Active and Passive Tracers

    NASA Technical Reports Server (NTRS)

    Canuto, V. M.; Cheng, Y.; Howard, A. M.

    2010-01-01

    The climate models that include a carbon-cycle need the vertical diffusivity of a passive tracer. Since an expression for the latter is not available, it has been common practice to identify it with that of salt. The identification is questionable since T, S are active, not passive tracers. We present the first derivation of the diffusivity of a passive tracer in terms of Ri (Richardson number) and Rq (density ratio, ratio of salinity over temperature z-gradients). The following results have emerged: (a) The passive tracer diffusivity is an algebraic function of Ri, Rq. (b) In doubly stable regimes (DS, partial derivative of T with respect to z > 0, partial derivative of S with respect to z < 0), the passive scalar diffusivity is nearly the same as that of salt/heat for any values of Rq < 0 and Ri > 0. (c) In DC regimes (diffusive convection, partial derivative of T with respect to z < 0, partial derivative of S with respect to z < 0, Rq > 1), the passive scalar diffusivity is larger than that of salt. At Ri = O(1), it can be more than twice as large. (d) In SF regimes (salt fingers, partial derivative of T with respect to z > 0, partial derivative of S with respect to z > 0, Rq < 1), the passive scalar diffusivity is smaller than that of salt. At Ri = O(1), it can be less than half of it. (e) The passive tracer diffusivity predicted at the location of NATRE (North Atlantic Tracer Release Experiment) is discussed. (f) Perhaps the most relevant conclusion is that the common identification of the tracer diffusivity with that of salt is valid only in DS regimes. In the Southern Ocean, where there is the largest CO2 absorption, the dominant regime is diffusive convection discussed in (c) above.

  2. COMPARISON OF MODELLED AND MEASURED TRACER GAS CONCENTRATIONS DURING THE ACROSS NORTH AMERICA TRACER EXPERIMENT (ANATEX)

    EPA Science Inventory

    The 24-hour surface concentrations of several perfluorocarbon tracer gases measured during the 1987 Across North America Tracer Experiment (ANATEX) provided a unique continental-scale data set with which to evaluate long-range transport and diffusion models. One such model, a mul...

  3. Long residence times - bad tracer tests?

    NASA Astrophysics Data System (ADS)

    Ghergut, Julia; Behrens, Horst; Sauter, Martin

    2015-04-01

    Tracer tests conducted at geothermal well doublets or triplets in the Upper Rhine Rift Valley [1] all face, with very few exceptions so far, one common issue: lack of conclusive tracer test results, or tracer signals still undetectable for longer than one or two years after tracer injection. While the reasons for this surely differ from site to site (Riehen, Landau, Insheim, Bruchsal, ...), its effects on how the usefulness of tracer tests is perceived by the non-tracer community are pretty much the same. The 'poor-signal' frustration keeps nourishing two major 'alternative' endeavours : (I) design and execute tracer tests in single-well injection-withdrawal (push-pull), 'instead of' inter-well flow-path tracing configurations; (II) use 'novel' tracer substances instead of the 'old' ones which have 'obviously failed'. Frustration experienced with most inter-well tracer tests in the Upper Rhine Rift Valley has also made them be regarded as 'maybe useful for EGS' ('enhanced', or 'engineered' geothermal systems, whose fluid RTD typically include a major share of values below one year), but 'no longer worthwhile a follow-up sampling' in natural, large-scale hydrothermal reservoirs. We illustrate some of these arguments with the ongoing Bruchsal case [2]. The inter-well tracer test conducted at Bruchsal was (and still is!) aimed at assessing inter-well connectivity, fluid residence times, and characterizing the reservoir structure [3]. Fluid samples taken at the geothermal production well after reaching a fluid turnover of about 700,000 m3 showed tracer concentrations in the range of 10-8 Minj per m3, in the liquid phase of each sample (Minj being the total quantity of tracer injected as a short pulse at the geothermal re-injection well). Tracer signals might actually be higher, owing to tracer amounts co-precipitated and/or adsorbed onto the solid phase whose accumulation in the samples was unavoidable (due to pressure relief and degassing during the very sampling

  4. Blood-nerve barrier: distribution of anionic sites on the endothelial plasma membrane and basal lamina of dorsal root ganglia.

    PubMed

    Bush, M S; Reid, A R; Allt, G

    1991-09-01

    Previous investigations of the blood-nerve barrier have correlated the greater permeability of ganglionic endoneurial vessels, compared to those of nerve trunks, with the presence of fenestrations and open intercellular junctions. Recent studies have demonstrated reduced endothelial cell surface charge in blood vessels showing greater permeability. To determine the distribution of anionic sites on the plasma membranes and basal laminae of endothelial cells in dorsal root ganglia, cationic colloidal gold and cationic ferritin were used. Electron microscopy revealed the existence of endothelial microdomains with differing labelling densities. Labelling indicated that caveolar and fenestral diaphragms and basal laminae are highly anionic at physiological pH, luminal plasma membranes and endothelial processes are moderately charged and abluminal plasma membranes are weakly anionic. Tracers did not occur in caveolae or cytoplasmic vesicles. In vitro tracer experiments at pH values of 7.3, 5.0, 3.5 and 2.0 indicated that the anionic charge on the various endothelial domains was contributed by chemical groups with differing pKa values. In summary, the labelling of ganglionic and sciatic nerve vessels was similar except for the heavy labelling of diaphragms in a minority of endoneurial vessels in ganglia. This difference is likely to account in part for the greater permeability of ganglionic endoneurial vessels. The results are discussed with regard to the blood-nerve and -brain barriers and vascular permeability in other tissues and a comparison made between the ultrastructure and anionic microdomains of epi-, peri- and endoneurial vessels of dorsal root ganglia and sciatic nerves. PMID:1960538

  5. Comparison of modelled and measured tracer gas concentrations during the Across North America Tracer Experiment (ANATEX)

    SciTech Connect

    Clark, T.L.; Cohn, R.D.; Seilkop, S.K.; Draxler, R.R.; Heffter, J.L.

    1989-01-01

    The 24-hour surface concentrations of several perfluorocarbon tracer gases measured during the 1987 Across North America Tracer Experiment (ANATEX) provided a unique continental-scale data set with which to evaluate long-range transport and diffusion models. One such model, a multilayer Lagrangian model, was evaluated in the ANATEX Model Evaluation Study (AMES) by comparing distributions and time series of calculated and measured tracer concentrations at bands of sampling sites nearly equidistant from one of the two tracer release sites and by computing spatial differences in the concentration-weighted centroids of 20, 24-hour tracer footprints or composite plumes. The results for this model indicated that it overemphasized the effects of the stronger upper-level winds. In spite of the bias in transport speed, the distributions of the calculated and measured concentrations were quite similar.

  6. Exploring Hydrofluorocarbons as Groundwater Age Tracers (Invited)

    NASA Astrophysics Data System (ADS)

    Haase, K. B.; Busenberg, E.; Plummer, L. N.; Casile, G.; Sanford, W. E.

    2013-12-01

    Groundwater dating tracers are an essential tool for analyzing hydrologic conditions in groundwater systems. Commonly used tracers for dating post-1940's groundwater include sulfur hexafluoride (SF6), chlorofluorocarbons (CFCs), 3H-3He, and other isotopic tracers (85Kr, δ2H and δ18O isotopes, etc.). Each tracer carries a corresponding set of advantages and limitations imposed by field, analytical, and interpretive methods. Increasing the number available tracers is appealing, particularly if they possess inert chemical properties and unique temporal emission histories from other tracers. Atmospherically derived halogenated trace gases continue to hold untapped potential for new tracers, as they are generally inert and their emission histories are well documented. SF5CF3, and CFC-13 were previously shown to have application as dating tracers, though their low mixing ratios and low solubility require large amounts of water to be degassed for their quantification. Two related groups of compounds, hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) are hypothesized to be potential age tracers, having similar mixing ratios to the CFCs and relatively high solubility. However, these compounds yield gas chromatography electron capture detector (GC-ECD) responses that are 10-2 -10-5 less than CFC-12, making purge and trap or field stripping GC-ECD approaches impractical. Therefore, in order to use dissolved HCFCs and HFCs as age tracers, different approaches are needed. To solve this problem, we developed an analytical method that uses an atomic emission detector (GC-AED) in place of an ECD to detect fluorinated compounds. In contrast to the ECD, the AED is a universally sensitive, highly linear, elementally specific detector. The new GC-AED system is being used to measure chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a), and other fluorinated compounds in one liter water samples to study their potential as age dating tracers. HCFC-22 is a

  7. Thermal Stability of Chelated Indium Activable Tracers

    SciTech Connect

    Chrysikopoulos, Costas; Kruger, Paul

    1986-01-21

    The thermal stability of indium tracer chelated with organic ligands ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) was measured for reservoir temperatures of 150, 200, and 240 C. Measurements of the soluble indium concentration was made as a function of time by neutron activation analysis. From the data, approximate thermal decomposition rates were estimated. At 150 C, both chelated tracers were stable over the experimental period of 20 days. At 200 C, the InEDTA concentration remained constant for 16 days, after which the thermal decomposition occurred at a measured rate constant of k = 0.09 d{sup -1}. The thermal decomposition of InNTA at 200 C showed a first order reaction with a measured rate constant of k = 0.16 d{sup -1}. At 240 C, both indium chelated tracers showed rapid decomposition with rate constants greater than 1.8 d{sup -1}. The data indicate that for geothermal reservoir with temperatures up to about 200 C, indium chelated tracers can be used effectively for transit times of at least 20 days. These experiments were run without reservoir rock media, and do not account for concomitant loss of indium tracer by adsorption processes.

  8. Sulfur hexafluoride gas tracer studies in streams

    SciTech Connect

    Hibbs, D.E.; Gulliver, J.S.; Parkhill, K.L.

    1998-08-01

    Gas tracers are useful investigative tools in the study of reaeration and the fate of volatile organic contaminants in many natural streams. They enable the direct measurement of a variety of stream parameters, including the gas exchange rates between the stream and the atmosphere, as well as the spreading rate for dissolved pollutants downstream of a discharge point or spill site. The air-water mass transfer coefficients, dispersion coefficients, and mean residence times in two experimental streams and one natural stream are measured using a variation of the standard volatile tracer-dye technique. Sulfur hexafluoride (SF{sub 6}) is used as the volatile tracer and rhodamine WT is used as the conservative tracer. The low limit of quantification of SF{sub 6} makes it possible to inject SF{sub 6}-rich water into many streams and avoid complications with dosing a stream with a gaseous tracer. The experimental methods are described in detail. The SF{sub 6} measurements were extremely precise, producing smooth concentration time curves. The SF{sub 6} measurements collected in side-by-side experimental channels yielded similar values of the gas transfer coefficient.

  9. Novel pseudo-delocalized anions for lithium battery electrolytes.

    PubMed

    Jónsson, Erlendur; Armand, Michel; Johansson, Patrik

    2012-05-01

    A novel anion concept of pseudo-delocalized anions, anions with distinct positive and negative charge regions, has been studied by a computer aided synthesis using DFT calculations. With the aim to find safer and better performing lithium salts for lithium battery electrolytes two factors have been evaluated: the cation-anion interaction strength via the dissociation reaction LiAn ⇌ Li(+) + An(-) and the anion oxidative stability via a vertical ionisation from anion to radical. Based on our computational results some of these anions have shown promise to perform well as lithium salts for modern lithium batteries and should be interesting synthetic targets for future research. PMID:22441354

  10. Simulation and interpretation of inter-well tracer tests

    NASA Astrophysics Data System (ADS)

    Huseby, Olaf; Sagen, Jan; Viig, Sissel; Dugstad, Øyvind

    2013-05-01

    In inter-well tracer tests (IWTT), chemical compounds or radioactive isotopes are used to label injection water and gas to establish well connections and fluid patterns in petroleum reservoirs. Tracer simulation is an invaluable tool to ease the interpretation of IWTT results and is also required for assisted history matching application of tracer data. In this paper we present a new simulation technique to analyse and interpret tracer results. Laboratory results are used to establish and test formulations of the tracer conservation equations, and the technique is used to provide simulated tracer responses that are compared with observed tracer data from an extensive tracer program. The implemented tracer simulation methodology use a fast post-processing of previously simulated reservoir simulation runs. This provides a fast, flexible and powerful method for analysing gas tracer behaviour in reservoirs. We show that simulation time for tracers can be reduced by factor 100 compared to solving the tracer flow equations simultaneously with the reservoir fluid flow equations. The post-processing technique, combined with a flexible built-in local tracer-grid refinement is exploited to reduce numerical smearing, particularly severe for narrow tracer pulses.

  11. Studies of anions sorption on natural zeolites.

    PubMed

    Barczyk, K; Mozgawa, W; Król, M

    2014-12-10

    This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method. PMID:25002191

  12. Molecular pharmacology of renal organic anion transporters.

    PubMed

    Van Aubel, R A; Masereeuw, R; Russel, F G

    2000-08-01

    Renal organic anion transport systems play an important role in the elimination of drugs, toxic compounds, and their metabolites, many of which are potentially harmful to the body. The renal proximal tubule is the primary site of carrier-mediated transport from blood to urine of a wide variety of anionic substrates. Recent studies have shown that organic anion secretion in renal proximal tubule is mediated by distinct sodium-dependent and sodium-independent transport systems. Knowledge of the molecular identity of these transporters and their substrate specificity has increased considerably in the past few years by cloning of various carrier proteins. However, a number of fundamental questions still have to be answered to elucidate the participation of the cloned transporters in the overall tubular secretion of anionic xenobiotics. This review summarizes the latest knowledge on molecular and pharmacological properties of renal organic anion transporters and homologs, with special reference to their nephron and plasma membrane localization, transport characteristics, and substrate and inhibitor specificity. A number of the recently cloned transporters, such as the p-aminohippurate/dicarboxylate exchanger OAT1, the anion/sulfate exchanger SAT1, the peptide transporters PEPT1 and PEPT2, and the nucleoside transporters CNT1 and CNT2, are key proteins in organic anion handling that possess the same characteristics as has been predicted from previous physiological studies. The role of other cloned transporters, such as MRP1, MRP2, OATP1, OAT-K1, and OAT-K2, is still poorly characterized, whereas the only information that is available on the homologs OAT2, OAT3, OATP3, and MRP3-6 is that they are expressed in the kidney, but their localization, not to mention their function, remains to be elucidated. PMID:10919840

  13. Particle and tracer diffusion in complex liquids

    NASA Astrophysics Data System (ADS)

    Koynov, Kaloian; Butt, Hans-Jürgen

    2013-02-01

    The diffusion of fluorescent tracers can be studied using fluorescence correlation spectroscopy (FCS). This powerful method offers the possibility to monitor very small tracers at low concentrations, down to single molecules. Furthermore it possesses a sub-femtoliter detection volume that can be precisely positioned in a heterogeneous environment to probe the local dynamics. Despite its great potential and high versatility in addressing the diffusion and transport properties in complex systems, FCS has been predominantly applied in molecular and cell biology. Here we present some applications that are more relevant for material and soft matter science. First, we study the diffusion of single tracers with molecular sizes in undiluted polymer systems. Next, the diffusion of small molecules and semiconductor nanoparticles (quantum dots) in silica inverse opals is studied and correlated to the size and morphology of the inverse opals. Finally, we show how FCS can be used to measure the diffusion coefficient of nanoparticles at water-oil interfaces.

  14. Enhanced Oil Recovery: Aqueous Flow Tracer Measurement

    SciTech Connect

    Joseph Rovani; John Schabron

    2009-02-01

    A low detection limit analytical method was developed to measure a suite of benzoic acid and fluorinated benzoic acid compounds intended for use as tracers for enhanced oil recovery operations. Although the new high performance liquid chromatography separation successfully measured the tracers in an aqueous matrix at low part per billion levels, the low detection limits could not be achieved in oil field water due to interference problems with the hydrocarbon-saturated water using the system's UV detector. Commercial instrument vendors were contacted in an effort to determine if mass spectrometry could be used as an alternate detection technique. The results of their work demonstrate that low part per billion analysis of the tracer compounds in oil field water could be achieved using ultra performance liquid chromatography mass spectrometry.

  15. Prediction of the existence of the N2H- molecular anion

    NASA Astrophysics Data System (ADS)

    Lique, François; Halvick, Philippe; Stoecklin, Thierry; Hochlaf, Majdi

    2012-06-01

    We predict the existence of the N2H- anion from first principle calculations. We present the three-dimensional potential energy surface and the bound states of the N2H-/D- van der Waals anion. The electronic calculations were performed using state-of-the-art ab initio methods and the nuclear motions were solved using a quantum close-coupling scattering theory. A T-shaped equilibrium structure was found, with a well depth of 349.1 cm-1, where 18 bound states have been located for N2H- and 25 for N2D- for total angular momentum J = 0. We also present the absorption spectra of the N2H- complex. This anion could be formed after low energy collisions between N2 and H- through radiative association. The importance of this prediction in astrophysics and the possible use of N2H- as a tracer of N2 and H- in the interstellar medium is discussed.

  16. Dynamics and mechanics of tracer particles

    NASA Astrophysics Data System (ADS)

    Phillips, C. B.; Jerolmack, D. J.

    2014-06-01

    Understanding the mechanics of bed load at the flood scale is necessary to link hydrology to landscape evolution. Here we report on observations of the transport of coarse sediment tracer particles in a cobble-bedded alluvial river and a step-pool tributary, at the individual flood and multi-annual timescales. Tracer particle data for each survey are composed of measured displacement lengths for individual particles, and the number of tagged particles mobilized. For single floods we find that: measured tracer particle displacement lengths are exponentially distributed; the number of mobile particles increases linearly with peak flood Shields stress, indicating partial bed load transport for all observed floods; and modal displacement lengths scale linearly with excess shear velocity. These findings provide quantitative field support for a recently proposed modelling framework based on momentum conservation at the grain scale. Tracer displacement shows a weak correlation with particle size at the individual flood scale, however cumulative travel distance begins to show an inverse relation to grain size when measured over many transport events. The observed spatial sorting of tracers approaches that of the river bed, and is consistent with size-selective deposition models and laboratory experiments. Tracer displacement data for the step-pool and alluvial channels collapse onto a single curve - despite more than an order of magnitude difference in channel slope - when variations of critical Shields stress and flow resistance between the two are accounted for. Results show how bed load dynamics may be predicted from a record of river stage, providing a direct link between climate and sediment transport.

  17. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-12-11

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  18. ANNUAL REPORT. SUPRAMOLECULAR CHEMISTRY OF SELECTIVE ANION RECOGNITION FOR ANIONS OF ENVIRONMENTAL RELEVANCE

    EPA Science Inventory

    This project involves the design and synthesis of receptors for anions of environmental importance, including emphasis on high level and low activity waste. Polyammonium macrocycles as receptors and nitrate as target anion were the focus of the first phase of this project. A seco...

  19. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Bowman-James, Kristen

    2004-12-01

    This project have focuses on the basic chemical aspects of anion receptor design of functional pH independent systems, with the ultimate goal of targeting the selective binding of sulfate, as well as design of separations strategies for selective and efficient removal of targeted anions. Key findings include: (1) the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate anion from acidic, nitrate-containing aqueous media. Areas probed during the last funding period include: the design, synthesis, and physical and structural characterization of receptors and investigation of anion and dual ion pair extraction using lipophilic amide receptors for anion binding. A new collaboration has been added to the project in addition to the one with Dr. Bruce Moyer at Oak Ridge National Laboratory, with Professor Jonathan Sessler at the University of Texas at Austin.

  20. Galaxy tracers in N-body simulations

    NASA Technical Reports Server (NTRS)

    Summers, F. J.; Evrard, August E.; Davis, Marc

    1993-01-01

    Using the method of smoothed particle hydrodynamics, we have modeled the formation of a compact group of galaxies with sufficient resolution to trace galaxies. Radiative cooling allows the baryons to dissipate their thermal energy and collapse to overdensities characteristic of real galaxies. With their cross section greatly reduced, these galaxy tracers remain distinct during cluster formation while their dark matter halos merge. In addition, the number density, the mass distribution function, and even the morphology of these objects are similar to those of observed galaxies. A viable population of galaxy tracers can be unambiguously defined.

  1. Analysis of fluorescent particle tracer data

    SciTech Connect

    Clements, W.E.

    1980-01-01

    Four fluorescent particle tracer experiments were conducted during the July 1979 ASCOT experiment in the Anderson Creek Valley of northern California. The purpose of the experiment was to examine the transport and elongation of a plume traveling in the Anderson Creek nocturnal drainage flow and investigate the interaction of the Anderson Creek and Putah Creek flow fields. Sequential samples of tracer material at three downwind locations in Anderson Creek gave effective transport velocities of 1 to 2 m/s and showed an approximately linear relationship between plume elongation and travel distance. Integrated samples taken in both the Anderson Creek and Putah Creek air sheds indicated considerable interaction between the two flow fields.

  2. Geologic flow characterization using tracer techniques

    SciTech Connect

    Klett, R. D.; Tyner, C. E.; Hertel, Jr., E. S.

    1981-04-01

    A new tracer flow-test system has been developed for in situ characterization of geologic formations. This report describes two sets of test equipment: one portable and one for testing in deep formations. Equations are derived for in situ detector calibration, raw data reduction, and flow logging. Data analysis techniques are presented for computing porosity and permeability in unconfined isotropic media, and porosity, permeability and fracture characteristics in media with confined or unconfined two-dimensional flow. The effects of tracer pulse spreading due to divergence, dispersion, and porous formations are also included.

  3. Radiopharmaceutical Tracers for Neural Progenitor Cells

    SciTech Connect

    Mangner, Thomas J.

    2006-09-29

    The Technical Report summarizes the results of the synthesis and microPET animal scanning of several compounds labeled with positron-emitting isotopes in normal, neonatal and kainic acid treated (seizure induced) rats as potential PET tracers to image the process of neurogenesis using positron emission tomography (PET). The tracers tested were 3'-deoxy-3'-[F-18]fluorothymidine ([F-18]FLT) and 5'-benzoyl-FTL, 1-(2'-deoxy-2'-[F-18]fluoro-B-D-arabinofuranosyl)-5-bromouracil (FBAU) and 3',5'-dibenzoyl-FBAU, N-[F-18]fluoroacetyl-D-glucosamine (FLAG) and tetraacetyl-FLAG, and L-[1-C-11]leucine.

  4. Method of dispersing particulate aerosol tracer

    DOEpatents

    O'Holleran, Thomas P.

    1988-01-01

    A particulate aerosol tracer which comprises a particulate carrier of sheet silicate composition having a particle size up to one micron, and a cationic dopant chemically absorbed in solid solution in the carrier. The carrier is preferably selected from the group consisting of natural mineral clays such as bentonite, and the dopant is selected from the group consisting of rare earth elements and transition elements. The tracers are dispersed by forming an aqueous salt solution with the dopant present as cations, dispersing the carriers in the solution, and then atomizing the solution under heat sufficient to superheat the solution droplets at a level sufficient to prevent reagglomeration of the carrier particles.

  5. Correction of the anion gap for albumin in order to detect occult tissue anions in shock

    PubMed Central

    Hatherill, M; Waggie, Z; Purves, L; Reynolds, L; Argent, A

    2002-01-01

    Background: It is believed that hypoalbuminaemia confounds interpretation of the anion gap (AG) unless corrected for serum albumin in critically ill children with shock. Aim: To compare the ability of the AG and the albumin corrected anion gap (CAG) to detect the presence of occult tissue anions. Methods: Prospective observational study in children with shock in a 22 bed multidisciplinary paediatric intensive care unit of a university childrenrsquo;s hospital. Blood was sampled at admission and at 24 hours, for acid-base parameters, serum albumin, and electrolytes. Occult tissue anions (lactate + truly "unmeasured" anions) were calculated from the strong ion gap. The anion gap ((Na + K) - (Cl + bicarbonate)) was corrected for serum albumin using the equation of Figge: AG + (0.25 x (44 - albumin)). Occult tissue anions (TA) predicted by the anion gap were calculated by (anion gap - 15 mEq/l). Optimal cut off values of anion gap were compared by means of receiver operating characteristic (ROC) curves. Ninety three sets of data from 55 children (median age 7 months, median weight 4.9 kg) were analysed. Data are expressed as mean (SD), and mean bias (limits of agreement). Results: The incidence of hypoalbuminaemia was 76% (n = 42/55). Mean serum albumin was 25 g/l (SD 8). Mean AG was 15.0 mEq/l (SD 6.1), compared to the CAG of 19.9 mEq/l (SD 6.6). Mean TA was 10.2 mmol/l (SD 6.3). The AG underestimated TA with mean bias 10.2 mmol/l (4.1–16.1), compared to the CAG, mean bias 5.3 mmol/l (0.4–10.2). A clinically significant increase of TA >5 mmol/l was present in 83% (n = 77/93) of samples, of which the AG detected 48% (n = 36/77), and the CAG 87% (n = 67/77). Post hoc ROC analysis revealed optimal cut off values for detection of TA >5 mmol/l to be AG >10 mEq/l, and CAG >15.5 mEq/l. Conclusion: Hypoalbuminaemia is common in critically ill children with shock, and is associated with a low observed anion gap that may fail to detect clinically significant amounts of

  6. Electron impact induced anion production in acetylene.

    PubMed

    Szymańska, Ewelina; Čadež, Iztok; Krishnakumar, E; Mason, Nigel J

    2014-02-28

    A detailed experimental investigation of electron induced anion production in acetylene, C2H2, in the energy range between 1 and 90 eV is presented. The anions are formed by two processes in this energy range: dissociative electron attachment (DEA) and dipolar dissociation (DD). DEA in C2H2 is found to lead to the formation of H(-) and C2(-)/C2H(-) through excitation of resonances in the electron energy range 1-15 eV. These anionic fragments are formed with super thermal kinetic energy and reveal no anisotropy in the angular distributions. DD in C2H2 leads to the formation of H(-), C(-)/CH(-) and C2(-)/C2H(-) with threshold energies of 15.7, 20.0 and 16.5 eV respectively. The measured anion yields have been used to calculate anion production rates for H(-), C(-)/CH(-) and C2(-)/C2H(-) in Titan's ionosphere. PMID:24343432

  7. Electroosmotic Flow Hysteresis for Dissimilar Anionic Solutions.

    PubMed

    Lim, An Eng; Lim, Chun Yee; Lam, Yee Cheong

    2016-08-16

    Electroosmotic flow (EOF) with two or more fluids is often encountered in various microfluidic applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during displacement flow of solutions with dissimilar anion species. In this investigation, EOF of dissimilar anionic solutions was studied experimentally through the current monitoring method and numerically through finite element simulations. As opposed to other conventional displacement flows, EOF involving dissimilar anionic solutions exhibits counterintuitive behavior, whereby the current-time curve does not reach the steady-state value of the displacing electrolyte. Two distinct mechanics have been identified as the causes for this observation: (a) ion concentration adjustment when the displacing anions migrate upstream against EOF due to competition between the gradients of electromigrative and convective fluxes and (b) ion concentration readjustment induced by the static diffusive interfacial region between the dissimilar fluids which can only be propagated throughout the entire microchannel with the presence of EOF. The resultant ion distributions lead to the flow rate to be directional-dependent, indicating that the flow conditions are asymmetric between these two different flow directions. The outcomes of this investigation contribute to the in-depth understanding of flow behavior in microfluidic systems involving inhomogeneous fluids, particularly dissimilar anionic solutions. The understanding of EOF hysteresis is fundamentally important for the accurate prediction of analytes transport in microfluidic devices under EOF. PMID:27426052

  8. Infrared spectroscopy of anionic hydrated fluorobenzenes

    SciTech Connect

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-09-21

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C{sub 6}F{sub 6}{sup -}{center_dot}H{sub 2}O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules.

  9. An anionic surfactant for EOR applications

    NASA Astrophysics Data System (ADS)

    Sagir, Muhammad; Tan, Isa M.; Mushtaq, Muhammad

    2014-10-01

    This work is to investigate the new anionic surfactants for the Enhanced Oil Recovery (EOR) application. Sulfonated anionic surfactant was produced by attaching SO3 to an ethoxylated alcohol to increase the performance of the surfactant. Methallyl chloride and ethoxylated alcohol was reacted followed by the reaction with sodium bisulfite to produce anionic sulfonated surfactant in 80.3 % yield. The sulfonation reaction parameters such as reactants mole ratio, reaction temperature and catalyst amount were optimized. The generation and stability of foam from the synthesized surfactant is also tested and results are reported. The synthesized novel surfactant was further investigated for the effect on the CO2 mobility in porous media and the findings are presented here. This in house developed surfactant has a great potential for CO2- EOR applications.

  10. Infrared Spectroscopy of Hydrated Nitromethane Anions

    NASA Astrophysics Data System (ADS)

    Marcum, Jesse C.; Weber, J. Mathias

    2009-06-01

    The hydration of molecular anions is still not as thoroughly explored as for atomic anions. We present IR spectra and quantum chemical calculations of hydrated nitromethane anions. In the monohydrate, the nitro group of the ion interacts with the water molecule via two hydrogen bonds, one from each O atom. This motif is partially conserved in the dihydrate. Adding the third water molecule results in a ring-like structure of the water ligands, each of which forms one H bond to one of the O atoms of the nitro group and another to a neighboring water ligand, reminiscent of the hydration motif of the heavier halides. Interestingly, while the methyl group is not directly involved in the interaction with the water ligands, its infrared signature is strongly affected by the changes in the intramolecular charge distribution through hydration.

  11. Using Neural Networks to Describe Tracer Correlations

    NASA Technical Reports Server (NTRS)

    Lary, D. J.; Mueller, M. D.; Mussa, H. Y.

    2003-01-01

    Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). In this study a neural network using Quickprop learning and one hidden layer with eight nodes was able to reproduce the CH4-N2O correlation with a correlation co- efficient of 0.9995. Such an accurate representation of tracer-tracer correlations allows more use to be made of long-term datasets to constrain chemical models. Such as the dataset from the Halogen Occultation Experiment (HALOE) which has continuously observed CH4, (but not N2O) from 1991 till the present. The neural network Fortran code used is available for download.

  12. Blood Tracer Kinetics in the Arterial Tree

    PubMed Central

    Kellner, Elias; Gall, Peter; Günther, Matthias; Reisert, Marco; Mader, Irina; Fleysher, Roman; Kiselev, Valerij G.

    2014-01-01

    Evaluation of blood supply of different organs relies on labeling blood with a suitable tracer. The tracer kinetics is linear: Tracer concentration at an observation site is a linear response to an input somewhere upstream the arterial flow. The corresponding impulse response functions are currently treated empirically without incorporating the relation to the vascular morphology of an organ. In this work we address this relation for the first time. We demonstrate that the form of the response function in the entire arterial tree is reduced to that of individual vessel segments under approximation of good blood mixing at vessel bifurcations. The resulting expression simplifies significantly when the geometric scaling of the vascular tree is taken into account. This suggests a new way to access the vascular morphology in vivo using experimentally determined response functions. However, it is an ill-posed inverse problem as demonstrated by an example using measured arterial spin labeling in large brain arteries. We further analyze transport in individual vessel segments and demonstrate that experimentally accessible tracer concentration in vessel segments depends on the measurement principle. Explicit expressions for the response functions are obtained for the major middle part of the arterial tree in which the blood flow in individual vessel segments can be treated as laminar. When applied to the analysis of regional cerebral blood flow measurements for which the necessary arterial input is evaluated in the carotid arteries, present theory predicts about 20% underestimation, which is in agreement with recent experimental data. PMID:25299048

  13. Subsurface barrier integrity verification using perfluorocarbon tracers

    SciTech Connect

    Sullivan, T.M.; Heiser, J.; Milian, L.; Senum, G.

    1996-12-01

    Subsurface barriers are an extremely promising remediation option to many waste management problems. Gas phase tracers include perfluorocarbon tracers (PFT`s) and chlorofluorocarbon tracers (CFC`s). Both have been applied for leak detection in subsurface systems. The focus of this report is to describe the barrier verification tests conducted using PFT`s and analysis of the data from the tests. PFT verification tests have been performed on a simulated waste pit at the Hanford Geotechnical facility and on an actual waste pit at Brookhaven National Laboratory (BNL). The objective of these tests were to demonstrate the proof-of-concept that PFT technology can be used to determine if small breaches form in the barrier and for estimating the effectiveness of the barrier in preventing migration of the gas tracer to the monitoring wells. The subsurface barrier systems created at Hanford and BNL are described. The experimental results and the analysis of the data follow. Based on the findings of this study, conclusions are offered and suggestions for future work are presented.

  14. Tracer Transport in the Tropical Tropopause Layer

    NASA Astrophysics Data System (ADS)

    Jensen, E. J.; Pfister, L.; Bergman, J. W.; Atlas, E. L.

    2013-12-01

    Trace species such as carbon monoxide, ozone, and very short-lived halocarbons in the Tropical Tropopause Layer (TTL) are important for chemistry and the radiation budget. Also, these species can be used to diagnose transport pathways into and through the TTL. TTL tracer concentrations are controlled primarily by input from extreme deep convective systems that rapidly transport air from the lower troposphere into the TTL, rapid horizontal transport, and slow vertical transport, with the rapid convective transport directly to the uppermost TTL being particularly important for species with short lifetimes. The extreme deep convection overshooting to near the tropical tropopause is poorly represented by convective parameterizations used in global models. Here, we investigate tracer transport using trajectories along with explicit calculations of convective influence. The times and locations of convective influence on the trajectory parcels are determined by tracing the trajectories through two-dimensional, three-hourly fields of convective cloud top height from geostationary satellite and TRMM. The tracer simulations are constrained by measurements from the Aura MLS and ACE-FTS satellites, as well as measurements from recent high-altitude aircraft campaigns. The model is used to evaluate the sensitivity of TTL tracer concentrations to diabatic heating rate (approximately in balance with vertical motion) and the occurrence frequency of extreme convection.

  15. Travel-time-based thermal tracer tomography

    NASA Astrophysics Data System (ADS)

    Somogyvári, Márk; Bayer, Peter; Brauchler, Ralf

    2016-05-01

    Active thermal tracer testing is a technique to get information about the flow and transport properties of an aquifer. In this paper we propose an innovative methodology using active thermal tracers in a tomographic setup to reconstruct cross-well hydraulic conductivity profiles. This is facilitated by assuming that the propagation of the injected thermal tracer is mainly controlled by advection. To reduce the effects of density and viscosity changes and thermal diffusion, early-time diagnostics are used and specific travel times of the tracer breakthrough curves are extracted. These travel times are inverted with an eikonal solver using the staggered grid method to reduce constraints from the pre-defined grid geometry and to improve the resolution. Finally, non-reliable pixels are removed from the derived hydraulic conductivity tomograms. The method is applied to successfully reconstruct cross-well profiles as well as a 3-D block of a high-resolution fluvio-aeolian aquifer analog data set. Sensitivity analysis reveals a negligible role of the injection temperature, but more attention has to be drawn to other technical parameters such as the injection rate. This is investigated in more detail through model-based testing using diverse hydraulic and thermal conditions in order to delineate the feasible range of applications for the new tomographic approach.

  16. Identification and characterization of anion binding sites in RNA

    SciTech Connect

    Kieft, Jeffrey S.; Chase, Elaine; Costantino, David A.; Golden, Barbara L.

    2010-05-24

    Although RNA molecules are highly negatively charged, anions have been observed bound to RNA in crystal structures. It has been proposed that anion binding sites found within isolated RNAs represent regions of the molecule that could be involved in intermolecular interactions, indicating potential contact points for negatively charged amino acids from proteins or phosphate groups from an RNA. Several types of anion binding sites have been cataloged based on available structures. However, currently there is no method for unambiguously assigning anions to crystallographic electron density, and this has precluded more detailed analysis of RNA-anion interaction motifs and their significance. We therefore soaked selenate into two different types of RNA crystals and used the anomalous signal from these anions to identify binding sites in these RNA molecules unambiguously. Examination of these sites and comparison with other suspected anion binding sites reveals features of anion binding motifs, and shows that selenate may be a useful tool for studying RNA-anion interactions.

  17. Tris-ureas as transmembrane anion transporters.

    PubMed

    Olivari, Martina; Montis, Riccardo; Berry, Stuart N; Karagiannidis, Louise E; Coles, Simon J; Horton, Peter N; Mapp, Lucy K; Gale, Philip A; Caltagirone, Claudia

    2016-08-01

    Nine tris-urea receptors (L(1)-L(9)) have been synthesised and shown to coordinate to a range of anionic guests both by (1)H NMR titration techniques and single crystal X-ray structural analysis. The compounds have been shown to be capable of mediating the exchange of chloride and nitrate and also chloride and bicarbonate across POPC or POPC : cholesterol 7 : 3 vesicle bilayer membranes at low transporter loadings. An interesting dependency of anion transport on the nature of the cation is evidence to suggest that a M(+)/Cl(-) cotransport process may also contribute to the release of chloride from the vesicles. PMID:27383134

  18. Anionic polymerization of azo substituted methacrylates

    SciTech Connect

    Dimov, D.K.; Dalton, L.R.; Hogen-Esch, T.E.

    1993-12-31

    The anionic polymerization of 4-phenylazophenyl methacrylate (PAM) and 6-(4-phenylazophenoxy)-hexyl methacrylate (PAHM) initiated by {open_quotes}living{close_quotes} PMMA with lithium counterion was studied in THF at {minus}78{degrees}C. The polymerization of PAM was prevented by a side termination reaction. The polymerization of PAHM proceeded smoothly to furnish PMMA/azopolymer block copolymers. The process showed features typical of {open_quotes}living{close_quotes} anionic polymerization. No phase transitions could be detected by DSC to prove liquid crystalline mesophase formation by the block copolymers.

  19. Negative Ion Photoelectron Spectra of Halomethyl Anions

    NASA Astrophysics Data System (ADS)

    Vogelhuber, Kristen M.; Wren, Scott W.; McCoy, Anne B.; Ervin, Kent M.; Lineberger, W. Carl

    2009-06-01

    Halomethyl anions undergo a significant geometry change upon electron photodetachment, resulting in multiple extended vibrational progressions in the photoelectron spectra. The normal mode analysis that successfully models photoelectron spectra when geometry changes are modest is unable to reproduce the experimental data using physically reasonable parameters. A three-dimensional anharmonic coupled-mode analysis was employed to accurately reproduce the observed vibrational structure. We present the 364 nm negative ion photoelectron spectra of the halomethyl anions CHX_2^- and CDX_2^- (X = Cl, Br, I) and report electron affinities, vibrational frequencies, and geometries.

  20. Electron anions and the glass transition temperature.

    PubMed

    Johnson, Lewis E; Sushko, Peter V; Tomota, Yudai; Hosono, Hideo

    2016-09-01

    Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32](2+) ⋅ (e(-))2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design. PMID:27559083

  1. Tracer Partitioning in Two-Phase Flow

    NASA Astrophysics Data System (ADS)

    Sathaye, K.; Hesse, M. A.

    2012-12-01

    The concentration distributions of geochemical tracers in a subsurface reservoir can be used as an indication of the reservoir flow paths and constituent fluid origin. In this case, we are motivated by the origin of marked geochemical gradients in the Bravo Dome natural CO2 reservoir in northeastern New Mexico. This reservoir contains 99% CO2 with various trace noble gas components and overlies the formation brine in a sloping aquifer. It is thought that magmatic CO2 entered the reservoir, and displaced the brine. This displacement created gradients in the concentrations of the noble gases. Two models to explain noble gas partitioning in two-phase flow are presented here. The first model assumes that the noble gases act as tracers and uses a first order non-linear partial differential equation to compute the volume fraction of each phase along the displament path. A one-way coupled partial differential equation determines the tracer concentration, which has no effect on the overall flow or phase saturations. The second model treats each noble gas as a regular component resulting in a three-component, two-phase system. As the noble gas injection concentration goes to zero, we see the three-component system behave like the one-way coupled system of the first model. Both the analytical and numerical solutions are presented for these models. For the process of a gas displacing a liquid, we see that a noble gas tracer with greater preference for the gas phase, such as Helium, will move more quickly along the flowpath than a heavier tracer that will more easily enter the liquid phase, such as Argon. When we include partial miscibility of both the major and trace components, these differences in speed are shown in a bank of the tracer at the saturation front. In the three component model, the noble gas bank has finite width and concentration. In the limit where the noble gas is treated as a tracer, the width of the bank is zero and the concentration increases linearly

  2. Halon-1301, a new Groundwater Age Tracer

    NASA Astrophysics Data System (ADS)

    Beyer, Monique; van der Raaij, Rob; Morgenstern, Uwe; Jackson, Bethanna

    2015-04-01

    Groundwater dating is an important tool to assess groundwater resources in regards to direction and time scale of groundwater flow and recharge and to assess contamination risks and manage remediation. To infer groundwater age information, a combination of different environmental tracers, such as tritium and SF6, are commonly used. However ambiguous age interpretations are often faced, due to a limited set of available tracers and limitations of each tracer method when applied alone. There is a need for additional, complementary groundwater age tracers. We recently discovered that Halon-1301, a water soluble and entirely anthropogenic gaseous substance, may be a promising candidate [Beyer et al, 2014]. Halon-1301 can be determined along with SF6, SF5CF3 and CFC-12 in groundwater using a gas chromatography setup with attached electron capture detector developed by Busenberg and Plummer [2008]. Halon-1301 has not been assessed in groundwater. This study assesses the behaviour of Halon-1301 in water and its suitability as a groundwater age tracer. We determined Halon-1301 in 17 groundwater and various modern (river) waters sites located in 3 different groundwater systems in the Wellington Region, New Zealand. These waters have been previously dated with tritium, CFC-12, CFC-11 and SF6 with mean residence times ranging from 0.5 to over 100 years. The waters range from oxic to anoxic and some show evidence of CFC contamination or degradation. This allows us to assess the different properties affecting the suitability of Halon-1301 as groundwater age tracer, such as its conservativeness in water and local contamination potential. The samples are analysed for Halon-1301 and SF6simultaneously, which allows identification of issues commonly faced when using gaseous tracers such as contamination with modern air during sampling. Overall we found in the assessed groundwater samples Halon-1301 is a feasible new groundwater tracer. No sample indicated significantly elevated

  3. Resistance absorption of some groundwater tracers in porous media

    NASA Astrophysics Data System (ADS)

    Jafari, Fateme

    2010-05-01

    Absorption of tracer to the aquifer material is among the most important factors which should be considered when a tracing program is considered. In this study, the absorption of the tracer into the porous media is analyzed experimentally for some of the most important and applied tracers as uranine, rhodamine B, eosin, potassium permanganate, sodium chloride and potassium chloride. For each tracer, effect of initial tracer concentration and percentage of fine grain sediments on tracer absorption in porous media is analyzed. According to the final results, rhodamine B and potassium permanganate have the less resistance against absorption to aquifer material, whilst eosin and uranine are the most resistant tracers among the examined ones. Key Words: Tracer, Absorption, Aquifer, Column Method

  4. AIR INFILTRATION MEASUREMENTS USING TRACER GASES: A LITERATURE REVIEW

    EPA Science Inventory

    The report gives results of a literature review of air filtration measurements using tracer gases, including sulfur hexafluoride, hydrogen, carbon monoxide, carbon dioxide, nitrous oxide, and radioactive argon and krypton. Sulfur hexafluoride is the commonest tracer gas of choice...

  5. EFFICIENT HYDROLOGICAL TRACER-TEST DESIGN (EHTD) MODEL

    EPA Science Inventory

    Hydrological tracer testing is the most reliable diagnostic technique available for establishing flow trajectories and hydrologic connections and for determining basic hydraulic and geometric parameters necessary for establishing operative solute-transport processes. Tracer-test...

  6. Tracer Interpretation Using Temporal Moments on a Spreadsheet

    SciTech Connect

    G. Michael Shook; J. Hope Forsmann

    2005-06-01

    This report presents a method for interpreting geothermal tracer tests. The method is based on the first temporal moment (mean residence time) of the tracer in the subsurface. The individual steps required to interpret a tracer test are reviewed and discussed. And an example tracer test directs the user through the interpretation method. An Excel spreadsheet application of the interpretation method is a companion document to this report.

  7. A continuous fast-response dual-tracer analyzer for halogenated atmospheric tracer studies

    SciTech Connect

    Rydock, J.P.; Lamb, B.K.

    1994-10-01

    An apparatus for the simultaneous measurement of two tracers, sulfur hexafluoride (SF6) and a perfluorocarbon compound, is introduced. The new instrument is a modification of a commercially available fast-response, continuous analyzer for single halogenated atmospheric tracer studies. A two-channel flow system was implemented consisting of an alumina cartridge in one channel and a glass beads cartridge of equal flow resistance in the second channel. The alumina passes only sulfur hexafluoride, while the glass beads pass both SF6 and the perfluoroarbon tracer. The SF6 is quantified directly from the electron capture detector (ECD) signal in the alumina channel, and the perfluorocarbon concentration is obtained from the difference of the ECD responses in the two channels. The dual-tracer analyzer is field portable for mobile operations or fixed-location monitoring, has a response time of 1.2 s, and has limits of detection of about 15 pptv for SF6 and 10 pptv for perfluoro-methylcyclohexane, which was the principal perfluorocarbon tracer used in this study. The present instrument configuration, which requires periodic purging of the adsorbent trap, can obtain continuous measurements for a 10-15-min segment in every half hour of operation. Dual-tracer data from a field demonstration test are presented.

  8. Photoelectron spectroscopy and theoretical studies of anion-π interactions: binding strength and anion specificity.

    PubMed

    Zhang, Jian; Zhou, Bin; Sun, Zhen-Rong; Wang, Xue-Bin

    2015-02-01

    Proposed in theory and then their existence confirmed, anion-π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, anion-π interaction strengths that are free from complications of condensed-phase environments have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic, was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl(-), Br(-), I(-), linear thiocyanate SCN(-), trigonal planar nitrate NO3(-), pyramidic iodate IO3(-), and tetrahedral sulfate SO4(2-)). The binding energies of the resultant gaseous 1 : 1 complexes (1·Cl(-), 1·Br(-), 1·I(-), 1·SCN(-), 1·NO3(-), 1·IO3(-) and 1·SO4(2-)) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion-specific effects. The binding strengths of Cl(-), NO3(-), IO3(-) with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal mol(-1), but only about 40% of that between 1 and SO4(2-). Quantum chemical calculations reveal that all the anions reside in the center of the cavity of 1 with an anion-π binding motif in the complexes' optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and charge distribution analyses further support anion-π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work illustrates that size-selective photoelectron

  9. Industrial tracer application in People's Republic of China

    SciTech Connect

    Maoyi, S.

    1988-01-01

    A number of important applications of radioisotopes and their compounds used as tracers in petroleum industry, metallurgical industry, mechanical industry, chemical industry, electronic industry, hydrology and water conservancy in China are introduced in this paper. The tracer technique applied to entomology is also mentioned. The industrial tracer applications are successful and beneficial in People's Republic of China from the examples given.

  10. Methodology for Quantitative Rapid Multi-Tracer PET Tumor Characterizations

    PubMed Central

    Kadrmas, Dan J.; Hoffman, John M.

    2013-01-01

    Positron emission tomography (PET) can image a wide variety of functional and physiological parameters in vivo using different radiotracers. As more is learned about the molecular basis for disease and treatment, the potential value of molecular imaging for characterizing and monitoring disease status has increased. Characterizing multiple aspects of tumor physiology by imaging multiple PET tracers in a single patient provides additional complementary information, and there is a significant body of literature supporting the potential value of multi-tracer PET imaging in oncology. However, imaging multiple PET tracers in a single patient presents a number of challenges. A number of techniques are under development for rapidly imaging multiple PET tracers in a single scan, where signal-recovery processing algorithms are employed to recover various imaging endpoints for each tracer. Dynamic imaging is generally used with tracer injections staggered in time, and kinetic constraints are utilized to estimate each tracers' contribution to the multi-tracer imaging signal. This article summarizes past and ongoing work in multi-tracer PET tumor imaging, and then organizes and describes the main algorithmic approaches for achieving multi-tracer PET signal-recovery. While significant advances have been made, the complexity of the approach necessitates protocol design, optimization, and testing for each particular tracer combination and application. Rapid multi-tracer PET techniques have great potential for both research and clinical cancer imaging applications, and continued research in this area is warranted. PMID:24312149

  11. Potential soluble, reactive, adsorptive and particulate tracers for source-receptor experiments in MATEX

    SciTech Connect

    Senum, G.I.; Dietz, R.N.

    1985-07-01

    A survey of potential non-conservative tracers for use in source-receptor studies in acid deposition is presented. Classes of tracers considered were water soluble tracers, chemically reactive tracers, adsorptive tracers and particulate tracers. A criterion used for the selection of compounds for nonconservative tracers is that they be as reasonably compatible in the analytical detection system used for the conservative perfluorocarbon tracers. For each class of non-conservative tracers several example compounds are given and discussed, along with the research needed to develop these tracers. A reasonable development time for these tracers is as follows; adsorptive tracers, 2 years; particulate tracers, 2 1/2 years; soluble tracers, 3 years and reactive tracers, 3 1/2 years. By development, it is meant that 1 or 2 tracers have been developed and at least demonstrated in a small field test. 6 refs., 2 tabs.

  12. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2011-11-22

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  13. Anion-Conducting Polymer, Composition, and Membrane

    SciTech Connect

    Pivovar, Bryan S.; Thorn, David L.

    2008-10-21

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  14. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2010-12-07

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  15. Anion-conducting polymer, composition, and membrane

    DOEpatents

    Pivovar, Bryan S.; Thorn, David L.

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  16. Bipyrrole-Strapped Calix[4]pyrroles: Strong Anion Receptors That Extract the Sulfate Anion

    SciTech Connect

    Kim, Sung Kuk; Lee, Juhoon; Williams, Neil J; Lynch, Vincent M.; Hay, Benjamin; Moyer, Bruce A; Sessler, Jonathan L.

    2014-01-01

    Cage-type calix[4]pyrroles 2 and 3 bearing two additional pyrrole groups on the strap have been synthesized. Compared with the parent calix[4]pyrrole (1), they were found to exhibit remarkably enhanced affinities for anions, including the sulfate anion (TBA+ salts), in organic media (CD2Cl2). This increase is ascribed to participation of the bipyrrole units in anion binding. Receptors 2 and 3 extract the hydrophilic sulfate anion (as the methyltrialkyl(C8-10)ammonium (A336+) salt)) from aqueous media into a chloroform phase with significantly improved efficiency (>10-fold relative to calix[4]pyrrole 1). These two receptors also solubilize into chloroform the otherwise insoluble sulfate salt, (TMA)2SO4 (tetramethylammonium sulfate).

  17. SUPRAMOLECULAR CHEMISTRY OF SELECTIVE ANION RECOGNITION FOR ANIONS OF ENVIRONMENTAL RELEVANCE

    EPA Science Inventory

    The supramolecular chemistry of selective anion recognition by synthetic polyammonium macrocycles will be explored in a comprehensive, long term program designed to provide new solutions to problems critical to the environmental initiative of DOE. Highly shape- and charge selecti...

  18. Dual-tracer background subtraction approach for fluorescent molecular tomography

    PubMed Central

    Holt, Robert W.; El-Ghussein, Fadi; Davis, Scott C.; Samkoe, Kimberley S.; Gunn, Jason R.; Leblond, Frederic

    2013-01-01

    Abstract. Diffuse fluorescence tomography requires high contrast-to-background ratios to accurately reconstruct inclusions of interest. This is a problem when imaging the uptake of fluorescently labeled molecularly targeted tracers in tissue, which can result in high levels of heterogeneously distributed background uptake. We present a dual-tracer background subtraction approach, wherein signal from the uptake of an untargeted tracer is subtracted from targeted tracer signal prior to image reconstruction, resulting in maps of targeted tracer binding. The approach is demonstrated in simulations, a phantom study, and in a mouse glioma imaging study, demonstrating substantial improvement over conventional and homogenous background subtraction image reconstruction approaches. PMID:23292612

  19. Interpreting tracer breakthrough tailing from different forced-gradient tracer experiment configurations in fractured bedrock

    USGS Publications Warehouse

    Becker, M.W.; Shapiro, A.M.

    2003-01-01

    Conceptual and mathematical models are presented that explain tracer breakthrough tailing in the absence of significant matrix diffusion. Model predictions are compared to field results from radially convergent, weak-dipole, and push-pull tracer experiments conducted in a saturated crystalline bedrock. The models are based upon the assumption that flow is highly channelized, that the mass of tracer in a channel is proportional to the cube of the mean channel aperture, and the mean transport time in the channel is related to the square of the mean channel aperture. These models predict the consistent -2 straight line power law slope observed in breakthrough from radially convergent and weak-dipole tracer experiments and the variable straight line power law slope observed in push-pull tracer experiments with varying injection volumes. The power law breakthrough slope is predicted in the absence of matrix diffusion. A comparison of tracer experiments in which the flow field was reversed to those in which it was not indicates that the apparent dispersion in the breakthrough curve is partially reversible. We hypothesize that the observed breakthrough tailing is due to a combination of local hydrodynamic dispersion, which always increases in the direction of fluid velocity, and heterogeneous advection, which is partially reversed when the flow field is reversed. In spite of our attempt to account for heterogeneous advection using a multipath approach, a much smaller estimate of hydrodynamic dispersivity was obtained from push-pull experiments than from radially convergent or weak dipole experiments. These results suggest that although we can explain breakthrough tailing as an advective phenomenon, we cannot ignore the relationship between hydrodynamic dispersion and flow field geometry at this site. The design of the tracer experiment can severely impact the estimation of hydrodynamic dispersion and matrix diffusion in highly heterogeneous geologic media.

  20. Geometric Skewness in the Passive Tracer Problem

    NASA Astrophysics Data System (ADS)

    Aminian, Manuchehr; Bernardi, Francesca; Camassa, Roberto; McLaughlin, Richard

    2015-11-01

    The classic work by G.I. Taylor describes the enhanced longitudinal diffusivity of a passive tracer in laminar pipe flow. Much work since then has gone into extending this result particularly in calculating the evolution of the scalar variance. However, less work has been done to describe the asymmetry of the distribution. We present the results from a modeling effort for the general picture of how the higher moments of the tracer distribution depend on geometry. We do this via analysis of ``channel-limiting'' geometries (rectangular ducts and elliptical pipes parameterized by their aspect ratio), using both new analytical tools and Monte-Carlo simulation, which have revealed a wealth of nontrivial behavior of the distributions at short and intermediate time. Funding from NSF grant Nos.: RTG DMS-0943851, CMG ARC-1025523, and DMS-1009750.

  1. Estimating sewer leakage from continuous tracer experiments.

    PubMed

    Rieckermann, Jörg; Bares, Vojtech; Kracht, Oliver; Braun, Daniel; Gujer, Willi

    2007-05-01

    Direct measurements of sewer leakage with continuous dosing of tracers are often considered too imprecise for practical applications. However, no mathematical framework for data analysis is reported in literature. In this paper, we present an improved experimental design and data analysis procedure together with a comprehensive framework for uncertainty assessment. Test runs in a 700 m-long watertight sewer showed no significant bias and a very high precision of the methodology. The standard error in the results was assessed to 2.6% of the labeled flow with a simplified model. It could be reduced to 1.2% when a dynamic data analysis procedure was applied. The major error contribution was caused by transient transport phenomena, which suggests that careful choosing of the experimental time is more important than the choice of a very specific tracer substance. Although the method is not intended to replace traditional CCTV inspections, it can provide complementary information for rational rehabilitation planning. PMID:17363025

  2. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    SciTech Connect

    Jonathan L. Sessler

    2007-09-21

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  3. Understanding and modeling removal of anionic organic contaminants (AOCs) by anion exchange resins.

    PubMed

    Zhang, Huichun; Shields, Anthony J; Jadbabaei, Nastaran; Nelson, Maurice; Pan, Bingjun; Suri, Rominder P S

    2014-07-01

    Ionic organic contaminants (OCs) are a growing concern for water treatment and the environment and are removed inefficiently by many existing technologies. This study examined removal of anionic OCs by anion exchange resins (AXRs) as a promising alternative. Results indicate that two polystyrene AXRs (IRA910 and IRA96) have higher sorption capacities and selectivity than a polyacrylate resin (A860). For the polystyrene resins, selectivity follows: phenolates ≥ aromatic dicarboxylates > aromatic monocarboxylates > benzenesulfonate > aliphatic carboxylates. This trend can be explained based on hydration energy, the number of exchange groups, and aromaticity and hydrophobicity of the nonpolar moiety (NPM) of the anions. For A860, selectivity only varies within a narrow range (0.13-1.64). Despite the importance of the NPM of the anions, neutral solutes were sorbed much less, indicating synergistic combinations of electrostatic and nonelectrostatic interactions in the overall sorption. By conducting multiple linear regression between Abraham's descriptors and nature log of selectivity, induced dipole-related interactions and electrostatic interactions were found to be the most important interaction forces for sorption of the anions, while solute H-bond basicity has a negative effect. A predictive model was then developed for carboxylates and phenolates based on the poly parameter linear free energy relationships established for a diverse range of 16 anions and 5 neutral solutes, and was validated by accurate prediction of sorption of five test solutes within a wide range of equilibrium concentrations and that of benzoate at different pH. PMID:24877792

  4. Into the regolith: digging for hydrological tracers

    NASA Astrophysics Data System (ADS)

    Moragues-Quiroga, Cristina; Hissler, Christophe; Chabaux, François; Legout, Arnaud; Stille, Peter

    2016-04-01

    The mineralogical and trace element composition of regoliths is a source of potential tracers of water behaviour in catchment systems. We propose an assessment of the most suitable spatial tracers for water collection, mixing, storage and release processes by incorporating geochemical signatures derived from trace and major elements to the description of sources and pathways of water contributions in the stream. To date, stable isotopes are widely used to trace water sources and water transit times but they are still missing a complementary tool which allows for the identification of end-members and the understanding of mixing processes within the regolith. Trace elements are known to be powerful and precise geochemical tracers of environmental processes and, therefore, they can be useful indicators of the spatial origin and evolution of regolith materials and water chemistry. We studied a whole slate regolith profile for its mineralogical, major and trace element composition. The different regolith components were subjected to a leaching experiment in order to identify chemical zonations within and assess the potential elements mobility. Rain, soil, stream and ground waters were collected at the same location than the regolith system over 4 years, analysed for their trace and major elements composition and compared to regolith and regolith leachates data. The results deliver valuable information on exchange processes at the water-mineral interface in the different zones of the regolith. The geochemical scheme of a complete regolith and the waters it holds is here presented to prove the efficiency of trace and major elements as complementary hydrological and geochemical tracers of water migration throughout a regolith till the stream.

  5. The ATLAS DDM Tracer monitoring framework

    NASA Astrophysics Data System (ADS)

    Zang, Dongsong; Garonne, Vincent; Barisits, Martin; Lassnig, Mario; Stewart, Graeme Andrew; Molfetas, Angelos; Beermann, Thomas

    2012-12-01

    The DDM Tracer monitoring framework is aimed to trace and monitor the ATLAS file operations on the Worldwide LHC Computing Grid. The volume of traces has increased significantly since the framework was put in production in 2009. Now there are about 5 million trace messages every day and peaks can be near 250Hz, with peak rates continuing to climb, which gives the current structure a big challenge. Analysis of large datasets based on on-demand queries to the relational database management system (RDBMS), i.e. Oracle, can be problematic, and have a significant effect on the database's performance. Consequently, We have investigated some new high availability technologies like messaging infrastructure, specifically ActiveMQ, and key-value stores. The advantages of key value store technology are that they are distributed and have high scalability; also their write performances are usually much better than RDBMS, all of which are very useful for the Tracer monitoring framework. Indexes and distributed counters have been also tested to improve query performance and provided almost real time results. In this paper, the design principles, architecture and main characteristics of Tracer monitoring framework will be described and examples of its usage will be presented.

  6. Commercial applications of perfluorocarbon tracer (PFT) technology

    SciTech Connect

    Dietz, R.N.

    1991-06-01

    Tracer technology can be successfully applied to many leak-checking and monitoring evaluations of operating systems (e.g., building HVACs), manufacturing processes and products (e.g., air conditioners), and subsurface components and systems (e.g., underground storage tanks). Perfluorocarbon tracer (PFT) technology is the most sensitive of all tracer technologies because the ambient background levels of the five (5) routinely-used PFTs are in the range of parts per 10{sup 15} parts of air (i.e., parts per quadrillion-ppq) and this technology's instrumentation can measure down to those levels. The effectiveness of this technology is achieved both in terms of cost (very little PFT need to be used) and detectability; for example, very small leaks can be rapidly detected. The PFT compounds, which are environmentally and biologically safe to use, are commercially available as are the sampling and analysis instrumentation. This presentation concerns (1) the steps being taken to commercialize this technology, (2) new applications of processes currently under study, and (3) applications in areas of use that will be particularly beneficial to the environment. 21 refs., 2 figs., 2 tabs.

  7. Tracer modeling in an urban environment

    SciTech Connect

    Reisner, J.M.; Smith, W.S.; Bossert, J.E.; Winterkamp, J.L.

    1998-12-31

    The accurate simulation of the transport of a tracer released into an urban area requires sufficiently high model resolution to resolve buildings and urban street canyons. Within the authors' group a modeling effort has been underway to develop a model -- termed HIGRAD -- capable of simulating flow at the high spatial resolution required within the urban environment. HIGRAD uses state-of-the-art numerical techniques to accurately simulate the regions of strong shear found near edges of buildings. HIGRAD also employs a newly developed radiation package which in addition to standard shortwave and longwave heating/cooling effects can account for the shadowing effects of building complexes on the urban flow field. Idealized simulations have been conducted which clearly illustrate the role radiation plays in transport and dispersion in an urban setting. The authors have also modeled the flow of an inert tracer in a realistic, complex urban environment. Complex flow/building interactions were produced during the simulation and these interactions had a significant impact on the transport of the tracer.

  8. Reliable determination of 237Np in environmental solid samples using 242Pu as a potential tracer.

    PubMed

    Qiao, Jixin; Hou, Xiaolin; Roos, Per; Miró, Manuel

    2011-04-15

    This paper reports an analytical method for rapid determination of neptunium ((237)Np) in environmental solid samples exploiting automated sequential injection (SI)-based anion exchange separation. Pivotal issues on analytical method performance were investigated including sorption behavior of (237)Np onto various AG 1-type anion exchangers; suitability of (242)Pu as a tracer for (237)Np determination in environmental solid samples; and long-term chemical stability of tetravalent Np. Experimental results revealed that the degree of resin cross-linking has a significant influence on the separation efficiency in terms of chemical yields of (237)Np and removal of interfering nuclides. Although ca. 30% of sorbed Np onto AG 1- × 4 was stripped out during HCl rinsing step for the removal of Th, chemical yield ratios of (237)Np to (242)Pu were proven steady with an average value of 0.67 ± 0.04 (n=15) under selected experimental conditions. Disulfite-8M HNO(3) was selected as a redox pair for valence adjustment to Np(IV) and the tetravalent Np in the sample solution was demonstrated to be stabilized for up to 5 days under 3°C. The analytical results for reference materials showed a good agreement with the expected values, thereby demonstrating the usefulness of (242)Pu as a non-isotopic tracer for (237)Np chemical yield monitoring. The on-column separation procedure fosters rapid analysis as required in emergency situations since each individual sample can be handled within 2.5h, and leads to a significant decrease in labor intensity compared to conventional batch-wise protocols. PMID:21376978

  9. High Yield C-Derivatization of Weakly Coordinating Carborane Anions

    PubMed Central

    Nava, Matthew J.

    2010-01-01

    Unlike the “parent” carborane anion CHB11H11−, halogenated carborane anions such as CHB11H5Br6− can be readily C-functionalized in high yield and purity, enhancing their utility as weakly coordinating anions. PMID:20450167

  10. Reversible photochromism of an N-salicylidene aniline anion.

    PubMed

    Jacquemin, Pierre-Loïc; Robeyns, Koen; Devillers, Michel; Garcia, Yann

    2014-01-21

    The first N-salicylidene aniline anion showing reversible solid state thermochromic and photochromic properties is described. The photo-isomerization involves a trans-keto form which is stabilized thanks to the local anion surrounding. This photochromic anion can be used as a guest for the preparation of hybrid materials by insertion into a cationic host matrix. PMID:24022381

  11. Evaluation of cation-anion interaction strength in ionic liquids.

    PubMed

    Fernandes, Ana M; Rocha, Marisa A A; Freire, Mara G; Marrucho, Isabel M; Coutinho, João A P; Santos, Luís M N B F

    2011-04-14

    Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry. PMID:21425809

  12. Across North America tracer experiment (ANATEX): Sampling and analysis

    NASA Astrophysics Data System (ADS)

    Draxler, R. R.; Dietz, R.; Lagomarsino, R. J.; Start, G.

    Between 5 January 1987 and 29 March 1987, there were 33 releases of different tracers from each of two sites: Glasgow, MT and St. Cloud, MN. The perfluorocarbon tracers were routinely released in a 3-h period every 2.5 days, alternating between daytime and night-time tracer releases. Ground-level air samples of 24-h duration were taken at 77 sites mostly located near rawinsonde stations east of 105°W and between 26°N and 55°N. Weekly air samples were taken at 12 remote sites between San Diego, CA and Pt. Barrow, AK and between Norway and the Canary Islands. Short-term 6-h samples were collected at ground level and 200 m AGL along an arc of five towers between Tulsa, OK and Green Bay, WI. Aircraft sampling within several hundred kilometers of both tracer release sites was used to establish the initial tracer path. Experimental design required improved sampler performance, new tracers with lower atmospheric backgrounds, and improvements in analytic precision. The advances to the perfluorocarbon tracer system are discussed in detail. Results from the tracer sampling showed that the average and peak concentrations measured over the daily ground-level sampling network were consistent with what would be calculated using mass conservative approaches. however, ground-level samples from individual tracer patterns showed considerable complexity due to vertical stability or the interaction of the tracer plumes with low pressure and frontal systems. These systems could pass right through the tracer plume without appreciable effect. Aircraft tracer measurements are used to confirm the initial tracer trajectory when the narrow plume may miss the coarser spaced ground-level sampling network. Tower tracer measurements showed a more complex temporal structure than evident from the longer duration ground-level sampling sites. Few above background plume measurements were evident in the more distant remote sampling network due to larger than expected uncertainties in the ambient

  13. Recover Act. Verification of Geothermal Tracer Methods in Highly Constrained Field Experiments

    SciTech Connect

    Becker, Matthew W.

    2014-05-16

    pumping tests in identifying a poorly connected well. As a result, we were able to predict which well pairs would demonstrate channelized flow. The focus of the tracer investigation was multi-ionic tests. In multi-ionic tests several ionic tracers are injected simultaneously and the detected in a nearby pumping well. The time history of concentration, or breakthrough curve, will show a separation of the tracers. Anionic tracers travel with the water but cationic tracer undergo chemical exchange with cations on the surface of the rock. The degree of separation is indicative of the surface area exposed to the tracer. Consequently, flow channelization will tend to decrease the separation in the breakthrough. Estimation of specific surface area (the ration of fracture surface area to formation volume) is performed through matching the breakthrough curve with a transport model. We found that the tracer estimates of surface area were confirmed the prediction of channelized flow between well pairs produced by the periodic hydraulic tests. To confirm that the hydraulic and tracer tests were correctly predicting channelize flow, we imaged the flow field using surface GPR. Saline water was injected between the well pairs which produced a change in the amplitude and phase of the reflected radar signal. A map was produced of the migration of saline tracer from these tests which qualitatively confirmed the flow channelization predicted by the hydraulic and tracer tests. The resolution of the GPR was insufficient to quantitatively estimate swept surface area, however. Surface GPR is not applicable in typical geothermal fields because the penetration depths do not exceed 10’s of meters. Nevertheless, the method of using of phase to measure electrical conductivity and the assessment of antennae polarization represent a significant advancement in the field of surface GPR. The effect of flow character on fracture / rock thermal exchange was evaluated using heated water as a tracer. Water

  14. Properties of an ideal PET perfusion tracer: new PET tracer cases and data.

    PubMed

    Maddahi, Jamshid

    2012-02-01

    An ideal positron emission tomography (PET) tracer should be highly extractable by the myocardium and able to provide high-resolution images, should enable quantification of absolute myocardial blood flow (MBF), should be compatible with both pharmacologically induced and exercise-induced stress imaging, and should not require an on-site cyclotron. The PET radionuclides nitrogen-13 ammonia and oxygen-15 water require an on-site cyclotron. Rubidium-82 may be available locally due to the generator source, but greater utilization is limited because of its relatively low myocardial extraction fraction, long positron range, and generator cost. Flurpiridaz F 18, a novel PET tracer in development, has a high-extraction fraction, short positron range, and relatively long half-life (as compared to currently available tracers), and may be produced at regional cyclotrons. Results of early clinical trials suggest that both pharmacologically and exercise-induced stress PET imaging protocols can be completed more rapidly and with lower patient radiation exposure than with single-photon emission computerized tomography (SPECT) tracers. As compared to SPECT images in the same patients, flurpiridaz F 18 PET images showed better defect contrast. Flurpiridaz F 18 is a potentially promising tracer for assessment of myocardial perfusion, measurement of absolute MBF, calculation of coronary flow reserves, and assessment of cardiac function at the peak of the stress response. PMID:22259007

  15. Asian Tracer Experiment and Atmospheric Modeling (TEAM) Project: Draft Field Work Plan for the Asian Long-Range Tracer Experiment

    SciTech Connect

    Allwine, K Jerry; Flaherty, Julia E.

    2007-08-01

    This report provides an experimental plan for a proposed Asian long-range tracer study as part of the international Tracer Experiment and Atmospheric Modeling (TEAM) Project. The TEAM partners are China, Japan, South Korea and the United States. Optimal times of year to conduct the study, meteorological measurements needed, proposed tracer release locations, proposed tracer sampling locations and the proposed durations of tracer releases and subsequent sampling are given. Also given are the activities necessary to prepare for the study and the schedule for completing the preparation activities leading to conducting the actual field operations. This report is intended to provide the TEAM members with the information necessary for planning and conducting the Asian long-range tracer study. The experimental plan is proposed, at this time, to describe the efforts necessary to conduct the Asian long-range tracer study, and the plan will undoubtedly be revised and refined as the planning goes forward over the next year.

  16. The chemistry of gold as an anion.

    PubMed

    Jansen, Martin

    2008-09-01

    Due to relativistic and classical shell structure effects, the 6s orbital of gold is significantly contracted and energetically stabilized. This is reflected by a strikingly high electron affinity, and a distinct tendency to adopt negatively polarized valence states. This tutorial review focuses on the chemistry of gold as an anion, displaying the integral ionic charge number of 1-. Two synthetic approaches to compounds containing monoatomic gold anions have become available: (1) reacting elemental gold with molten caesium and an oxide, e.g. Cs2O; (2) metathesis reactions involving Au- dissolved in liquid ammonia. Both procedures have proven to be rather versatile. Aurides synthesized along these routes are surveyed, in particular with respect to their structures and bonding properties. PMID:18762832

  17. Anion photoelectron spectroscopy of radicals and clusters

    SciTech Connect

    Travis, Taylor R.

    1999-12-16

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying {sup 2}{Sigma} and {sup 2}{Pi} states of C{sub 2n}H (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C{sub 2}H and C{sub 4}H. Other radicals studied include NCN and I{sub 3}. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I{sub 3} revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  18. Specific anion effects in Artemia salina.

    PubMed

    Lo Nostro, Pierandrea; Ninham, Barry W; Carretti, Emiliano; Dei, Luigi; Baglioni, Piero

    2015-09-01

    The specific anion effect on the vitality of Artemia salina was investigated by measuring the Lethal Time LT50 of the crustaceans in the presence of different sodium salts solutions at room temperature and at the same ionic strength as natural seawater. Fluoride, thiocyanate and perchlorate are the most toxic agents, while chloride, bromide and sulfate are well tolerated. The rates of oxygen consumption of brine shrimps were recorded in mixed NaCl+NaF or NaCl+NaSCN solutions as a function of time. The results are discussed in terms of the Hofmeister series, and suggest that, besides the biochemical processes that involve F(-), SCN(-) and ClO4(-), the different physico-chemical properties of the strong kosmotropic and chaotropic anions may contribute in determining their strong toxicity for A. salina. PMID:25978674

  19. Lowest autodetachment state of the water anion

    NASA Astrophysics Data System (ADS)

    Houfek, Karel; Čížek, Martin

    2016-05-01

    The potential energy surface of the ground state of the water anion H2O- is carefully mapped using multireference CI calculations for a large range of molecular geometries. Particular attention is paid to a consistent description of both the O-+H2 and OH-+H asymptotes and to a relative position of the anion energy to the ground state energy of the neutral molecule. The autodetachment region, where the anion state crosses to the electronic continuum is identified. The local minimum in the direction of the O- + H2 channel previously reported by Werner et al. [J. Chem. Phys. 87, 2913 (1987)] is found to be slighly off the linear geometry and is separated by a saddle from the autodetachment region. The autodetachment region is directly accessible from the OH-+H asymptote. For the molecular geometries in the autodetachment region and in its vicinity we also performed fixed-nuclei electron-molecule scattering calculations using the R-matrix method. Tuning of consistency of a description of the correlation energy in both the multireference CI and R-matrix calculations is discussed. Two models of the correlation energy within the R-matrix method that are consistent with the quantum chemistry calculations are found. Both models yield scattering quantities in a close agreement. The results of this work will allow a consistent formulation of the nonlocal resonance model of the water anion in a future publication. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  20. Cooling dynamics of carbon cluster anions

    NASA Astrophysics Data System (ADS)

    Shiromaru, H.; Furukawa, T.; Ito, G.; Kono, N.; Tanuma, H.; Matsumoto, J.; Goto, M.; Majima, T.; Sundén, A. E. K.; Najafian, K.; Pettersson, M. S.; Dynefors, B.; Hansen, K.; Azuma, T.

    2015-09-01

    A series of ion storage experiments on small carbon cluster anions was conducted to understand size-dependent cooling processes. The laser-induced delayed electron detachment time profile show clear even/odd alternation due to the presence of the electronic cooling. The time evolution of the internal energy distribution was simulated for Cn- (n=4 to 7) with a common procedure taking vibrational and electronic cooling into account.

  1. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  2. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  3. Anion formation by neutral resonant ionization

    NASA Astrophysics Data System (ADS)

    Vogel, John S.

    2015-10-01

    A collision-radiation model of the cesium plasma that forms within a pitted or recessed sample in a Middleton-type sputter ion source showed that excited states of Cs formed. These excited states of neutral Cs undergo resonant electron transfer with neutral sputtered atoms of AMS samples to produce the accelerated anions. Numerous reported effects from over 30 years are readily explained by this mechanism, including several that puzzled Middleton.

  4. Electronically excited states of PANH anions.

    PubMed

    Theis, Mallory L; Candian, Alessandra; Tielens, Alexander G G M; Lee, Timothy J; Fortenberry, Ryan C

    2015-06-14

    The singly deprotonated anion derivatives of nitrogenated polycyclic aromatic hydrocarbons (PANHs) are investigated for their electronically excited state properties. These include single deprotonation of the two unique arrangements of quinoline producing fourteen different isomers. This same procedure is also undertaken for single deprotonation of the three nitrogenation isomers of acridine and the three of pyrenidine. It is shown quantum chemically that the quinoline-class of PANH anion derivatives can only produce a candidate dipole-bound excited state each, a state defined as the interaction of an extra electron with the dipole moment of the corresponding neutral. However, the acridine- and pyrenidine-classes possess valence excited states as well as the possible dipole-bound excited states where the latter is only possible if the dipole moment is sufficiently large to retain the extra electron; the valence excitation is independent of the radical dipolar strength. As a result, the theoretical vertically computed electronic spectra of deprotonated PANH anion derivatives is fairly rich in the 1.5 eV to 2.5 eV range significantly opening the possibilities for these molecules to be applied to longer wavelength studies of visible and near-IR spectroscopy. Lastly, the study of these systems is also enhanced by the inclusion of informed orbital arrangements in a simply constructed basis set that is shown to be more complete and efficient than standard atom-centered functions. PMID:25975430

  5. Effect of anionic amphophiles on erythrocyte properties.

    PubMed

    McMillan, D E; Utterback, N G; Wujek, J J

    1983-01-01

    This preliminary study describes effects of two pharmacologic agents on erythrocyte behavior. Increased erythrocyte aggregation has been proposed as important in the pathogenesis of a number of disorders, but the exact mechanism by which it plays a role in disease production remains unclear. Several anionic amphophiles have been reported to benefit diabetic vascular disease and atherosclerosis. If anionic amphophiles enter the erythrocyte plasma membrane they can increase its negative charge, reducing the energy of attraction between red blood cells and diminishing erythrocyte aggregation. Erythrocytes were studied after suspension in phosphate-buffered saline containing dextran as an aggregation-promoting agent. A marginal reduction of the suspension's viscosity was found at low shear rate when 2,5- dihydroxybenzene sulfonate was added. Additionally, erythrocyte sedimentation rate was marginally influenced. Both dihydroxybenzene sulfonate and acetylsalicylate protected human erythrocytes from hemolysis at concentrations from 10(-3) to 10(-5) M. The removal of erythrocyte sialic acid using neuraminidase to reduce surface negative charge led to unequivocal interference with aggregation (MAI technique of CHIEN et al., J. Gen. Physiol., 1973) by both anionic amphophiles were studied. Dihydroxybenzene sulfonate and actylsalicylate reduced the aggregation propensity of sialic-free erythrocytes, suggesting that the effect on the low shear rate viscosity of sialic acid-containing erythrocytes, though modest, is real. PMID:6587820

  6. Several hemicyanine dyes as fluorescence chemosensors for cyanide anions

    NASA Astrophysics Data System (ADS)

    Liang, Muhan; Wang, Kangnan; Guan, Ruifang; Liu, Zhiqiang; Cao, Duxia; Wu, Qianqian; Shan, Yanyan; Xu, Yongxiao

    2016-05-01

    Four hemicyanine dyes as chemosensors for cyanide anions were synthesized easily. Their photophysical properties and recognition properties for cyanide anions were investigated. The results indicate that all the dyes can recognize cyanide anions with obvious color, absorption and fluorescence change. The recognition mechanism analysis basing on in situ 1H NMR and Job plot data indicates that to the compounds with hydroxyl group, the recognition mechanism is intramolecular hydrogen bonding interaction. However, to the compounds without hydroxyl group, cyanide anion is bonded to carbon-carbon double bond in conjugated bridge and induces N+ CH3 to neutral NCH3. Fluorescence of the compounds is almost quenched upon the addition of cyanide anions.

  7. The 2-Arsaethynolate Anion: Synthesis and Reactivity Towards Heteroallenes.

    PubMed

    Hinz, Alexander; Goicoechea, Jose M

    2016-07-18

    The synthesis and isolation of the 2-arsaethynolate anion, AsCO(-) , and its subsequent reactivity towards heteroallenes is reported. Reactions with ketenes and carbodiimides afford four-membered anionic heterocycles in formal [2+2] cycloaddition reactions. By contrast, reaction with an isocyanate yielded a 1,4,2-diazaarsolidine-3,5-dionide anion and the unprecedented cluster anions As10 (2-) and As12 (4-) . These preliminary reactivity studies hint at the enormous potential synthetic utility of this novel anion, which may be employed as an arsenide (As(-) ) source. PMID:27093942

  8. 3-D numerical evaluation of density effects on tracer tests.

    PubMed

    Beinhorn, M; Dietrich, P; Kolditz, O

    2005-12-01

    In this paper we present numerical simulations carried out to assess the importance of density-dependent flow on tracer plume development. The scenario considered in the study is characterized by a short-term tracer injection phase into a fully penetrating well and a natural hydraulic gradient. The scenario is thought to be typical for tracer tests conducted in the field. Using a reference case as a starting point, different model parameters were changed in order to determine their importance to density effects. The study is based on a three-dimensional model domain. Results were interpreted using concentration contours and a first moment analysis. Tracer injections of 0.036 kg per meter of saturated aquifer thickness do not cause significant density effects assuming hydraulic gradients of at least 0.1%. Higher tracer input masses, as used for geoelectrical investigations, may lead to buoyancy-induced flow in the early phase of a tracer test which in turn impacts further plume development. This also holds true for shallow aquifers. Results of simulations with different tracer injection rates and durations imply that the tracer input scenario has a negligible effect on density flow. Employing model cases with different realizations of a log conductivity random field, it could be shown that small variations of hydraulic conductivity in the vicinity of the tracer injection well have a major control on the local tracer distribution but do not mask effects of buoyancy-induced flow. PMID:16183165

  9. Hydrocarbon precombusting catalyst survey and optimization for perfluorocarbon tracer analysis in subsurface tracer applications

    SciTech Connect

    Senum, G.I.; Cote, E.A.; D'Ottavio, T.W.; Dietz, R.N.

    1989-05-01

    The extension of the perfluorocarbon tracer (PFT) technology, as developed for atmospheric dispersion and transport studies to petroleum reservoir characterization studies, required the development of a more robust catalyst to remove analysis interferents caused by the adsorption of 5 liter hydrocarbon reservoir gas samples containing PFT onto carbonaceous adsorbent samplers. Two approaches were studied: (1) replacement of the present internal laboratory PFT analysis system catalyst with a more effective catalyst and, if this was not viable, (2) development of an external preprocessing catalyst train, to significantly reduce the hydrocarbon levels in the sample, without affecting the perfluorocarbon tracers. 13 figs., 13 tabs.

  10. Relationship between anion binding and anion permeability revealed by mutagenesis within the cystic fibrosis transmembrane conductance regulator chloride channel pore

    PubMed Central

    Linsdell, Paul

    2001-01-01

    Anion binding within the pores of wild-type and mutant cystic fibrosis transmembrane conductance regulator (CFTR) Cl− channels, expressed in two different mammalian cell lines, was assayed using patch clamp recording. Specifically, experiments measured both the conductance of different anions and the ability of other permeant anions to block Cl− permeation through the pore. Under symmetrical ionic conditions, wild-type CFTR channels showed the conductance sequence Cl− >NO3− >Br−≥formate >F− >SCN−≈ ClO4−. High SCN− conductance was not observed, nor was there an anomalous mole fraction effect of SCN− on conductance under the conditions used. Iodide currents could not be measured under symmetrical ionic conditions, but under bi-ionic conditions I− conductance appeared low. Chloride currents through CFTR channels were blocked by low concentrations (10 mM) of SCN−, I− and ClO4−, implying relatively tight binding of these anions within the pore. Two mutations in CFTR which alter the anion permeability sequence, F337S and T338A, also altered the anion conductance sequence. Furthermore, block by SCN−, I− and ClO4− were weakened in both mutants. Both these effects are consistent with altered anion binding within the pore. The effects of mutations on anion permeability and relative anion conductance suggested that, for most anions, increased permeability was associated with increased conductance. This indicates that the CFTR channel pore does not achieve its anion selectivity by selective anion binding within the mutated region. Instead, it is suggested that entry of anions into the region around F337 and T338 facilitates their passage through the pore. In wild-type CFTR channels, anion entry into this crucial pore region is probably dominated by anion hydration energies. PMID:11179391

  11. Relationship between anion binding and anion permeability revealed by mutagenesis within the cystic fibrosis transmembrane conductance regulator chloride channel pore.

    PubMed

    Linsdell, P

    2001-02-15

    1. Anion binding within the pores of wild-type and mutant cystic fibrosis transmembrane conductance regulator (CFTR) Cl- channels, expressed in two different mammalian cell lines, was assayed using patch clamp recording. Specifically, experiments measured both the conductance of different anions and the ability of other permeant anions to block Cl- permeation through the pore. 2. Under symmetrical ionic conditions, wild-type CFTR channels showed the conductance sequence Cl- > NO3- > Br- > or = formate > F- > SCN- congruent to ClO4-. 3. High SCN- conductance was not observed, nor was there an anomalous mole fraction effect of SCN- on conductance under the conditions used. Iodide currents could not be measured under symmetrical ionic conditions, but under bi-ionic conditions I- conductance appeared low. 4. Chloride currents through CFTR channels were blocked by low concentrations (10 mM) of SCN-, I- and ClO4-, implying relatively tight binding of these anions within the pore. 5. Two mutations in CFTR which alter the anion permeability sequence, F337S and T338A, also altered the anion conductance sequence. Furthermore, block by SCN-, I- and ClO4- were weakened in both mutants. Both these effects are consistent with altered anion binding within the pore. 6. The effects of mutations on anion permeability and relative anion conductance suggested that, for most anions, increased permeability was associated with increased conductance. This indicates that the CFTR channel pore does not achieve its anion selectivity by selective anion binding within the mutated region. Instead, it is suggested that entry of anions into the region around F337 and T338 facilitates their passage through the pore. In wild-type CFTR channels, anion entry into this crucial pore region is probably dominated by anion hydration energies. PMID:11179391

  12. Anion Chemistry On Titan: Probing the Destruction Mechanisms of Nitrile Anions by Interaction with Photons

    NASA Astrophysics Data System (ADS)

    Zabka, J.; Polášek, M.; Bradyová, M.; Flenerová, Z.; Obluková, M.; Ascenzi, D.; Vuitton, V.; Giuliani, A.; Nahon, L.; Milosavljevic, A.; Romanzin, C.; Alcaraz, C.

    2013-09-01

    The aim of this work is to study the interaction with VUV photons of mass-selected negative ions relevant for the understanding of Titan atmosphere. Characterization of their formation [1] and destruction rate is of fundamental importance for modeling Titan ionosphere chemistry and understanding the observations of heavy anions by the CAPS/ELS spectrometer on board of the CASSINI spacecraft. The objective here is to measure their transformation into smaller anions through photodissociation and their destruction through photodetachment. The parent anions CN- are produced from CH3CN in the APCI source of a commercial mass spectrometer LTQ XL (Thermo Scientific) [2,3] and reacted with HC3N in the trap to produce heavier anions through the CN-+ x HC3N(HC3N)yC2p+1 N-+ z HCN processes. These product anions are then mass-selected in the trap and irradiated with VUV photons (5-21 eV) from the DESIRS beamline. Their decay is followed as a function of irradiation time as illustrated in Figure 1.

  13. Hydroxy double salt anion exchange kinetics: effects of precursor structure and anion size.

    PubMed

    Kandare, Everson; Hossenlopp, Jeanne M

    2005-05-01

    (1)H NMR spectroscopy and powder X-ray diffraction have been used to explore the details of anion exchange reactions of two layered hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA), nickel zinc hydroxy acetate (NZA), and a related layered material, zinc hydroxy acetate (ZHA), at room temperature (21-22 degrees C). Reactions that followed Avrami-Erofe'ev kinetics with respect to temporal profiles for acetate release, ZCA with butyrate (k = 1.7 x 10(-3) s(-1)), and octanoate (k = 0.79 x 10(-3) s(-1)) anions, as well as ZHA with octanoate (k = 2.6 x 10(-3) s(-1)), demonstrate that rate constants for acetate release are influenced by the exchange anion relative size as well as by the solid precursor structure/composition. The reaction of NZA with octanoate deviated from expected Avrami-Erofe'ev behavior, with evidence for an intermediate species in the solid phase that may influence the rate of acetate release into solution. The reaction of ZCA with formate anions exhibited a unique zeroth-order kinetics release of acetate, providing the possibility of developing tunable nanostructured anion release sources by use of variations in the size of the exchange species. PMID:16851994

  14. The benzene radical anion: A computationally demanding prototype for aromatic anions

    SciTech Connect

    Bazante, Alexandre P. Bartlett, Rodney J.; Davidson, E. R.

    2015-05-28

    The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examine the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C{sub 2} symmetry is located below one D{sub 2h} stationary point on a C{sub 2h} pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (A{sub iso}) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ.

  15. The benzene radical anion: A computationally demanding prototype for aromatic anions.

    PubMed

    Bazante, Alexandre P; Davidson, E R; Bartlett, Rodney J

    2015-05-28

    The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examine the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C2 symmetry is located below one D2h stationary point on a C2h pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (Aiso) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ. PMID:26026444

  16. CityFlux perfluorocarbon tracer experiments

    NASA Astrophysics Data System (ADS)

    Petersson, F. K.; Martin, D.; White, I. R.; Henshaw, S. J.; Nickless, G.; Longley, I.; Percival, C. J.; Gallagher, M.; Shallcross, D. E.

    2010-01-01

    In June 2006, two perfluorocarbon tracer experiments were conducted in central Manchester UK as part of the CityFlux campaign. The main aim was to investigate vertical dispersion in an urban area during convective conditions, but dispersion mechanisms within the street network were also studied. Paired receptors were used in most cases where one receptor was located at ground level and one at roof level. One receptor was located on the roof of Portland Tower which is an 80 m high building in central Manchester. Source receptor distances in the two experiments varied between 120 and 600 m. The results reveal that maximum concentration was sometimes found at roof level rather than at ground level implying the effectiveness of convective forces on dispersion. The degree of vertical dispersion was found to be dependent on source receptor distance as well as on building height in proximity to the release site. Evidence of flow channelling in a street canyon was also found. Both a Gaussian profile and a street network model were applied and the results show that the urban topography may lead to highly effective flow channelling which therefore may be a very important dispersion mechanism should the right meteorological conditions prevail. The experimental results from this campaign have also been compared with a simple urban dispersion model that was developed during the DAPPLE framework and show good agreement with this. The results presented here are some of the first published regarding vertical dispersion. More tracer experiments are needed in order to further characterise vertical concentration profiles and their dependence on, for instance, atmospheric stability. The impact of urban topography on pollutant dispersion is important to focus on in future tracer experiments in order to improve performance of models as well as for our understanding of the relationship between air quality and public health.

  17. CityFlux perfluorocarbon tracer experiments

    NASA Astrophysics Data System (ADS)

    Petersson, F. K.; Martin, D.; White, I. R.; Henshaw, S. J.; Nickless, G.; Longley, I.; Percival, C. J.; Gallagher, M.; Shallcross, D. E.

    2010-07-01

    In June 2006, two perfluorocarbon tracer experiments were conducted in central Manchester UK as part of the CityFlux campaign. The main aim was to investigate vertical dispersion in an urban area during convective conditions, but dispersion mechanisms within the street network were also studied. Paired receptors were used in most cases where one receptor was located at ground level and one at roof level. One receptor was located on the roof of Portland Tower which is an 80 m high building in central Manchester. Source receptor distances in the two experiments varied between 120 and 600 m. The results reveal that maximum concentration was sometimes found at roof level rather than at ground level implying the effectiveness of convective forces on dispersion. The degree of vertical dispersion was found to be dependent on source receptor distance as well as on building height in proximity to the release site. Evidence of flow channelling in a street canyon was also found. Both a Gaussian profile and a street network model were applied and the results show that the urban topography may lead to highly effective flow channelling which therefore may be a very important dispersion mechanism should the right meteorological conditions prevail. The experimental results from this campaign have also been compared with a simple urban dispersion model that was developed during the DAPPLE framework and show good agreement with this. The results presented here are some of the first published regarding vertical dispersion. More tracer experiments are needed in order to further characterise vertical concentration profiles and their dependence on, for instance, atmospheric stability. The impact of urban topography on pollutant dispersion is important to focus on in future tracer experiments in order to improve performance of models as well as for our understanding of the relationship between air quality and public health.

  18. PIV tracer behavior on propagating shock fronts

    NASA Astrophysics Data System (ADS)

    Glazyrin, Fyodor N.; Mursenkova, Irina V.; Znamenskaya, Irina A.

    2016-01-01

    The present work was aimed at the quantitative particle image velocimetry (PIV) measurement of a velocity field near the front of a propagating shock wave and the study of the dynamics of liquid tracers crossing the shock front. For this goal, a shock tube with a rectangular cross-section (48  ×  24 mm) was used. The flat shock wave with Mach numbers M  =  1.4-2.0 propagating inside the tube channel was studied as well as an expanding shock wave propagating outside the channel with M  =  1.2-1.8 at its main axis. The PIV imaging of the shock fronts was carried out with an aerosol of dioctyl sebacate (DEHS) as tracer particles. The pressures of the gas in front of the shock waves studied ranged from 0.013 Mpa to 0.1 MPa in the series of experiments. The processed PIV data, compared to the 1D normal shock theory, yielded consistent values of wake velocity immediately behind the plain shock wave. Special attention was paid to the blurring of the velocity jump on the shock front due to the inertial particle lag and peculiarities of the PIV technique. A numerical algorithm was developed for analysis and correction of the PIV data on the shock fronts, based on equations of particle-flow interaction. By application of this algorithm, the effective particle diameter of the DEHS aerosol tracers was estimated as 1.03  ±  0.12 μm. A number of different formulations for particle drag were tested with this algorithm, with varying success. The results show consistency with previously reported experimental data obtained for cases of stationary shock waves.

  19. Radon as a Tracer for Lunar Volatiles

    NASA Technical Reports Server (NTRS)

    Friesen, Larry Jay

    1992-01-01

    Radon and its decay product polonium can be used as tracers to search for lunar volatiles. One effective technique to look for them would be by using alpha-particle spectrometers from lunar orbit. Alpha spectrometers were flown in the Apollo Service Modules during the Apollo 15 and 16 missions, and did observe Rn-222 and its decay product Po-210 on the lunar surface from orbit. This demonstrates that radon and polonium can be observed from orbit; what must next be shown is that such observations can reveal something about the locations of volatiles on the Moon.

  20. Fractal tracer distributions in turbulent field theories

    NASA Astrophysics Data System (ADS)

    Hansen, Jonas Lundbek; Bohr, Tomas

    1998-07-01

    We study the motion of passive tracers in a two-dimensional turbulent velocity field generated by the Kuramoto-Sivashinsky equation. By varying the direction of the velocity-vector with respect to the field-gradient we can continuously vary the two Lyapunov exponents for the particle motion and thereby find a regime in which the particle distribution is a strange attractor. We compare the Lyapunov dimension to the information dimension of actual particle distributions and show that there is good agreement with the Kaplan-Yorke conjecture. Similar phenomena have been observed experimentally.

  1. Metropolitan tracer experiment (METREX). Technical memo

    SciTech Connect

    Draxler, R.R.

    1985-10-01

    Several perfluorocarbon gas tracers were released at regular intervals for 1 year just outside of the metropolitan Washington, DC area. Continuous 8-h samples were collected at a central downtown site and two adjacent suburban locations. Monthly air samples were collected at 93 sites throughout the region at urban, suburban, and rural locations. Meteorological measurements were made on 5 towers instrumented for the experiment. The collected data can be used to quantify the errors from various dispersion-modeling techniques as well as study the influence of an urban area on the dispersion of pollutants.

  2. Pharmaceuticals as Groundwater Tracers - Applications and Limitations

    NASA Astrophysics Data System (ADS)

    Scheytt, T. J.; Mersmann, P.; Heberer, T.

    2003-12-01

    Pharmaceutically active substances and metabolites are found at concentrations up to the microgram/L-level in groundwater samples from the Berlin (Germany) area and from several other places world wide. Among the compounds detected in groundwater are clofibric acid, propyphenazone, diclofenac, ibuprofen, and carbamazepine. Clofibric acid, the active metabolite of clofibrate and etofibrate (blood lipid regulators) is detected in groundwater at maximum concentrations of 7300 ng/L. Among the most important input paths of drugs are excretion and disposal into the sewage system. Groundwater contamination is likely to be due to leaky sewage systems, influent streams, bank filtration, and irrigation with effluent water from sewage treatment plants. There are no known natural sources of the above mentioned pharmaceuticals. The use of pharmaceuticals as tracers may include: (a) Quantification of infiltration from underground septic tanks (b) Detection of leaky sewage systems / leaky sewage pipes (c) Estimation of the effectiveness of sewage treatment plants (d) Identification of transport pathways of other organic compounds (e) Quantification of surface water / groundwater interaction (f) Characterization of the biodegradation potential. The use of pharmaceuticals as tracers is limited by variations in input. These variations depend on the amount of drugs prescribed and used in the study area, the social structure of the community, the amount of hospital discharge, and temporal concentration variations. Furthermore, the analysis of trace amounts of pharmaceuticals is sophisticated and expensive and may therefore limit the applicability of pharmaceuticals as tracers. Finally, the transport and degradation behavior of pharmaceuticals is not fully understood. Preliminary experiments in the laboratory were conducted using sediment material and groundwater from the Berlin area to evaluate the transport and sorption behavior of selected drugs. Results of the column experiments

  3. Expanded Porphyrin-Anion Supramolecular Assemblies: Environmentally Responsive Sensors for Organic Solvents and Anions.

    PubMed

    Zhang, Zhan; Kim, Dong Sub; Lin, Chung-Yon; Zhang, Huacheng; Lammer, Aaron D; Lynch, Vincent M; Popov, Ilya; Miljanić, Ognjen Š; Anslyn, Eric V; Sessler, Jonathan L

    2015-06-24

    Porphyrins have been used frequently to construct supramolecular assemblies. In contrast, noncovalent ensembles derived from expanded porphyrins, larger congeners of naturally occurring tetrapyrrole macrocycles, are all but unknown. Here we report a series of expanded porphyrin-anion supramolecular assemblies. These systems display unique environmentally responsive behavior. Addition of polar organic solvents or common anions to the ensembles leads to either a visible color change, a change in the fluorescence emission features, or differences in solubility. The actual response, which could be followed easily by the naked eye, was found to depend on the specifics of the assembly, as well as the choice of analyte. Using the ensembles of this study, it proved possible to differentiate between common solvents, such as diethyl ether, THF, ethyl acetate, acetone, alcohol, acetonitrile, DMF, and DMSO, identify complex solvent systems, as well as distinguish between the fluoride, chloride, bromide, nitrate, and sulfate anions. PMID:25965790

  4. Supramolecular chemistry of selective anion recognition for anions of environmental relevance. 1998 annual progress report

    SciTech Connect

    Bowman-James, K.; Wilson, G.S.; Kuczera, K.; Moyer, B.

    1998-06-01

    'This project has as its focus the design and synthesis of polyammonium macrocyclic receptors for oxoanions of environmental importance. The basic research aspects of this project involve: (1) synthesis (and the search for improved synthetic methods); (2) solid state structure determination and thermodynamics studies (to ascertain structural criteria for and strength of anion binding); and (3) molecular dynamics simulations (to assess solution characteristics of the interactions between anions and their receptors). Applications-oriented goals include the fabrication of more selective anion-selective electrodes and the use of these compounds in liquid-liquid separations. The latter goal comprises the subcontract with Dr. Bruce Moyer at Oak Ridge National Laboratory. This report summarizes work after 1 year and 7 months of a 3-year project. To date, the authors have focussed on the design and synthesis of selective receptors for nitrate and phosphate.'

  5. Lidar Tracking of Multiple Fluorescent Tracers: Method and Field Test

    NASA Technical Reports Server (NTRS)

    Eberhard, Wynn L.; Willis, Ron J.

    1992-01-01

    Past research and applications have demonstrated the advantages and usefulness of lidar detection of a single fluorescent tracer to track air motions. Earlier researchers performed an analytical study that showed good potential for lidar discrimination and tracking of two or three different fluorescent tracers at the same time. The present paper summarizes the multiple fluorescent tracer method, discusses its expected advantages and problems, and describes our field test of this new technique.

  6. Evidence for anionic cation transport of lithium, sodium and potassium across the human erythrocyte membrane induced by divalent anions.

    PubMed Central

    Becker, B F; Duhm, J

    1978-01-01

    1. The passive net transport of Li+ and Na+ across the human red cell membrane was accelerated by the divalent anions carbonate, sulphite, oxalate, phosphite and malonate. Phthalate, maleate, sulphate and succinate were found additionally to stimulate downhill transport of K+. Marked differences in anion efficacy and selectivity were observed. 2. The effects of these 'carbonate type' anions were reversible and fully blocked by SITS, dipyridamole and other inhibitors of anion transfer. 3. Cation transport acceleration induced by the monovalent anions salicylate, benzoate, thiocyanate and 2,4-dinitrophenol were inhibited by dipyridamole, but not affected by SITS. A great number of mono- and polyvalent anions were without detectable influence on Li+ transport. 4. Li+ net uptake induced by oxalate exhibited a pH dependence similar to that reported for halide self exchange. 5. Transport acceleration by carbonate type anions displayed a linear, 1:1 dependence on the concentrations of both the anion and the cation and was symmetric with respect to the two sides of the membrane. 6. It is concluded that the divalent carbonate type anions form singly charged, negative 1:1 ion pairs with the respective alkali metal cations, the ion pairs traversing the red cell membrane via the anion exchange pathway. This concept of anionic formation of some of the ion pairs considered. The relative efficacies and cation selectivities of polyvalent anions can largely be explained on the basis of electrostatic interactions governing ion pair formation. However, the chelating properties, structural flexibility, polarizability of the anions and the accessibility of the ion pairs to the anion exchange pathway need also be considered. 7. An exchange of NaCO-3 ion pairs for internal HCO-3 or Cl- is discussed as a possible mode of cellular pH regulation. PMID:31458

  7. High Performance Simulation of Environmental Tracers in Heterogeneous Formations

    NASA Astrophysics Data System (ADS)

    Gardner, P.; Hammond, G. E.; Lichtner, P. C.; Arnold, B. W.

    2013-12-01

    Environmental tracers provide information on fluid flux, yielding important information for use in groundwater studies. Currently environmental tracer interpretation has been limited by computational expense. Here we use a scalable, massively parallel, flow and reactive transport code PFLOTRAN to simulate the concentrations of 3H, 3He, CFC-11, CFC-12, CFC-113, SF6, 39Ar, 81Kr , 4He and the mean groundwater age in 2D and 3D heterogeneous fields on grids with an excess of 10 million nodes. We utilize this computational platform to simulate the spatial distribution of environmental tracer concentration, tracer derived ages and modeled mean ground water age in heterogeneous aquifers. Modeled concentrations are then used to calculate tracer derived ages. The deviation of the tracer derived age distribution from the true groundwater age distribution increases with increasing heterogeneity of the system. The separation between the apparent age derived from different tracers also increases with increasing system heterogeneity. Age distributions in 3D aquifers differ significantly from 2D simulations with similar spatial statistics. The addition of the 3rd dimension increases connectivity, decreasing mean age and reducing age variability. High performance computation allows for investigation of tracer and groundwater age spatial distribution in unprecedented detail, providing a foundation for the next generation of environmental tracer interpretation.

  8. Tracer Testing for Estimating Heat Transfer Area in Fractured Reservoirs

    SciTech Connect

    Pruess, Karsten; van Heel, Ton; Shan, Chao

    2004-05-12

    A key parameter governing the performance and life-time of a Hot Fractured Rock (HFR) reservoir is the effective heat transfer area between the fracture network and the matrix rock. We report on numerical modeling studies into the feasibility of using tracer tests for estimating heat transfer area. More specifically, we discuss simulation results of a new HFR characterization method which uses surface-sorbing tracers for which the adsorbed tracer mass is proportional to the fracture surface area per unit volume. Sorption in the rock matrix is treated with the conventional formulation in which tracer adsorption is volume-based. A slug of solute tracer migrating along a fracture is subject to diffusion across the fracture walls into the adjacent rock matrix. Such diffusion removes some of the tracer from the fluid in the fractures, reducing and retarding the peak in the breakthrough curve (BTC) of the tracer. After the slug has passed the concentration gradient reverses, causing back-diffusion from the rock matrix into the fracture, and giving rise to a long tail in the BTC of the solute. These effects become stronger for larger fracture-matrix interface area, potentially providing a means for estimating this area. Previous field tests and modeling studies have demonstrated characteristic tailing in BTCs for volatile tracers in vapor-dominated reservoirs. Simulated BTCs for solute tracers in single-phase liquid systems show much weaker tails, as would be expected because diffusivities are much smaller in the aqueous than in the gas phase, by a factor of order 1000. A much stronger signal of fracture-matrix interaction can be obtained when sorbing tracers are used. We have performed simulation studies of surface-sorbing tracers by implementing a model in which the adsorbed tracer mass is assumed proportional to the fracture-matrix surface area per unit volume. The results show that sorbing tracers generate stronger tails in BTCs, corresponding to an effective

  9. The dispersion of atmospheric tracers in nocturnal drainage flows

    SciTech Connect

    Gudiksen, P. H.; Shearer, D. L.

    1989-07-01

    This paper summarizes the results of a series of perfluorocarbon tracer experiments that were carried out in the Brush Creek Valley in western Colorado under the auspices of the Atmospheric Studies in Complex Terrain (ASCOT) program. The results indicate that tracers entrained within the valley's nocturnal drainage flows displayed well defined plumes that were not influenced significantly by the larger scale flows above this deep and narrow valley. Thus, the spatial distributions of the tracers were primarily governed by the structure of the drainage flows. None of the tracers released within the valley were detected in significant quantities on the adjoining meses or within the adjacent valleys prior to sunrise.

  10. Gastric activity studies using a magnetic tracer.

    PubMed

    Cordova-Fraga, T; Bernal-Alvarado, J J; Gutierrez-Juarez, G; Sosa, M; Vargas-Luna, M

    2004-10-01

    A magnetic pulse generator has been set up in order to study gastric activity. Two coils 1.05 m in diameter, arranged in a Helmholtz configuration, were used. The system generated magnetic field pulses higher than 15 mT, of duration 17.3+/-1.2 ms. Measurements were performed in 11 male volunteers, with average age 29.3+/-6.4 years and body mass index 26.0+/-4.8 kg m(-2). Magnetite (Fe3O4) particles with diameters from 75 to 125 microm were used as magnetic tracers, which were mixed in 250 ml of yogurt in concentrations from 2 to 5 g. Signals were registered by using a high speed 3 axis fluxgate digital magnetometer and processed to determine the relaxation of the magnetic tracers by fitting a first-order exponential function to the data, a mean relaxation constant K = 116+/-40 s(-1) was obtained. Also, an average gastric peristaltic frequency was measured; a value of 3.2+/-0.3 cpm was determined. PMID:15535190

  11. Tracer exchange between tropics and middle latitudes

    NASA Technical Reports Server (NTRS)

    Rood, Richard; Douglass, Anne; Weaver, Clark

    1992-01-01

    The interaction between the tropics and middle latitudes is studied using a tracer emitted at 50 hPa along a great circle route between Los Angeles, USA and Sydney, Australia. Though designed to examine the impact of stratospheric aircraft, the study more generally addresses the transport between tropics and middle latitudes for a three month period from January through March 1989. The results show that air is transported from the tropics to middle latitudes by planetary scale and tropospheric cyclonic scale waves. Except for intrusions by these wave events, the tropics are substantially isolated throughout the lower stratosphere. These waves draw material out of the tropics which ends up in the middle latitude westerly jets, with little material entering the winter polar latitudes prior to the springtime transition. The summer Southern Hemisphere is characterized by tracer being drawn out in streamers that extend from north and west to south and east. The material in the tropics is zonally asymmetric. The material that reaches the troposphere comes down in the synoptic scale eddies and is concentrated in the middle latitude jet stream. These characteristics are similar to those observed during the dispersion of volcanic clouds.

  12. Probes for anionic cell surface detection

    DOEpatents

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  13. Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

    PubMed

    Yin, Li-Chang; Wang, Ping; Kang, Xiang-Dong; Sun, Cheng-Hua; Cheng, Hui-Ming

    2007-03-28

    Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate. PMID:17356758

  14. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions.

    PubMed

    Wang, Lai-Sheng

    2015-07-28

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES. PMID:26233095

  15. Charge regulation enables anionic hydroxypropyl guar-borate adsorption onto anionic and cationic polystyrene latex.

    PubMed

    Zhang, Liang; Pelton, Robert; Ketelson, Howard; Meadows, David

    2011-01-15

    Reported are adsorption isotherms for guar and hydroxypropyl guar (HPG), with and without the presence of borate ions, onto surfactant free anionic polystyrene latex. Guar and HPG formed adsorbed monolayers on the hydrophobic latex. The presence of borate ions converted the nonionic guar and HPG into an anionic polyelectrolyte. However, there was no measurable influence of bound borate ions on the adsorption of guar or HPG onto anionic, hydrophobic latex. To underscore the unusual behavior of HPG-borate, a sample of HPG was oxidized to introduce carboxyl groups, and the adsorption of the carboxylated HPG onto anionic polystyrene was measured. Unlike HPG-borate, oxidized HPG did not adsorb onto negative polystyrene latex at neutral pH because of electrostatic repulsion. To explain the adsorption of negative HPG-borate onto negative latex, we proposed that as HPG-borate segments approach the latex surface, the negative electrostatic potential near the latex surface induces the detachment of the labile borate groups from HPG. PMID:21030034

  16. PROGRESS REPORT. SUPRAMOLECULAR CHEMISTRY OF SELECTIVE ANION RECOGNITION FOR ANIONS OF ENVIRONMENTAL RELEVANCE

    EPA Science Inventory

    This project involves the design and synthesis of receptors for oxoanions of environmental importance and specifically those found in high level waste tanks. Polyammonium macrocycles as receptors and nitrate as anion were the focus of the first phase of this project. A second pha...

  17. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    SciTech Connect

    Wang, Lai-Sheng

    2015-07-28

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

  18. The chemistry of molecular anions in circumstellar sources

    NASA Astrophysics Data System (ADS)

    Agúndez, Marcelino; Cernicharo, José; Guélin, Michel

    2015-01-01

    The detection of negatively charged molecules in the interstellar and circumstellar medium in the past four years has been one of the most impacting surprises in the area of molecular astrophysics. It has motivated the interest of astronomers, physicists, and chemists on the study of the spectroscopy, chemical kinetics, and prevalence of molecular anions in the different astronomical regions. Up to six different molecular anions have been discovered in space to date, the last one being the small ion CN-, which has been observed in the envelope of the carbon star IRC +10216 and which contrary to the other larger anions is not formed by electron attachment to CN, but through reactions of large carbon anions with nitrogen atoms. Here we briefly review the current status of our knowledge of the chemistry of molecular anions in space, with particular emphasis on the circumstellar source IRC +10216, which to date is the astronomical source harboring the largest variety of anions.

  19. Process for removing sulfate anions from waste water

    DOEpatents

    Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

    1997-01-01

    A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

  20. The chemistry of molecular anions in circumstellar sources

    SciTech Connect

    Agúndez, Marcelino; Cernicharo, José; Guélin, Michel

    2015-01-22

    The detection of negatively charged molecules in the interstellar and circumstellar medium in the past four years has been one of the most impacting surprises in the area of molecular astrophysics. It has motivated the interest of astronomers, physicists, and chemists on the study of the spectroscopy, chemical kinetics, and prevalence of molecular anions in the different astronomical regions. Up to six different molecular anions have been discovered in space to date, the last one being the small ion CN{sup −}, which has been observed in the envelope of the carbon star IRC +10216 and which contrary to the other larger anions is not formed by electron attachment to CN, but through reactions of large carbon anions with nitrogen atoms. Here we briefly review the current status of our knowledge of the chemistry of molecular anions in space, with particular emphasis on the circumstellar source IRC +10216, which to date is the astronomical source harboring the largest variety of anions.

  1. Photoelectron Spectroscopy and Theoretical Studies of Anion-pi Interactions: Binding Strength and Anion Specificity

    SciTech Connect

    Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.

    2015-01-01

    Proposed in theory and confirmed to exist, anion–π interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, intrinsic anion–π interaction strengths that are free from complications of condensed phases’ environments, have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl⁻, Br⁻, I⁻, linear thiocyanate SCN⁻, trigonal planar nitrate NO₃⁻, pyramidic iodate IO₃⁻, and tetrahedral sulfate SO₄²⁻). The binding energies of the resultant gaseous 1:1 complexes (1•Cl⁻,1•Br⁻, 1•I⁻, 1•SCN⁻, 1•NO₃⁻, 1•IO₃⁻ and 1•SO₄²⁻) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion specific effects. The binding strengths of Cl⁻, NO₃⁻, IO₃⁻ with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal/mol, but only about 40% of that between 1 and SO₄²⁻. Quantum chemical calculations reveal that all anions reside in the center of the cavity of 1 with anion–π binding motif in the complexes’ optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and natural bond orbital charge distribution analysis further support anion–π binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work

  2. Preorganized anion traps for exploiting anion-π interactions: an experimental and computational study.

    PubMed

    Bretschneider, Anne; Andrada, Diego M; Dechert, Sebastian; Meyer, Steffen; Mata, Ricardo A; Meyer, Franc

    2013-12-01

    1,3-Bis(pentafluorophenyl-imino)isoindoline (A(F)) and 3,6-di-tert-butyl-1,8-bis(pentafluorophenyl)-9H-carbazole (B(F)) have been designed as preorganized anion receptors that exploit anion-π interactions, and their ability to bind chloride and bromide in various solvents has been evaluated. Both receptors A(F) and B(F) are neutral but provide a central NH hydrogen bond that directs the halide anion into a preorganized clamp of the two electron-deficient appended arenes. Crystal structures of host-guest complexes of A(F) with DMSO, Cl(-), or Br(-) (A(F):DMSO, A(F):Cl(-), and A(2)(F):Br(-)) reveal that in all cases the guest is located in the cleft between the perfluorinated flaps, but NMR spectroscopy shows a more complex situation in solution because of E,Z/Z,Z isomerism of the host. In the case of the more rigid receptor B(F), Job plots evidence 1:1 complex formation with Cl(-) and Br(-), and association constants up to 960 M(-1) have been determined depending on the solvent. Crystal structures of B(F) and B(F):DMSO visualize the distinct preorganization of the host for anion-π interactions. The reference compounds 1,3-bis(2-pyrimidylimino)isoindoline (A(N)) and 3,6-di-tert-butyl-1,8-diphenyl-9H-carbazole (B(H)), which lack the perfluorinated flaps, do not show any indication of anion binding under the same conditions. A detailed computational analysis of the receptors A(F) and B(F) and their host-guest complexes with Cl(-) or Br(-) was carried out to quantify the interactions in play. Local correlation methods were applied, allowing for a decomposition of the ring-anion interactions. The latter were found to contribute significantly to the stabilization of these complexes (about half of the total energy). Compounds A(F) and B(F) represent rare examples of neutral receptors that are well preorganized for exploiting anion-π interactions, and rare examples of receptors for which the individual contributions to the binding energy have been quantified. PMID

  3. Multiple-anion nonvolatile acetal (MANA) resists

    NASA Astrophysics Data System (ADS)

    Guevremont, Jeffrey M.; Brainard, Robert L.; Reeves, Scott D.; Zhou, Xin; Nguyen, Thinh B.; Mackevich, Joseph F.; Anderson, Erik H.; Taylor, Gary N.

    2001-08-01

    New acetal or ketal blocking reagents were investigated for use in e-beam lithography and compared with the performance of ethyl vinyl either (EVE). Three blocking groups, (alpha) -Angelicalactone (AL), 6-methylene-5,6-benzo-1,4- dioxane (MBD), and MANA50 (an undisclosed blocking group used to show the potential of this chemistry) were reacted with poly(p-hydroxystyrene) (PHS) under acid catalyzed conditions to form AL-PHS, MBD-PHS, MANA50-PHS. The performance objectives pursued in the design of these new materials was to use acetal (ketal) chemistry to deliver wide process latitudes (e.g. good PED performance and minimal PEB sensitivity), use high molecular weight blocking groups to eliminate outgassing, and use the novel concept of multiple anions to deliver lithographic performance. These new materials are called Multiple Anion Nonvolatile Acetal (MANA) resists. Resists films were exposed with 50kV electrons, post exposure baked (PEB), and developed with 0.26 N TMAH. Resists prepared with the third blocking group, MANA50, gave contrast and imaging performance independent of PEB humidity and were relatively insensitive to PEB temperature and post exposure delay (PED). These resists gave the best resolution (90 nm) and profiles of all the materials tested, as well as showing no outgassing (as measured by film thickness loss).

  4. Anionic derivatives of uracil: fragmentation and reactivity.

    PubMed

    Cole, Callie A; Wang, Zhe-Chen; Snow, Theodore P; Bierbaum, Veronica M

    2014-09-01

    Uracil is an essential biomolecule for terrestrial life, yet its prebiotic formation mechanisms have proven elusive for decades. Meteorites have been shown to contain uracil and the interstellar abundance of aromatic species and nitrogen-containing molecules is well established, providing support for uracil's presence in the interstellar medium (ISM). The ion chemistry of uracil may provide clues to its prebiotic synthesis and role in the origin of life. The fragmentation of biomolecules provides valuable insights into their formation. Previous research focused primarily on the fragmentation and reactivity of cations derived from uracil. In this study, we explore deprotonated uracil-5-carboxylic acid and its anionic fragments to elucidate novel reagents of uracil formation and to characterize the reactivity of uracil's anionic derivatives. The structures of these fragments are identified through theoretical calculations, further fragmentation, experimental acidity bracketing, and reactivity with several detected and potential interstellar species (SO2, OCS, CS2, NO, N2O, CO, NH3, O2, and C2H4). Fragmentation is achieved through collision induced dissociation (CID) in a commercial ion trap mass spectrometer, and all reaction rate constants are measured using a modification of this instrument. Experimental data are supported by theoretical calculations at the B3LYP/6-311++G(d,p) level of theory. Lastly, the astrochemical implications of the observed fragmentation and reaction processes are discussed. PMID:25036757

  5. Isobar Separator for Anions: Current status

    NASA Astrophysics Data System (ADS)

    Alary, Jean-François; Javahery, Gholamreza; Kieser, William; Zhao, Xiao-Lei; Litherland, Albert; Cousins, Lisa; Charles, Christopher

    2015-10-01

    The Isobar Separator for Anions (ISA) is an emerging separation technique of isobars applied first to the selective removal of 36S from 36Cl, achieving a relative suppression ratio of 6 orders of magnitude. Using a radio-frequency quadrupole (RFQ) column incorporating low energy gas cells, this innovative technique enables the use of a wide range of low energy ion-molecule reactions and collisional-induced dissociation processes for suppressing specific atomic of molecular anions with a high degree of selectivity. Other elemental pairs (analyte/isobar) successfully separated at AMS level include Ca/K, Sr/(Y, Zr), Cs/Ba, Hf/W and Pu/U. In view of these initial successes, an effort to develop a version of the ISA that can be used as a robust technique for routine AMS analysis has been undertaken. We will discuss the detailed layout of a practical ISA and the functional requirements that a combined ISA/AMS should meet. These concepts are currently being integrated in a pre-commercial ISA system that will be installed soon at the newly established A.E. Lalonde Laboratory in Ottawa, Canada.

  6. Nanoheterostructure Cation Exchange: Anionic Framework Conservation

    SciTech Connect

    Jain, Prashant K.; Amirav, Lilac; Aloni, Shaul; Alivisatos, A. Paul

    2010-05-11

    In ionic nanocrystals the cationic sub-lattice can be replaced with a different metal ion via a fast, simple, and reversible place-exchange, allowing post-synthetic modification of the composition of the nanocrystal, while preserving its size and shape. Here, we demonstrate for the first time that during such an exchange, the anionic framework of the crystal is preserved. When applied to nanoheterostructures, this phenomenon ensures that compositional interfaces within the heterostructure are conserved throughout the transformation. For instance, a morphology composed of a CdSe nanocrystal embedded in a CdS rod (CdSe/CdS) was exchanged to a PbSe/PbS nanorod via a Cu2Se/Cu2S structure. During every exchange cycle, the seed size and position within the nanorod were preserved, as evident by excitonic features, Z-contrast imaging, and elemental line-scans. Anionic framework conservation extends the domain of cation exchange to the design of more complex and unique nanostructures.

  7. An intracellular anion channel critical for pigmentation

    PubMed Central

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-01-01

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation. DOI: http://dx.doi.org/10.7554/eLife.04543.001 PMID:25513726

  8. Anions in laser-induced plasmas

    NASA Astrophysics Data System (ADS)

    Shabanov, S. V.; Gornushkin, I. B.

    2016-07-01

    The equation of state for plasmas containing negative atomic and molecular ions (anions) is modeled. The model is based on the assumption that all ionization processes and chemical reactions are at local thermal equilibrium and the Coulomb interaction in the plasma is described by the Debye-Hückel theory. In particular, the equation of state is obtained for plasmas containing the elements Ca, Cl, C, Si, N, and Ar. The equilibrium reaction constants are calculated using the latest experimental and ab initio data of spectroscopic constants for the molecules CaCl_2, CaCl, Cl_2, N_2, C_2, Si_2, CN, SiN, SiC, and their positive and negative ions. The model is applied to laser-induced plasmas (LIPs) by including the equation of state into a fluid dynamic numerical model based on the Navier-Stokes equations describing an expansion of LIP plumes into an ambient gas as a reactive viscous flow with radiative losses. In particular, the formation of anions Cl-, C-, Si-, {{Cl}}2^{ - }, {{Si}}2^{ - }, {{C}}2^{ - }, CN-, SiC-, and SiN- in LIPs is investigated in detail.

  9. Protein Camouflage: Supramolecular Anion Recognition by Ubiquitin.

    PubMed

    Mallon, Madeleine; Dutt, Som; Schrader, Thomas; Crowley, Peter B

    2016-04-15

    Progress in the field of bio-supramolecular chemistry, the bottom-up assembly of protein-ligand systems, relies on a detailed knowledge of molecular recognition. To address this issue, we have characterised complex formation between human ubiquitin (HUb) and four supramolecular anions. The ligands were: pyrenetetrasulfonic acid (4PSA), p-sulfonato-calix[4]arene (SCLX4), bisphosphate tweezers (CLR01) and meso-tetrakis (4-sulfonatophenyl)porphyrin (TPPS), which vary in net charge, size, shape and hydrophobicity. All four ligands induced significant changes in the HSQC spectrum of HUb. Chemical shift perturbations and line-broadening effects were used to identify binding sites and to quantify affinities. Supporting data were obtained from docking simulations. It was found that these weakly interacting ligands bind to extensive surface patches on HUb. A comparison of the data suggests some general indicators for the protein-binding specificity of supramolecular anions. Differences in binding were observed between the cavity-containing and planar ligands. The former had a preference for the arginine-rich, flexible C terminus of HUb. PMID:26818656

  10. Porating anion-responsive copolymeric gels.

    PubMed

    England, Dustin; Yan, Feng; Texter, John

    2013-09-24

    A polymerizable ionic liquid surfactant, 1-(11-acryloyloxyundecyl)-3-methylimidiazolium bromide (ILBr), was copolymerized with methyl methacrylate (MMA) in aqueous microemulsions at 30% (ILBr w/w) and various water to MMA ratios. The ternary phase diagram of the ILBr/MMA/water system was constructed at 25 and 60 °C. Homopolymers and copolymers of ILBr and MMA were produced by thermally initiated chain radical microemulsion polymerization at various compositions in bicontinuous and reverse microemulsion subdomains. Microemulsion polymerization reaction products varied from being gel-like to solid, and these materials were analyzed by thermal and scanning electron microscopy methods. Microemulsion polymerized materials were insoluble in all solvents tested, consistent with light cross-linking. Ion exchange between Br(-) and PF6(-) in these copolymeric materials resulted in the formation of open-cell porous structures in some of these materials, as was confirmed by scanning electron microscopy (SEM). Several compositions illustrate the capture of prepolymerization nanoscale structure by thermally initiated polymerization, expanding the domain of compositions exhibiting this feat and yet to be demonstrated in any other system. Regular cylindrical pores in interpenetrating ILBr-co-MMA and PMMA networks are produced by anion exchange in the absence of templates. A percolating cluster/bicontinuous transition is "captured" by SEM after using anion exchange to visualize the mixed cluster/pore morphology. Some design principles for achieving this capture and for obtaining stimuli responsive solvogels are articulated, and the importance of producing solvogels in capturing the nanoscale is highlighted. PMID:23968242

  11. Advancements in Anion Exchange Membrane Cations

    SciTech Connect

    Sturgeon, Matthew R.; Long, Hai; Park, Andrew M.; Pivovar, Bryan S.

    2015-10-15

    Anion-exchange membrane fuel cells (AME-FCs) are of increasingly popular interest as they enable the use of non-Pt fuel cell catalysts, the primary cost limitation of proton exchange membrane fuel cells. Benzyltrimethyl ammonium (BTMA) is the standard cation that has historically been utilized as the hydroxide conductor in AEMs. Herein we approach AEMs from two directions. First and foremost we study the stability of several different cations in a hydroxide solution at elevated temperatures. We specifically targeted BTMA and methoxy and nitro substituted BTMA. We've also studied the effects of adding an akyl spacer units between the ammonium cation and the phenyl group. In the second approach we use computational studies to predict stable ammonium cations, which are then synthesized and tested for stability. Our unique method to study cation stability in caustic conditions at elevated temperatures utilizes Teflon Parr reactors suitable for use under various temperatures and cation concentrations. NMR analysis was used to determine remaining cation concentrations at specific time points with GCMS analysis verifying product distribution. We then compare the experimental results with calculated modeling stabilities. Our studies show that the electron donating methoxy groups slightly increase stability (compared to that of BTMA), while the electron withdrawing nitro groups greatly decrease stability in base. These results give insight into possible linking strategies to be employed when tethering a BTMA like ammonium cation to a polymeric backbone; thus synthesizing an anion exchange membrane.

  12. Isatin phenylhydrazones: anion enhanced photochromic behaviour.

    PubMed

    Cigáň, M; Jakusová, K; Gáplovský, M; Filo, J; Donovalová, J; Gáplovský, A

    2015-11-01

    The photochemical properties of two basic easily synthesized isatin N(2)-phenylhydrazones were investigated. Contrary to the corresponding isatin N(2)-diphenylhydrazones, only Z-isomers were isolated from the reaction mixtures during the synthesis due to their stabilization by intramolecular hydrogen bonding. Although the presence of the C=N double bond creates conditions for the formation of a simple on-off photoswitch, the low photochemical quantum yield and particularly the low switching amplitude in absorbance hamper their photochromic applications. However, the addition of strongly basic anions to phenylhydrazone solutions leads to isatin NH group deprotonation and creates a new diazene T-type Vis-Vis photochromic system with sufficiently separated absorption maxima. Interestingly, although the thermally stable A-form is also photostable in ambient light, its irradiation with a stronger LED source leads to thermally unstable B-form formation which rapidly isomerizes back to the corresponding A-form. The process is reversible and switching cycles can be repeated in both directions. The important advantages of this two-component organic chromophore-inorganic anion photochromic system are its easy synthesis, easy handling due to its insensitivity to room light, easy further structural modification and reversibility. The corresponding photochemical quantum yield, however, remains relatively low (Φ ∼ 0.001). The theoretically calculated properties are in agreement with the obtained experimental results and support the proposed reaction mechanism. PMID:26412034

  13. An intracellular anion channel critical for pigmentation.

    PubMed

    Bellono, Nicholas W; Escobar, Iliana E; Lefkovith, Ariel J; Marks, Michael S; Oancea, Elena

    2014-01-01

    Intracellular ion channels are essential regulators of organellar and cellular function, yet the molecular identity and physiological role of many of these channels remains elusive. In particular, no ion channel has been characterized in melanosomes, organelles that produce and store the major mammalian pigment melanin. Defects in melanosome function cause albinism, characterized by vision and pigmentation deficits, impaired retinal development, and increased susceptibility to skin and eye cancers. The most common form of albinism is caused by mutations in oculocutaneous albinism II (OCA2), a melanosome-specific transmembrane protein with unknown function. Here we used direct patch-clamp of skin and eye melanosomes to identify a novel chloride-selective anion conductance mediated by OCA2 and required for melanin production. Expression of OCA2 increases organelle pH, suggesting that the chloride channel might regulate melanin synthesis by modulating melanosome pH. Thus, a melanosomal anion channel that requires OCA2 is essential for skin and eye pigmentation. PMID:25513726

  14. Tracer Dispersion Within an Urban Environment.

    NASA Astrophysics Data System (ADS)

    Martin, D.; Shallcross, D.; Price, C.; Nickless, G.; Simmonds, P.

    2003-12-01

    The transport and dispersion of pollutants has extremely important implications for the environment on urban, regional and global scales. At the urban level localised emissions of both biogenic and anthropogenic pollutants can directly impact the health of the inhabitants. The DAPPLE (Dispersion of Air Pollutants and their Penetration into the Local Environment) project is a consortium of six universities, which involves a multidisciplinary approach to characterise relatively small-scale urban atmospheric dispersion including wind tunnel modelling, computer simulations, fieldwork and analysis. This work describes the tracer technology used to characterise atmospheric dispersion as well as preliminary results from the first tracer release experiment in Central London. A steady state finite duration release of both perfluoromethylcyclohexane (PMCH) and Sulfur Hexafluoride (SF6 ) was performed as part of the first DAPPLE campaign. These compounds were released over a fifteen-minute integrated time period with the SF6 release staggered one and a half minutes behind the PMCH. The low background concentrations of PMCH (~ 5 x 10-3 pptv) and SF6 (~5pptv) along with non-depositing and non-reactive characteristics allow for the implementation of near ideal fluid dynamic experiments. Sampling consists of a multiport ladder fitting with solenoid valves onto which a succession of sampling bags is attached. These are electrically actuated in sequential order with an integrated sampling time of three minutes. The samplers are placed at various receptor positions in the DAPPLE zone in predefined positions designed to best validate these model simulated meteorological dispersion processes. Analysis of PMCH is carried out using sample enrichment on carbon based adsorbents, separation by capillary Gas Chromatography and Negative Ion Chemical Ionisation Mass Spectrometry detection (GC-MS-NICI). SF6 concentrations are determined using fixed volume loop injections with Gas

  15. Purification Or Organic Acids Using Anion Exchange Chromatography.

    DOEpatents

    Ponnampalam; Elankovan

    2001-09-04

    Disclosed is a cost-effective method for purifying and acidifying carboxylic acids, including organic acids and amino acids. The method involves removing impurities by allowing the anionic form of the carboxylic acid to bind to an anion exchange column and washing the column. The carboxylic anion is displaced as carboxylic acid by washing the resin with a strong inorganic anion. This method is effective in removing organic carboxylic acids and amino acids from a variety of industrial sources, including fermentation broths, hydrolysates, and waste streams.

  16. Nonvalence correlation-bound anion states of spherical fullerenes.

    PubMed

    Voora, Vamsee K; Jordan, Kenneth D

    2014-08-13

    We present a one-electron model Hamiltonian for characterizing nonvalence correlation-bound anion states of fullerene molecules. These states are the finite system analogs of image potential states of metallic surfaces. The model potential accounts for both atomic and charge-flow polarization and is used to characterize the nonvalence correlation-bound anion states of the C60, (C60)2, C240, and C60@C240 fullerene systems. Although C60 is found to have a single (s-type) nonvalence correlation-bound anion state, the larger fullerenes are demonstrated to have multiple nonvalence correlation-bound anion states. PMID:24978808

  17. Identification and characterization of anion binding sites in RNA.

    PubMed

    Kieft, Jeffrey S; Chase, Elaine; Costantino, David A; Golden, Barbara L

    2010-06-01

    Although RNA molecules are highly negatively charged, anions have been observed bound to RNA in crystal structures. It has been proposed that anion binding sites found within isolated RNAs represent regions of the molecule that could be involved in intermolecular interactions, indicating potential contact points for negatively charged amino acids from proteins or phosphate groups from an RNA. Several types of anion binding sites have been cataloged based on available structures. However, currently there is no method for unambiguously assigning anions to crystallographic electron density, and this has precluded more detailed analysis of RNA-anion interaction motifs and their significance. We therefore soaked selenate into two different types of RNA crystals and used the anomalous signal from these anions to identify binding sites in these RNA molecules unambiguously. Examination of these sites and comparison with other suspected anion binding sites reveals features of anion binding motifs, and shows that selenate may be a useful tool for studying RNA-anion interactions. PMID:20410239

  18. Approach to the Patient With a Negative Anion Gap.

    PubMed

    Emmett, Michael

    2016-01-01

    When anion gap calculation generates a very small or negative number, an explanation must be sought. Sporadic (nonreproducible) measurement errors and systematic (reproducible) laboratory errors must be considered. If an error is ruled out, 2 general possibilities exist. A true anion gap reduction can be generated by either reduced concentrations of unmeasured anions such as albumin or increased concentrations of unmeasured cations such as magnesium, calcium, or lithium. This teaching case describes a patient with aspirin (salicylate) poisoning whose anion gap was markedly reduced (-47 mEq/L). The discussion systematically reviews the possibilities and provides the explanation for this unusual laboratory result. PMID:26363848

  19. Anion recognition by oligo-(thio)urea-based receptors.

    PubMed

    Jia, Chuandong; Zuo, Wei; Zhang, Dan; Yang, Xiao-Juan; Wu, Biao

    2016-07-26

    Oligo-(thio)ureas have proven to be a promising class of receptors that are widely applied in anion recognition. This article aims to present some recent progress in the construction of oligoureas and their anion coordination (recognition) chemistry. Typical examples of metal-coordination assisted and covalently connected oligo-(thio)urea receptors are summarized, with focus on geometry characteristics required for achieving complementary binding of a target anion. Special emphasis is given to ortho-phenylene-connected oligoureas in the application of anion binding and the self-assembly of important supramolecular architectures, including helicates, tetrahedral cages, and so on. PMID:27352298

  20. Aza-Bambusurils En Route to Anion Transporters.

    PubMed

    Singh, Mandeep; Solel, Ephrath; Keinan, Ehud; Reany, Ofer

    2016-06-20

    Previous calculations of anion binding with various bambusuril analogs predicted that the replacement of oxygen by nitrogen atoms to produce semiaza-bambus[6]urils would award these new cavitands with multiple anion binding properties. This study validates the hypothesis by efficient synthesis, crystallography, thermogravimetric analysis and calorimetry. These unique host molecules are easily accessible from the corresponding semithio-bambusurils in a one-pot reaction, which converts a single anion receptor into a potential anion channel. Solid-state structures exhibit simultaneous accommodation of three anions, linearly positioned within the cavity along the main symmetry axis. The ability to hold anions at a short distance of about 4 Å is reminiscent of natural chloride channels in E. coli, which exhibit similar distances between their adjacent anion binding sites. The calculated transition-state energy for double-anion movement through the channel suggests that although these host-guest complexes are thermodynamically stable they enjoy high kinetic flexibility to render them efficient anion channels. PMID:27225332

  1. Inhibition of nuclear waste solutions containing multiple aggressive anions

    SciTech Connect

    Congdon, J.W.

    1988-05-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions; however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion.

  2. Aluminum Zintl anion moieties within sodium aluminum clusters

    SciTech Connect

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Grubisic, Andrej; Li, Xiang; Ganteför, Gerd; Bowen, Kit H. E-mail: kiran@mcneese.edu; Schnöckel, Hansgeorg; Eichhorn, Bryan W.; Lee, Mal-Soon; Jena, P.; Kandalam, Anil K. E-mail: kiran@mcneese.edu; Kiran, Boggavarapu E-mail: kiran@mcneese.edu

    2014-02-07

    Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium–aluminum cluster anions, Na{sub m}Al{sub n}{sup −}, were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectra were measured by a magnetic bottle, electron energy analyzer. Calculations on a select sub-set of stoichiometries provided geometric structures and full charge analyses for both cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra), and fragment molecular orbital based correlation diagrams.

  3. Aluminum Zintl anion moieties within sodium aluminum clusters

    NASA Astrophysics Data System (ADS)

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Grubisic, Andrej; Li, Xiang; Ganteför, Gerd; Schnöckel, Hansgeorg; Eichhorn, Bryan W.; Lee, Mal-Soon; Jena, P.; Kandalam, Anil K.; Kiran, Boggavarapu; Bowen, Kit H.

    2014-02-01

    Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium-aluminum cluster anions, NamAln-, were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectra were measured by a magnetic bottle, electron energy analyzer. Calculations on a select sub-set of stoichiometries provided geometric structures and full charge analyses for both cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra), and fragment molecular orbital based correlation diagrams.

  4. Aluminum Zintl anion moieties within sodium aluminum clusters.

    PubMed

    Wang, Haopeng; Zhang, Xinxing; Ko, Yeon Jae; Grubisic, Andrej; Li, Xiang; Ganteför, Gerd; Schnöckel, Hansgeorg; Eichhorn, Bryan W; Lee, Mal-Soon; Jena, P; Kandalam, Anil K; Kiran, Boggavarapu; Bowen, Kit H

    2014-02-01

    Through a synergetic combination of anion photoelectron spectroscopy and density functional theory based calculations, we have established that aluminum moieties within selected sodium-aluminum clusters are Zintl anions. Sodium-aluminum cluster anions, Na(m)Al(n)(-), were generated in a pulsed arc discharge source. After mass selection, their photoelectron spectra were measured by a magnetic bottle, electron energy analyzer. Calculations on a select sub-set of stoichiometries provided geometric structures and full charge analyses for both cluster anions and their neutral cluster counterparts, as well as photodetachment transition energies (stick spectra), and fragment molecular orbital based correlation diagrams. PMID:24511934

  5. Estimating groundwater recharge in Hebei Plain, China under varying land use practices using tritium and bromide tracers

    USGS Publications Warehouse

    Wang, B.; Jin, M.; Nimmo, J.R.; Yang, L.; Wang, W.

    2008-01-01

    Tritium and bromide were used as applied tracers to determine groundwater recharge in Hebei Plain, North China, to evaluate the impacts of different soil types, land use, irrigation, and crop cultivation practice on recharge. Additional objectives were to evaluate temporal variability of recharge and the effect on results of the particular tracer used. Thirty-nine profiles at representative locations were chosen for investigation. Average recharge rates and recharge coefficient determined by tritium and bromide tracing for different sites were 0.00-1.05 mm/d and 0.0-42.5%, respectively. The results showed relative recharge rates for the following paired influences (items within each pair are listed with the influence producing greater recharge first): flood-irrigated cropland and non-irrigated non-cultivation land, flood irrigation (0.42-0.58 mm/d) and sprinkling irrigation (0.17-0.23 mm/d), no stalk mulch (0.56-0.80 mm/d) and stalk mulch (0.44-0.60 mm/d), vegetable (e.g. Chinese cabbage and garlic, 0.70 mm/d) and wheat-maize (0.38 mm/d), peanut (0.51 mm/d) and peach (0.43 mm/d). The results also showed greater recharge for the first year of tracer travel than for the second. Because total precipitation and irrigation were greater in the first year than in the second, this may reflect temporal variability of recharge. The method may not be applicable where the water table is shallow (less than 3 m). A comparison of the near-ideal tritium tracer with the more common but less ideal bromide showed that bromide moved approximately 23% faster than tritiated water, perhaps because of anion exclusion. ?? 2008 Elsevier B.V.

  6. Estimating groundwater recharge in Hebei Plain, China under varying land use practices using tritium and bromide tracers

    NASA Astrophysics Data System (ADS)

    Wang, Bingguo; Jin, Menggui; Nimmo, John R.; Yang, Lei; Wang, Wenfeng

    2008-07-01

    SummaryTritium and bromide were used as applied tracers to determine groundwater recharge in Hebei Plain, North China, to evaluate the impacts of different soil types, land use, irrigation, and crop cultivation practice on recharge. Additional objectives were to evaluate temporal variability of recharge and the effect on results of the particular tracer used. Thirty-nine profiles at representative locations were chosen for investigation. Average recharge rates and recharge coefficient determined by tritium and bromide tracing for different sites were 0.00-1.05 mm/d and 0.0-42.5%, respectively. The results showed relative recharge rates for the following paired influences (items within each pair are listed with the influence producing greater recharge first): flood-irrigated cropland and non-irrigated non-cultivation land, flood irrigation (0.42-0.58 mm/d) and sprinkling irrigation (0.17-0.23 mm/d), no stalk mulch (0.56-0.80 mm/d) and stalk mulch (0.44-0.60 mm/d), vegetable (e.g. Chinese cabbage and garlic, 0.70 mm/d) and wheat-maize (0.38 mm/d), peanut (0.51 mm/d) and peach (0.43 mm/d). The results also showed greater recharge for the first year of tracer travel than for the second. Because total precipitation and irrigation were greater in the first year than in the second, this may reflect temporal variability of recharge. The method may not be applicable where the water table is shallow (less than 3 m). A comparison of the near-ideal tritium tracer with the more common but less ideal bromide showed that bromide moved approximately 23% faster than tritiated water, perhaps because of anion exclusion.

  7. 10 CFR 39.45 - Subsurface tracer studies.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 1 2010-01-01 2010-01-01 false Subsurface tracer studies. 39.45 Section 39.45 Energy NUCLEAR REGULATORY COMMISSION LICENSES AND RADIATION SAFETY REQUIREMENTS FOR WELL LOGGING Equipment § 39.45 Subsurface tracer studies. (a) The licensee shall require all personnel handling...

  8. 10 CFR 39.45 - Subsurface tracer studies.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 1 2013-01-01 2013-01-01 false Subsurface tracer studies. 39.45 Section 39.45 Energy NUCLEAR REGULATORY COMMISSION LICENSES AND RADIATION SAFETY REQUIREMENTS FOR WELL LOGGING Equipment § 39.45 Subsurface tracer studies. (a) The licensee shall require all personnel handling...

  9. 10 CFR 39.45 - Subsurface tracer studies.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 1 2014-01-01 2014-01-01 false Subsurface tracer studies. 39.45 Section 39.45 Energy NUCLEAR REGULATORY COMMISSION LICENSES AND RADIATION SAFETY REQUIREMENTS FOR WELL LOGGING Equipment § 39.45 Subsurface tracer studies. (a) The licensee shall require all personnel handling...

  10. 10 CFR 39.45 - Subsurface tracer studies.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 1 2012-01-01 2012-01-01 false Subsurface tracer studies. 39.45 Section 39.45 Energy NUCLEAR REGULATORY COMMISSION LICENSES AND RADIATION SAFETY REQUIREMENTS FOR WELL LOGGING Equipment § 39.45 Subsurface tracer studies. (a) The licensee shall require all personnel handling...