Sample records for exchange isotopic

  1. Diffusional exchange of isotopes in a metal hydride sphere.

    Energy Technology Data Exchange (ETDEWEB)

    Wolfer, Wilhelm G.; Hamilton, John C.; James, Scott Carlton


    This report describes the Spherical Particle Exchange Model (SPEM), which simulates exchange of one hydrogen isotope by another hydrogen isotope in a spherical metal hydride particle. This is one of the fundamental physical processes during isotope exchange in a bed of spherical metal particles and is thus one of the key components in any comprehensive physics-based model of exchange. There are two important physical processes in the model. One is the entropy of mixing between the two isotopes; the entropy of mixing is increased by having both isotopes randomly placed at interstitial sites on the lattice and thus impedes the exchange process. The other physical process is the elastic interaction between isotope atoms on the lattice. The elastic interaction is the cause for {beta}-phase formation and is independent of the isotope species. In this report the coupled diffusion equations for two isotopes in the {beta}-phase hydride are solved. A key concept is that the diffusion of one isotope depends not only on its concentration gradient, but also on the concentration gradient of the other isotope. Diffusion rate constants and the chemical potentials for deuterium and hydrogen in the {beta}-phase hydride are reviewed because these quantities are essential for an accurate model of the diffusion process. Finally, a summary of some of the predictions from the SPEM model are provided.

  2. Isotopically exchangeable Al in coastal lowland acid sulfate soils

    Energy Technology Data Exchange (ETDEWEB)

    Yvanes-Giuliani, Yliane A.M. [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia); Centre Européen de Recherche et d' Enseignement des Géosciences de l' Environnement, Aix-Marseille Université, Aix en Provence (France); Fink, D. [Centre Européen de Recherche et d' Enseignement des Géosciences de l' Environnement, Aix-Marseille Université, Aix en Provence (France); Rose, J. [Institute for Environmental Research, Australian Nuclear Science and Technology Organisation, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Waite, T. David [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia); Collins, Richard N., E-mail: [UNSW Water Research Centre, School of Civil and Environmental Engineering, UNSW Australia, Sydney, NSW 2052 (Australia)


    Periodic discharges of high concentrations of aluminium (Al) causing fish kills and other adverse effects occur worldwide in waterways affected by coastal lowland acid sulfate soils (CLASS). The exchangeability — a metal's ability to readily transfer between the soil solid- and solution-phases — of Al in these soils is therefore of particular importance as it has implications for metal transport, plant availability and toxicity to living organisms. In the present study, the concentrations of isotopically exchangeable Al (E values) were measured in 27 CLASS and compared with common salt extractions (i.e. KCl and CuCl{sub 2}) used to estimate exchangeable soil pools of Al. E values of Al were high in the soils, ranging from 357 to 3040 mg·kg{sup −1}. Exchangeable concentrations estimated using 1 M KCl were consistently lower than measured E values, although a reasonable correlation was obtained between the two values (E = 1.68 × Al{sub KCl}, r{sup 2} = 0.66, n = 25). The addition of a 0.2 M CuCl{sub 2} extraction step improved the 1:1 agreement between extractable and isotopically exchangeable Al concentrations, but lead to significant mobilisation of non-isotopically exchangeable Al in surficial ‘organic-rich’ CLASS having E values < 1000 mg·kg{sup −1}. It was concluded that currently used (i.e. 1 M KCl) methodology severely underestimates exchangeable Al and total actual acidity values in CLASS and should be corrected by a factor similar to the one determined here. - Highlights: • Isotopically exchangeable Al was compared to 1 M KCl or 0.2 M CuCl{sub 2} extractable Al. • 1 M KCl always underestimated isotopically exchangeable Al concentrations. • 0.2 M CuCl{sub 2} mobilised non-isotopically exchangeable Al • 1 M KCl values require correction of ~ 1.7 to reflect exchangeable Al concentrations.

  3. A stochastic modeling of isotope exchange reactions in glutamine synthetase (United States)

    Kazmiruk, N. V.; Boronovskiy, S. E.; Nartsissov, Ya R.


    The model presented in this work allows simulation of isotopic exchange reactions at chemical equilibrium catalyzed by a glutamine synthetase. To simulate the functioning of the enzyme the algorithm based on the stochastic approach was applied. The dependence of exchange rates for 14C and 32P on metabolite concentration was estimated. The simulation results confirmed the hypothesis of the ascertained validity for preferred order random binding mechanism. Corresponding values of K0.5 were also obtained.

  4. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry


    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  5. Isotope exchange by Ion Cyclotron Wall Conditioning on JET

    Energy Technology Data Exchange (ETDEWEB)

    Wauters, T., E-mail: [Laboratory for Plasma Physics, ERM/KMS, TEC Partner, 1000 Brussels (Belgium); Douai, D.; Kogut, D. [CEA, IRFM, F-13108 St-Paul-Lez-Durance (France); Lyssoivan, A. [Laboratory for Plasma Physics, ERM/KMS, TEC Partner, 1000 Brussels (Belgium); Brezinsek, S. [Forschungszentrum Jülich, Institut für Energie- und Klimaforschung Plasmaphysik, 52425 Jülich (Germany); Belonohy, E. [Max-Planck Institut für Plasmaphysik, 85748 Garching (Germany); Blackman, T. [JET-EFDA, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Bobkov, V. [Max-Planck Institut für Plasmaphysik, 85748 Garching (Germany); Crombé, K. [Laboratory for Plasma Physics, ERM/KMS, TEC Partner, 1000 Brussels (Belgium); Drenik, A. [Jožef Stefan Institute, 1000 Ljubljana (Slovenia); Graham, M. [JET-EFDA, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Joffrin, E. [CEA, IRFM, F-13108 St-Paul-Lez-Durance (France); Lerche, E. [Laboratory for Plasma Physics, ERM/KMS, TEC Partner, 1000 Brussels (Belgium); Loarer, T. [CEA, IRFM, F-13108 St-Paul-Lez-Durance (France); Lomas, P.L.; Mayoral, M.-L.; Monakhov, I. [JET-EFDA, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Oberkofler, M. [Max-Planck Institut für Plasmaphysik, 85748 Garching (Germany); Philipps, V. [Forschungszentrum Jülich, Institut für Energie- und Klimaforschung Plasmaphysik, 52425 Jülich (Germany); Plyusnin, V. [IST, Instituto de Plasmas e Fusão Nuclear, 1049-001 Lisboa (Portugal); and others


    The isotopic exchange efficiencies of JET Ion Cyclotron Wall Conditioning (ICWC) discharges produced at ITER half and full field conditions are compared for JET carbon (C) and ITER like wall (ILW). Besides an improved isotope exchange rate on the ILW providing cleaner plasma faster, the main advantage compared to C-wall is a reduction of the ratio of retained discharge gas to removed fuel. Complementing experimental data with discharge modeling shows that long pulses with high (∼240 kW coupled) ICRF power maximizes the wall isotope removal per ICWC pulse. In the pressure range 1–7.5 × 10{sup −3} Pa, this removal reduces with increasing discharge pressure. As most of the wall-released isotopes are evacuated by vacuum pumps in the post discharge phase, duty cycle optimization studies for ICWC on JET-ILW need further consideration. The accessible reservoir by H{sub 2}-ICWC at ITER half field conditions on the JET-ILW preloaded by D{sub 2} tokamak operation is estimated to be 7.3 × 10{sup 22} hydrogenic atoms, and may be exchanged within 400 s of cumulated ICWC discharge time.

  6. Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

    DEFF Research Database (Denmark)



    of isotope exchange, specific radioactivities of the reduced sulfur pools were poorly defined and could not be used to calculate their rates of formation. Such isotope exchange reactions between the reduced inorganic sulfur compounds will affect the stable isotope distribution and are expected to decrease...

  7. Retention of inorganic carbon-14 by isotopic exchange in soils

    Energy Technology Data Exchange (ETDEWEB)

    Sheppard, S.C.; Evenden, W.G


    Carbon-14 is present naturally and is a waste product of the nuclear industry. It is readily incorporated into biological materials and potential impacts have to be considered carefully. From underground waste repositories, much of any {sup 14}C released will be inorganic and will pass rapidly through most terrestrial environments because of gaseous transfer. However, there will be some {sup 14}C retained in soils, in both organic and inorganic forms. This study addresses retention of inorganic {sup 14}C through isotopic exchange with soil carbonates. An outdoor study with incubations lasting up to 24 mo was conducted. A carbonated sandy soil was used unamended, amended with additional carbonate, or amended with ground alfalfa (Medicago sativa L.). One set of soil containers was left open and another set gamma-sterilized and sealed. Volatilization of some of the {sup 14}C happened within minutes, with 98% lost in the alfalfa-amended soils and 56% lost in the carbonate-amended soil. However, the fractions remaining in all the soils had residence half-times of over 1000 d. Much of this retained {sup 14}C was still inorganic and had undergone isotopic exchange with the solid {sup 12}C minerals in the soil. A progressive extraction method was used to monitor the degree of isotopic exchange, and in certain treatments the exchange process was still measurably progressing after 12 mo of incubation. Clearly, assessments of the impacts of {sup 14}C releases to the terrestrial environment must account for these long-term reactions and retention of {sup 14}C in soils. (author)

  8. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange. (United States)

    Zheng, Yong-Fei


    Oxygen isotope fractionation factors for phosphates were calculated by means of the increment method. The results suggest that Ag3PO4 and BiPO4 are enriched in (18)O relative to AgPO4, and the three phosphates are consistently depleted in (18)O relative to Ba3[PO4]2; fluorapatite and chlorapatite exhibit a similar behaviour of oxygen isotope fractionation with consistent enrichment of (18)O relative to hydroxyapatite. The valence, radii and coordination of metal cations play a quantitative role in dictating the (18)O/(16)O partitioning in these phosphates of different compositions. The calculated fractionation factors for the Ag3PO4-H2O system are in agreement with experimental determinations derived from enzyme-catalysed isotope exchange between dissolved inorganic phosphate and water at the longest reaction durations at low temperatures. This demonstrates that the precipitated Ag3PO4 has completely captured the oxygen isotope fractionation in the dissolved inorganic phosphate. The calculated fractionation factors for the F/Cl-apatite-water systems are in agreement with the enzyme-catalysed experimental fractionations for the dissolved phosphate-water system at the longest reaction durations but larger than fractionations derived from bacteria-facilitated exchange and inorganic precipitation experiments as well as natural observations. For the experimental calibrations of oxygen isotope fractionation involving the precipitation of dissolved phosphate species from aqueous solutions, the fractionation between precipitate and water is primarily dictated by the isotope equilibration between the dissolved complex anions and water prior to the precipitation. Therefore, the present results provide a quantitative means to interpret the temperature dependence of oxygen isotope fractionation in inorganic and biogenic phosphates.

  9. Hydrogen and oxygen isotope exchange reactions between clay minerals and water (United States)

    O'Neil, J.R.; Kharaka, Y.K.


    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  10. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water (United States)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.


    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  11. Isotope exchange reactions involving HCO+ with CO: A theoretical approach (United States)

    Mladenović, M.; Roueff, E.


    Aims: We aim to investigate fractionation reactions involved in the 12C/13C, 16O/18O, and 17O balance. Methods: Full-dimensional rovibrational calculations were used to compute numerically exact rovibrational energies and thermal equilibrium conditions to derive the reaction rate coefficients. A nonlinear least-squares method was employed to represent the rate coefficients by analytic functions. Results: New exothermicities are derived for 30 isotopic exchange reactions of HCO+ with CO. For each of the reactions, we provide the analytic three-parameter Arrhenius-Kooij formula for both the forward reaction and backward reaction rate coefficients, that can further be used in astrochemical kinetic models. Rotational constants derived here for the 17O containing forms of HCO+ may assist detection of these cations in outer space.

  12. Hydrogen isotope exchange experiments with Mt Mazama ash (United States)

    Nolan, G. S.; Bindeman, I. N.; Palandri, J. L.


    minor (~20%) hydroxyl loss. 5) Native ash dried to <3% water and ~-145% ∂2H), and reacted with the 650 % prepared water evinces a much higher rate of 2H incorporation compared to rates with the native ash under all the same conditions. Given linearity of ∂2H exchange through time and modeling the reaction as (pseudo) first order in concentration of deuterium yields the following isotopic half life values: for 70° C 1.43 years, for 40° C 4.1 years, and for 25 °C 12.1 years. An Arrhenius treatment yields an activation energy of 32-38 kjoules. 6) A second order kinetic treatment can be used to follow the reaction. A calculation using the reaction constant k at 25 °C assuming native ash exposed to -60 % ∂2H water indicates it would take 2 years to rise from a starting value of -150 to approximately -100 % ∂2H. Results of these experiments put quantitative limits on reliability of ∂2H in ash in paleo-climate studies that are primarily controlled by the isotopic environments and temperatures. We hypothesize that hydrogen-deuterium exchange occurs in native ash exposed to isotopically labeled water. The effect is mediated through surface correlated water in addition to diffusion with both having a rate determining effect. There is nothing to suggest that deuterium-hydrogen exchange is selective for molecular or SiOH hydrogen in the ash.

  13. Isotope exchange kinetics in metal hydrides I : TPLUG model.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Rich; James, Scott Carlton; Nilson, Robert H.


    A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show

  14. Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A

    Directory of Open Access Journals (Sweden)

    P.U. Singare


    Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.

  15. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump. (United States)

    Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi


    The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Observation of large enhancements of charge exchange cross sections with neutron-rich carbon isotopes (United States)

    Tanihata, I.; Terashima, S.; Kanungo, R.; Ameil, F.; Atkinson, J.; Ayyad, Y.; Cortina-Gil, D.; Dillmann, I.; Estradé, A.; Evdokimov, A.; Farinon, F.; Geissel, H.; Guastalla, G.; Janik, R.; Knoebel, R.; Kurcewicz, J.; Litvinov, Yu. A.; Marta, M.; Mostazo, M.; Mukha, I.; Nociforo, C.; Ong, H. J.; Pietri, S.; Prochazka, A.; Scheidenberger, C.; Sitar, B.; Strmen, P.; Takechi, M.; Tanaka, J.; Toki, H.; Vargas, J.; Winfield, J. S.; Weick, H.


    Production cross sections of nitrogen isotopes from high-energy (˜ 950 MeV per nucleon) carbon isotopes on hydrogen and carbon targets have been measured for the first time for a wide range of isotopes (A = 12 to 19). The fragment separator FRS at GSI was used to deliver C-isotope beams. The cross sections of the production of N-isotopes were determined by charge measurements of forward-going fragments. The cross sections show a rapid increase with the number of neutrons in the projectile. Since the production of nitrogen is mostly due to charge-exchange (Cex) reactions below the proton separation energies, the present data suggests a concentration of Gamow-Teller and/or Fermi transition strength at low excitation energies for neutron-rich carbon isotopes. It was also observed that the Cex cross sections were enhanced much more strongly for neutron-rich isotopes in the C-target data.

  17. Radium isotopes as a tracer of sediment-water column exchange in the North Sea

    NARCIS (Netherlands)

    Burt, W.J.; Thomas, H.; Pätsch, J.; Omar, A.; Schrum, C.; Daewel, U.; Brenner, H.; de Baar, H.J.W.


    Sediment-water column exchange plays an important role in coastal biogeochemistry. We utilize short-lived radium isotopes (224Ra and 223Ra) to understand and quantify the dominant processes governing sediment-water column exchange throughout the North Sea. Our comprehensive survey, conducted in

  18. Radium isotopes as a tracer of sediment-water column exchange in the North Sea

    NARCIS (Netherlands)

    Burt, W. J.; Thomas, H.; Paetsch, J.; Omar, A. M.; Schrum, C.; Daewel, U.; Brenner, H.; de Baar, H. J. W.

    Sediment-water column exchange plays an important role in coastal biogeochemistry. We utilize short-lived radium isotopes (Ra-224 and Ra-223) to understand and quantify the dominant processes governing sediment-water column exchange throughout the North Sea. Our comprehensive survey, conducted in

  19. Energetics and control of ultracold isotope-exchange reactions between heteronuclear dimers in external fields (United States)

    Tomza, Michal


    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products.

  20. Anion-exchange chromatographic separation of Hg for isotope ratio measurements by multicollector ICPMS. (United States)

    Malinovsky, Dmitry; Sturgeon, Ralph E; Yang, Lu


    A procedure is described for precise Hg isotope ratio measurements by solution nebulization multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Hg was released from geological samples using aqua regia extraction and then separated from other matrix elements with the aid of anion-exchange chromatography using strongly basic Dowex 1-X8 anion-exchange resin. Performance of the chromatographic procedure was evaluated using various types of replacement anions for elution of mercury, including l-cysteine, thiourea, NO3-, and SO42-. A solution of 0.15% l-cysteine in 0.06 M HCl was found to be the most convenient eluent for subsequent MC-ICPMS measurements. The optimized procedure provides separation of Hg from virtually all concomitant matrix elements while maintaining quantitative (>95%) recovery. In addition, band displacement chromatographic experiments were conducted to assess whether the anion-exchange purification can produce Hg isotope fractionation artifacts. No isotope fractionation between the Hg(II)-l-cysteine complex in aqueous solution and Hg ions in the anion-exchange resin was observed. Hg isotope ratio measurements were performed using the bracketing standards approach and on-line correction for instrumental mass discrimination using Tl spiking and normalization to the 205Tl/203Tl ratio. The absence of spectral interference during Hg isotope ratio measurements was verified using a three-isotope plot. Uncertainties of Hg isotope ratio measurements for replication of the entire procedure, expressed as two standard deviations, are better than +/-0.08 per thousand/amu. The described procedure facilitates study of variations in the isotopic composition of Hg in nature.

  1. Isotope exchange investigation of nitrogen redistribution in expanded austenite

    DEFF Research Database (Denmark)

    Christiansen, Thomas Lundin; Drouet, M.; Martinavičius, A.


    Sequential plasma and gaseous nitriding of Fe–18Cr–10Ni–3Mo stainless steel at 390°C with 14N and 15N isotopes followed by denitriding in flowing hydrogen was investigated. Redistribution of plasma-inserted nitrogen atoms (15N) by subsequent gaseous nitriding (14N) was observed. Denitriding after...... plasma- and gaseous nitriding resulted in predominant retraction of 14N, and only a minor amount of 15N. The nitrogen isotope diffusion behaviour is explained by two different states of nitrogen bonding and short-range ordering between nitrogen and chromium....

  2. Characterising the exchangeability of phenanthrene associated with naturally occurring soil colloids using an isotopic dilution technique. (United States)

    Tavakkoli, Ehsan; Juhasz, Albert; Donner, Erica; Lombi, Enzo


    The association of polycyclic aromatic hydrocarbons (PAHs) with inorganic and organic colloids is an important factor influencing their bioavailability, mobility and degradation in the environment. Despite this, our understanding of the exchangeability and potential bioavailability of PAHs associated with colloids is limited. The objective of this study was to use phenanthrene as a model PAH compound and develop a technique using (14)C phenanthrene to quantify the isotopically exchangeable and non-exchangeable forms of phenanthrene in filtered soil water or sodium tetraborate extracts. The study was also designed to investigate the exchangeability of colloidal phenanthrene as a function of particle size. Our findings suggest that the exchangeability of phenanthrene in sodium tetraborate is controlled by both inorganic and organic colloids, while in aqueous solutions inorganic colloids play the dominant role (even though coating of these by organic matter cannot be excluded). Filter pore size did not have a significant effect on phenanthrene exchangeability. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate. (United States)

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky


    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Hydrogen recycle and isotope exchange from dense carbon films

    Energy Technology Data Exchange (ETDEWEB)

    Clausing, R.E.; Heatherly, L.


    Dense carbon films were prepared by deposition from hydrogen plasmas to which methane was added. The initial hydrogen recycle coefficient from the films ranges from more than two to less than one. The films contain large amounts of hydrogen (up to 50 at. %). They adjust themselves to provide recycling coefficients near unity. Isotope changeover times tend to be long. The reservoir of hydrogen instantly available to the plasma to maintain or stabilize the recycle coefficient and isotopic composition of the plasma is 10/sup 15/ cm/sup -2/ or greater depending on film preparation, temperature, and prior plasma exposure conditions. Simulator observations tend to support and improve the understanding of the observations in TEXTOR and JET; however, they also point out the need for control of film deposition and operating parameters to provide desirable and reproducible properties. The films and the hydrogen isotopes they contain can be removed easily by plasma processes. Since the hydrogen in these films is relatively immobile except in the zone reached by energetic particles, or at temperatures above 400/sup 0/C, dense carbon films may be useful in managing the tritium recovery from near-term fusion experiments.

  5. Adsorption, desorption and isotopic exchange of cadmium on illite: evidence for complete reversibility

    NARCIS (Netherlands)

    Comans, R.N.J.


    Adsorption, desorption and isotopic exchange of Cd on illite clay have been studied at low Cd concentrations and low ionic strength. The results indicate that under the conditions of the experiments Cd sorption on illite is completely reversible. Long equilibration times (7–8 weeks) were shown to be

  6. The fractionation of selenium isotopic exchange between Se (0) and Se (IV) (United States)

    Can, T. D.; Jianming, Z.; Qin, H.; Xu, W.


    Selenium (Se) has six naturally stable isotopes, 74Se, 76Se, 77Se, 78Se, 80Se, and 82Se; with the relative abundance of 0.89%, 9.37%, 7.64%, 23.77%, 49.61%, and 8.73%, respectively. According to the previous work, the variations in δ82/76Se suggested that biogeochemical cycling in earth surface can lead to significant Se isotopic fractionation [1]. It was now believed that the abiotic and biotic reduction for Se (IV) and Se (VI) oxyanion was the main processes for Se isotope fractionation in natural systems. However, recently, the theoretical calculation by first-principles shows that equilibrium Se isotope fractionation between SeO32-and SeO42- can reach Δ82/76Se =13.3‰ at the 25 °, and have a trend of heavy Se isotopes enrichment as SeO42- > SeO3 2- > HSeO3- > SeO2 > selenoamino acids > alkylselenides > Se (0) or H2Se >HSe-[2]. So we take a new idea that the significant isotopic fractionation of Se may be caused by the combined role of Se reduction and isotopic exchange. In the past years, the study of the mechanism of Se isotope fractionation was mainly focused on the reduction of Se oxyanion, but for the fractionation by the isotope exchange between different Se speciation is poorly studied. Therefore, we take the isotope exchange between Se (0) and Se (IV) as an example, to compare the isotope fractionation of Se under the different reaction conditions. Experiment was conducted using 10 mg Se (0) particles mixed with 2 mg/L Se (IV) solution in different medium (MQ-water, 0.1mol/L and 1mol / L NaOH), and the time lasted for 96 days. The value of δ82/76Se in Se (IV) solution from the initial -1.20 ‰ to 2.22‰, 4.20‰ and 6.69‰, respectively. From this experiment we can know, with the increasement of alkalinity in medium solution, the rate for oxidation of Se (0) oxidized by the dissolved oxygen is gradually to increase, and can gain more free electrons for the reaction of the isotopic exchange between Se (0) and Se (IV), and make the rate of isotopic

  7. Assessing the identifiability in isotope exchange depth profiling measurements

    DEFF Research Database (Denmark)

    Ciucci, Francesco; Panagakos, Grigorios; Chen, Chi


    Accurate identification of the physical parameters describing the surface exchange kinetic coefficient k and oxygen diffusion coefficient D is key in solid state ionics, because the performance of many ionic devices is connected to such quantities. In this work we extend and generalize the concept...

  8. Multiphysics Model of Palladium Hydride Isotope Exchange Accounting for Higher Dimensionality

    Energy Technology Data Exchange (ETDEWEB)

    Gharagozloo, Patricia E.; Eliassi, Mehdi; Bon, Bradley Luis


    This report summarizes computational model developm ent and simulations results for a series of isotope exchange dynamics experiments i ncluding long and thin isothermal beds similar to the Foltz and Melius beds and a lar ger non-isothermal experiment on the NENG7 test bed. The multiphysics 2D axi-symmetr ic model simulates the temperature and pressure dependent exchange reactio n kinetics, pressure and isotope dependent stoichiometry, heat generation from the r eaction, reacting gas flow through porous media, and non-uniformities in the bed perme ability. The new model is now able to replicate the curved reaction front and asy mmetry of the exit gas mass fractions over time. The improved understanding of the exchange process and its dependence on the non-uniform bed properties and te mperatures in these larger systems is critical to the future design of such sy stems.

  9. Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, M.; Baba, A. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Kawamura, Y.; Nishi, M.


    Though lithium ceramic materials such as Li{sub 2}O, LiAlO{sub 2}, Li{sub 2}ZrO{sub 3}, Li{sub 2}TiO{sub 3} and Li{sub 4}SiO{sub 4} are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H{sub 2} and D{sub 2}O or that between D{sub 2} and H{sub 2}O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li{sub 2}ZrO{sub 3} blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

  10. [Solid state isotope hydrogen exchange for deuterium and tritium in human gene-engineered insulin]. (United States)

    Zolotarev, Yu A; Dadayan, A K; Kozik, V S; Gasanov, E V; Nazimov, I V; Ziganshin, R Kh; Vaskovsky, B V; Murashov, A N; Ksenofontov, A L; Haribin, O N; Nikolaev, E N; Myasoedov, N F


    The reaction of high temperature solid state catalytic isotope exchange in peptides and proteins under the action of catalyst-activated spillover hydrogen was studied. The reaction of human gene-engineered insulin with deuterium and tritium was conducted at 120-140° C to produce insulin samples containing 2-6 hydrogen isotope atoms. To determine the distribution of the isotope label over tritium-labeled insulin's amino acid residues, oxidation of the S-S bonds of insulin by performic acid was performed and polypeptide chains isolated; then their acid hydrolysis, amino acid analysis and liquid scintillation counts of tritium in the amino acids were conducted. The isotope label was shown to be incorporated in all amino acids of the protein, with the peptide fragment FVNQHLCGSHLVE of the insulin β-chain showing the largest incorporation. About 45% of the total protein isotope label was incorporated in His5 and His10 of this fragment. For the analysis of isotope label distribution in labeled insulin's peptide fragments, the recovery of the S-S bonds by mercaptoethanol, the enzymatic hydrolysis by glutamyl endopeptidase from Bacillus intermedius and HPLC division of the resulting peptides were carried out. Attribution of the peptide fragments formed due to hydrolysis at the Glu-X bond in the β-chain was accomplished by mass spectrometry. Mass spectrometry analysis data of the deuterium-labeled insulin samples' isotopomeric composition showed that the studied solid state isotope exchange reaction equally involved all the protein molecules. Biological studying of tritium-labeled insulin showed its physiological activity to be completely retained.

  11. Magnesium isotope fractionation in volcanic soils controlled by clay mineralogy and exchangeable Mg (United States)

    Opfergelt, S.; Georg, B.; Burton, K.; Delvaux, B.; Siebert, C.; Guicharnaud, R.; Cabidoche, Y.; Halliday, A.


    Continental weathering of calcium-magnesium silicates exerts a strong control on atmospheric CO2 concentrations. Mg stable isotopes are used here as a biogeochemical tracer to quantify the contributions from soil weathering processes and vegetation on the Mg budget and the chemistry of soil solutions exported to the hydrosphere. We report the isotopic budget of Mg in distinct Mg pools (bedrock, vegetation, bulk soils, clay fractions, exchangeable Mg, soil pore waters) in tropical (Guadeloupe, Basse-Terre) and temperate volcanic soils (Iceland, Borgarfjordur catchment). Exchangeable Mg was collected by percolation of ammonium acetate 1N at pH7. Mg isotope ratios were measured by MC-ICP-MS (Nu Plasma HR) with an external reproducibility for DSM3 standard (Galy et al., 2003, JAAS 18, 1352-1356) of ± 0.15 ‰, 2SD, for δ26Mg. We investigated two soil sequences from Guadeloupe, both derived from andesitic ash, with the mineralogical sequence evolving towards Mg-bearing and non Mg-bearing secondary phases, respectively: (1) Andosol - Cambisol - Vertisol with the mineralogical sequence A - All - H,S - S (*), and (2) Andosol - Nitisol - Ferralsol with the sequence A - G,All - H,F - K,G,F. The basaltic soils from Iceland include Histosol and Histic, Gleyic and Brown Andosol with clay fractions mainly constituted of All, H and F. This selection of soils, with contrasting Mg-bearing and non-bearing secondary phases, and contrasting amount of Mg exchangeable (1.2 to 6.6, allows for a direct assessment of the weathering control on Mg isotope ratios and the Mg budget in both tropical and temperate conditions. In Guadeloupe, bulk soils and clay fractions were isotopically heavier (-0.41 to -0.10 ‰) than the andesite bedrock (-0.47 ‰). Icelandic bulk soils were isotopically similar or lighter (-0.80 to -0.25 ‰) than the parental basalt (-0.31 ‰). In both Guadeloupe and Iceland, soils were isotopically lighter with increasing amount of exchangeable Mg


    Energy Technology Data Exchange (ETDEWEB)

    Krot, A N; Chaussidon, M; Yurimoto, H; Sakamoto, N; Nagashima, K; Hutcheon, I D; MacPherson, G J


    that CAIs 100, 160 and CG5 experienced melting in an {sup 16}O-rich ({Delta}{sup 17}O < -20{per_thousand}) nebular gas in the CAI-forming region. The Type C and Type-B-like portions of CAI 6-1-72 experienced melting in an {sup 16}O-depleted ({Delta}{sup 17}O {ge} -13{per_thousand}) nebular gas. CAIs ABC, TS26 and 93 experienced isotopic exchange during re-melting in the presence of an {sup 16}O-poor ({Delta}{sup 17}O {ge} -10{per_thousand}) nebular gas in the chondrule-forming region(s). Subsequently, Allende Type C CAIs experienced post-crystallization isotopic exchange with an {sup 16}O-poor reservoir that affected largely melilite and anorthite. Because pseudomorphic replacement of lacy melilite by grossular, monticellite and forsterite occurred during thermal metamorphism, some oxygen isotopic exchange of melilite and anorthite must have continued after formation of these secondary minerals. We suggest that some or all oxygen isotopic exchange in melilite and anorthite occurred during fluid-assisted thermal metamorphism on the CV parent asteroid. Similar processes may have also affected melilite and anorthite of CAIs in metamorphosed CO chondrites.

  13. High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes (United States)

    Sadat-Noori, Mahmood; Santos, Isaac R.; Tait, Douglas R.; Reading, Michael J.; Sanders, Christian J.


    We hypothesise that mangroves play an important role in groundwater exchange processes in sub-tropical and tropical estuarine waters. To investigate this, multiple high resolution time series measurements of radium across a tidal estuary (Coffs Creek, NSW, Australia) were performed as well as a spatial survey in both bottom and surface layers. Results from the spatial survey revealed increasing radium concentrations in parts of the estuary surrounded by mangroves. The average radium concentration in estuary areas lined with mangroves was 2.5 times higher than the average concentration at the mouth of the estuary and 6.5-fold higher than upstream freshwater areas. Additionally, the area enriched in radium coincided with low dissolved oxygen concentrations, implying that porewater exchange may drive anoxia. A radium mass balance model based on 223Ra and 224Ra isotopes at different sections of the estuary confirmed higher porewater exchange rates from areas fringed with mangrove vegetation. Estimated porewater exchange rates were 27.8 ± 5.3 and 13.6 ± 2.1 cm d-1 (0.8 ± 0.1 and 0.4 ± 0.1 m3 s-1) based on 223Ra and 224Ra isotopes, respectively. The average saline porewater exchange was ∼ 10-fold larger than the upstream surface freshwater inputs to the estuary. We suggest that mangrove environments within subtropical estuaries are hotspots for porewater exchange due to the complex belowground structure of crab burrows and the effect of tidal pumping. Because porewater exchange releases carbon and nitrogen from coastal sediments, development and modification of mangrove areas in subtropical estuaries have a significant effect on coastal biogeochemical cycles.

  14. Isotopic evidence of limited exchange between Mediterranean and eastern North Atlantic fin whales. (United States)

    Giménez, Joan; Gómez-Campos, Encarna; Borrell, Asunción; Cardona, Luis; Aguilar, Alex


    The relationship between stocks of fin whales inhabiting the temperate eastern North Atlantic and the Mediterranean Sea is subject to controversy. The use of chemical markers facilitates an alternative insight into population structure and potential borders between stocks because the two areas present dissimilar isotopic baselines. Baleen plates, composed of inert tissue that keeps a permanent chronological record of the isotopic value of body circulating fluids, were used to investigate connectivity and boundaries between the stocks. Values were determined by continuous flow isotope ratio mass spectrometry. Stable isotopes confirm that, while the two subpopulations generally forage in well-differentiated grounds, some individuals with characteristic Atlantic values do penetrate into the Mediterranean Sea up to the northernmost latitudes of the region. As a consequence, the border between the two putative subpopulations may be not as definite as previous acoustic investigations suggested. The discriminant function obtained in this study may assist researchers to use baleen plate isotopic data to assign the origin of fin whales of uncertain provenance. This study strengthens the stock subdivision currently accepted for management and conservation while recognizes a low level of exchange between the Mediterranean and temperate eastern North Atlantic subdivisions. Copyright © 2013 John Wiley & Sons, Ltd.

  15. Diffusion, trapping, and isotope exchange of plasma implanted deuterium in ion beam damaged tungsten (United States)

    Barton, Joseph Lincoln

    Tritium accumulation in nuclear fusion reactor materials is a major concern for practical and safe fusion energy. This work examines hydrogen isotope exchange as a tritium removal technique, analyzes the effects of neutron damage using high energy copper ion beams, and introduces a diffusion coefficient that is a function of the concentration of trapped atoms. Tungsten samples were irradiated with high energy (0.5 - 5 MeV) copper ions for controlled levels of damage - 10-3 to 10-1 displacements per atom (dpa) - at room temperature. Samples were then exposed to deuterium plasma at constant temperature (˜ 380 K) to a high fluence of 1024 ions/m2, where retention is at is maximized (i.e. saturated). By then subsequently exposing these samples to fractions of this fluence with hydrogen plasma, isotope exchange rates were observed. The resulting deuterium still trapped in the tungsten is then measured post mortem. Nuclear reaction analysis (NRA) gives the depth resolved deuterium retention profile with the 3He(D,p) 4He reaction, and thermal desorption spectroscopy (TDS) gives the total amount of deuterium trapped in the tungsten by heating a sample in vacuum up to 1200 K and measuring the evaporated gas molecules with a residual gas analyzer. Isotope exchange data show that hydrogen atoms can displace trapped deuterium atoms efficiently only up to the first few microns, but does not affect the atoms trapped at greater depths. In ion damaged tungsten, measurements showed a significant increase in retention in the damage region proportional to dpa 0.66, which results in a significant spike in total retention, and isotope exchange in damaged samples is still ineffective at depths greater than a few microns. Thus, isotope exchange is not an affective tritium removal technique; however, these experiments have shown that trapping in material defects greatly affects diffusion. These experiments lead to a simplified diffusion model with defect densities as the only free

  16. Experimental investigation of rates and mechanisms of isotope exchange (O, H) between volcanic ash and isotopically-labeled water (United States)

    Nolan, Gary S.; Bindeman, Ilya N.


    The hydrogen and oxygen isotope ratios in hydrous minerals and volcanic glass are routinely used as paleo-proxies to infer the isotopic values of meteoric waters and thus paleo-climatic conditions. We report a series of long-term exposure experiments of distal 7700 BP Mt. Mazama ash (-149‰ δ2H, +7‰ δ18O, 3.8 wt.% H2O) with isotopically-labeled water (+650‰ δ2H, +56‰ δ18O). Experiments were done at 70, 40 and 20 °C, and ranged in duration from 1 to 14454 h (˜20 months), to evaluate the rates of deuterium and 18O exchange, and investigate the relative role of exchange and diffusion. We also investigate the effect of drying on H2Otot and δ2H in native and reacted ash that can be used in defining the protocols for natural sample preparation. We employ Thermal Conversion Elemental Analyzer (TCEA) mass spectrometry, thermogravimetric analysis and a KBr pellet technique with infrared spectroscopy to measure the evolution of δ2H, total water, and OH water peaks in the course of exposure experiments, and in varying lengths of vacuum drying. Time series experiments aided by infrared measurements demonstrate the following new results: (i) It wasobserved that from 5 to >100‰ δ2H increases with time, with faster deuterium exchange at higher temperatures. Times at 15% of theoretical "full δ2H exchange" are: 15.8 years at 20 °C, 5.2 years at 40 °C, and 0.4 years at 70 °C. (ii) Even at extended exposure durations experiments show no net increase in water weight percent nor in δ18O in ash; water released from ash rapidly by thermal decomposition is not enriched in δ18O. This observation clearly suggests that it is hydrogen exchange, and not water addition or oxygen exchange that characterizes the process. (iii) Our time series drying, Fourier transform infrared (FTIR)-KBr and Thermogravimetric Analyzer (TGA) analyses collectively suggest a simple mechanistic view that there are three kinds of "water" in ash: water (mostly H2O) that is less strongly bonded

  17. Does Size Really Matter? The Steric Isotope Effect in a Supramolecular Host?Guest Exchange Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth


    Isotope effects (IEs), which arise from differences in zero point energies (ZPEs) between a parent and isotopically substituted bond, have been used extensively by chemists to probe molecular interactions and reactivity. Due to the anharmonicity of the C-H/D vibrational potential energy function and the lower ZPE of a C-D bond, the average C-D bond length is typically {approx}0.005 {angstrom} shorter than an equivalent C-H bond. It is this difference in size that is often invoked to explain the observation of secondary, inverse kinetic isotope effects (KIEs) in chemical processes which proceed through a sterically strained transition state. This so-called 'steric isotope effect' (SIE) has been observed in processes such as the racemization of ortho-substituted biphenyls[6] and phenanthrenes, ring flipping of cyclophanes, and more recently in the deslipping of rotaxanes, where substitution of the sterically less demanding deuterium for protium results in rate accelerations for these processes. Herein, we use deuterium substitution in a cationic guest molecule to probe the sensitivity limits of the guest exchange process from a highly-charged supramolecular host.

  18. Stochastic Simulation of Isotopic Exchange Mechanisms for Fe(II)-Catalyzed Recrystallization of Goethite

    Energy Technology Data Exchange (ETDEWEB)

    Zarzycki, Piotr [Energy; Institute; Rosso, Kevin M. [Pacific Northwest


    Understanding Fe(II)-catalyzed transformations of Fe(III)- (oxyhydr)oxides is critical for correctly interpreting stable isotopic distributions and for predicting the fate of metal ions in the environment. Recent Fe isotopic tracer experiments have shown that goethite undergoes rapid recrystallization without phase change when exposed to aqueous Fe(II). The proposed explanation is oxidation of sorbed Fe(II) and reductive Fe(II) release coupled 1:1 by electron conduction through crystallites. Given the availability of two tracer exchange data sets that explore pH and particle size effects (e.g., Handler et al. Environ. Sci. Technol. 2014, 48, 11302-11311; Joshi and Gorski Environ. Sci. Technol. 2016, 50, 7315-7324), we developed a stochastic simulation that exactly mimics these experiments, while imposing the 1:1 constraint. We find that all data can be represented by this model, and unifying mechanistic information emerges. At pH 7.5 a rapid initial exchange is followed by slower exchange, consistent with mixed surface- and diffusion-limited kinetics arising from prominent particle aggregation. At pH 5.0 where aggregation and net Fe(II) sorption are minimal, that exchange is quantitatively proportional to available particle surface area and the density of sorbed Fe(II) is more readily evident. Our analysis reveals a fundamental atom exchange rate of ~10-5 Fe nm-2 s-1, commensurate with some of the reported reductive dissolution rates of goethite, suggesting Fe(II) release is the rate-limiting step in the conduction mechanism during recrystallization.

  19. Site selective syntheses of [(3)H]omeprazole using hydrogen isotope exchange chemistry. (United States)

    Pollack, Scott R; Schenk, David J


    Omeprazole (Prilosec®) is a selective and irreversible proton pump inhibitor used to treat various medical conditions related to the production of excess stomach acids. It functions by suppressing secretion of those acids. Radiolabeled compounds are commonly employed in the drug discovery and development process to support efforts including library screening, target identification, receptor binding, assay development and validation and safety assessment. Herein, we describe synthetic approaches to the controlled and selective labeling of omeprazole with tritium via hydrogen isotope exchange chemistry. The chemistry may also be used to prepare tritium labeled esomeprazole (Nexium®), the active pure (S)-enantiomer of omeprazole. Copyright © 2015 John Wiley & Sons, Ltd.

  20. [Net CO2 exchange and carbon isotope flux in Acacia mangium plantation]. (United States)

    Zou, Lu-Liu; Sun, Gu-Chou; Zhao, Ping; Cai, Xi-An; Zeng, Xiao-Ping; Wang, Quan


    By using stable carbon isotope technique, the leaf-level 13C discrimination was integrated to canopy-scale photosynthetic discrimination (Deltacanopy) through weighted the net CO2 assimilation (Anet) of sunlit and shaded leaves and the stand leaf area index (L) in an A. mangium plantation, and the carbon isotope fluxes from photosynthesis and respiration as well as their net exchange flux were obtained. There was an obvious diurnal variation in Deltacanopy, being lower at dawn and at noon time (18.47 per thousand and 19.87 per thousand, respectively) and the highest (21.21 per thousand) at dusk. From the end of November to next May, the Deltacanopy had an increasing trend, with an annual average of (20.37 +/- 0.29) per thousand. The carbon isotope ratios of CO2 from autotrophic respiration (excluding daytime foliar respiration) and heterotrophic respiration were respectively (- 28.70 +/- 0.75) per thousand and (- 26.75 +/- 1.3) per thousand in average. The delta13 C of nighttime ecosystem-respired CO2 in May was the lowest (-30.14 per thousand), while that in November was the highest (-28.01 per thousand). The carbon isotope flux of CO2 between A. mangium forest and atmosphere showed a midday peak of 178.5 and 217 micromol x m(-2) x s(-1) x per thousand in May and July, with the daily average of 638.4 and 873.2 micromol x m(-2) x s(-1) x per thousand, respectively. The carbon isotope flux of CO2 absorbed by canopy leaves was 1.6-2.5 times higher than that of CO2 emitted from respiration, suggesting that a large sum of CO2 was absorbed by A. mangium, which decreased the atmospheric CO2 concentration and improved the environment.


    Energy Technology Data Exchange (ETDEWEB)

    Fox, E


    Proton Exchange Membrane Electrolyzers have potential interest for use for hydrogen isotope separation from water. In order for PEME to be fully utilized, more information is needed on the stability of Nafion when exposed to radiation. This work examines Nafion 117 under varying exposure conditions, including dose rate, total dosage and atmospheric condition. Analytical tools, such as FT-IR, ion exchange capacity, DMA and TIC-TOC were used to characterize the exposed membranes. Analysis of the water from saturated membranes can provide important data on the stability of the membranes during radiation exposure. It was found that the dose rate of exposure plays an important role in membrane degradation. Potential mechanisms for membrane degradation include peroxide formation by free radicals.

  2. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates (United States)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.


    Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H 2O) 63+), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen) 2(H 2O) 2] 3+ [ 1] and [Rh(phen) 2(H 2O)Cl] 2+ [ 2] where (phen) = 1,10-phenanthroline. Complex [ 1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [ 2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of 18O and 16O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k0298 = 5 × 10 -8(±0.5 × 10 -8) s -1 for [ 1] and k0298 = 2.5 × 10 -9(±1 × 10 -9) for [ 2]. Enthalpy and entropy activation parameters (Δ H‡ and Δ S‡) were measured to be 119(±3) kJ mol -1, and 14(±1) J mol -1 K -1, respectively for [ 1]. The corresponding parameters for the mono-aquo complex, [ 2], are 132(±3) kJ mol -1 and 41.5(±2) J mol -1 K -1. Rates increase by many orders of magnitude

  3. Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Mike, E-mail: [CSIRO Land and Water, PMB No 2, Glen Osmond, SA, 5064 (Australia); Kookana, Rai [CSIRO Land and Water, PMB No 2, Glen Osmond, SA, 5064 (Australia)


    Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating {sup 12}C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with {sup 14}C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.

  4. Mass-independent isotopic fractionation of tin in a chemical exchange reaction (United States)

    Fujii, T.; Moynier, F.


    Tin isotopes were fractionated by the liquid-liquid extraction technique with a crown ether, dicyclohexano-18- crown-6 (DC18C6). Tin dichloride was dissolved in HCl to create solutions, 0.1 mol dm-3 (M) Sn(II) in various [HCl]. The organic phase was 0.1 M DC18C6 in 1,2-dichloroethane. A 5 cm3 aqueous solution and a 5 cm3 organic solution were mixed in a glass vial with a stirrer bar, and the glass vial was sealed. The two phases were stirred by a magnetic stirrer, and after the equilibrium, the two phases were separated by centrifugation. An aliquot of the upper aqueous solution was taken for analysis. These procedures were carried out at room temperature. The Sn concentration in the equilibrated aqueous phase was analyzed by ICP-AES. In order to avoid any matrix effect, possible trace of organic materials from DC18C6 was separated from the Sn on a micro-column anion-exchange resin in HBr/HNO3. An aliquot of the aqueous phase was once dried by heating and then dissolved into a HBr solution. Sn was strongly adsorbed while organic materials went through. Finally Sn was collected in a HNO3 solution. A solution containing 300 ppb of Sn in 0.05 M HNO3 was prepared for isotopic analysis. Isotopic ratios of Sn in all samples were analyzed with the MC-ICP-MS Nu plasma 500 HR at ENS Lyon coupled with a desolvating nebulizer Nu DSN-100 (with a typical precision of <100 ppm). The instrumental mass bias was controlled by bracketing each of the samples with standards. Because 120Sn is the most abundant isotopes, the isotope ratios have been measured as mSn/120Sn (m : 116, 117, 118, 119, 122, and 124). 114Sn and 115Sn were not analyzed due to their low abundances. Possible interferences with Cd on the masses 116, with Te on the mass 120, 122 and 124 were verified to be under the detection of the ICP-MS. Odd atomic mass isotopes (117Sn and 119Sn) showed deficits of enrichment comparing to the even atomic mass isotopes (116Sn, 118Sn, 122Sn, and 124Sn). This odd-even staggering

  5. Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary (United States)

    Chen, Mengli; Lee, Jong-Mi; Nurhati, Intan; Zurbrick, Cheryl; Switzer, Adam D.; Carrasco, Gonzalo


    Atmospheric aerosols are the dominant source of Pb to the modern marine environment, and as a result, in most regions of the ocean the Pb isotopic composition of dissolved Pb in the surface ocean (and in corals) matches that of the regional aerosols. In the Singapore Strait, however, there is a large offset between seawater dissolved and coral Pb isotopes and that of the regional aerosols. We propose that this difference results from isotope exchange between dissolved Pb supplied by anthropogenic aerosol deposition and adsorbed natural crustal Pb on weathered particles delivered to the ocean by coastal rivers. To investigate this issue, Pb isotope exchange was assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (which discharges to the Singapore Strait). During the experiment, a known amount of dissolved Pb with the isotopic composition of NBS-981 (206Pb/207Pb = 1.093) was spiked into the unfiltered Johor water (dissolved and particulate 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. The mixing ratio of the estuarine and spike Pb should have produced a dissolved 206Pb/207Pb isotopic composition of 1.161, but within a week, the 206Pb/207Pb in the water increased to 1.190 and continued to increase to 1.197 during the next two months without significant changes of the dissolved Pb concentration. The kinetics of isotope exchange was assessed using a simple Kd model, which assumes multiple sub-reservoirs within the particulate matter with different exchange rate constants. The Kd model reproduced 56% of the observed Pb isotope variance. Both the closed-system experiment and field measurements imply that isotope exchange can be an important mechanism for controlling Pb and Pb isotopes in coastal waters. A similar process may occur for other trace elements. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element

  6. An improved method of ion exchange for nitrogen isotope analysis of water nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Xing Meng [State Key Laboratory of Loess and Quaternary Geology, IEE, CAS, Xi' an, 710075 (China); Graduate School of Chinese Academy of Sciences, Beijing, 100039 (China); Liu Weiguo, E-mail: [State Key Laboratory of Loess and Quaternary Geology, IEE, CAS, Xi' an, 710075 (China); Xi' an Jiaotong University, Xi' an, 710049 (China)


    Nitrate nitrogen and oxygen isotopes have been widely used to trace the nitrogen biogeochemical cycle by identifying NO{sub 3}{sup -} sources. An improved method of anion exchange was developed to measure {delta}{sup 15}N-NO{sub 3}{sup -} in fresh water by continuous-flow elemental analyzer/isotope ratio mass spectrometry (EA-IRMS). We used a custom-built exchange resin column, a peristaltic pump and the oven-drying method in our experiments. Consequently, the amount of Ag{sub 2}O used as a neutralizer was reduced, time was saved, and operation became simpler than before. Meanwhile, analytical precision remained identical to previous studies. KNO{sub 3} solutions were prepared at 0.2, 5 and 25 mg-N L{sup -1} from KNO{sub 3} standard salt ({delta}{sup 15}N = +6.27 per mille ), and the average {delta}{sup 15}N values of the solutions after having been absorbed on and subsequently stripped from anion columns were +6.62 {+-} 0.22 per mille (n = 6), +6.38 {+-} 0.09 per mille (n = 6), and +6.26 {+-} 0.07 per mille (n = 6), respectively. In addition, the 'natural' water sample {delta}{sup 15}N-NO{sub 3}{sup -} showed consistency in comparison to standards, and the mean standard deviation by the different approaches was 0.08 per mille . Accordingly, by these improvements the anion exchange resin technique is demonstrated to be more suitable for measuring {delta}{sup 15}N in NO{sub 3}{sup -} than original techniques.

  7. Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols. (United States)

    Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L


    This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis (United States)

    Ball, J.W.; Bassett, R.L.


    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  9. Carbon mass-balance modeling and carbon isotope exchange processes in the Curonian Lagoon (United States)

    Barisevičiūtė, Rūta; Žilius, Mindaugas; Ertürk, Ali; Petkuvienė, Jolita


    The Curonian lagoon one of the largest coastal lagoons in Europe is located in the southeastern part of the Baltic Sea and lies along the Baltic coast of Lithuania and the Kaliningrad region of Russia. It is influenced by a discharge of the Nemunas and other smaller rivers and saline water of the Baltic Sea. The narrow (width 0.4 km, deep 8-14 m) Klaipėda Strait is the only way for fresh water run-off and brackish water intrusions. This research is focused on carbon isotope fractionations related with air - water exchange, primary production and organic carbon sedimentation, mineralization and uptake from both marine and terrestrial sources.

  10. Process Model for Studying Regional 13C Stable Isotope Exchange between Vegetation and Atmosphere (United States)

    Chen, J. M.; Chen, B.; Huang, L.; Tans, P.; Worthy, D.; Ishizawa, M.; Chan, D.


    The variation of the stable isotope 13CO2 in the air in exchange with land ecosystems results from fractionation processes in both plants and soil during photosynthesis and respiration. Its diurnal and seasonal variations therefore contain information on the carbon cycle. We developed a model (BEPS-iso) to simulate its exchange between vegetation and the atmosphere. To be useful for regional carbon cycle studies, the model has the following characteristics: (i) it considers the turbulent mixing in the vertical profile from the soil surface to the top of the planetary boundary layer (PBL); (ii) it scales individual leaf photosynthetic discrimination to the whole canopy through the separation of sunlit and shaded leaf groups; (iii) through simulating leaf-level photosynthetic processes, it has the capacity to mechanistically examine isotope discrimination resulting from meteorological forcings, such as radiation, precipitation and humidity; and (iv) through complete modeling of radiation, energy and water fluxes, it also simulates soil moisture and temperature needed for estimating ecosystem respiration and the 13C signal from the soil. After validation using flask data acquired at 20 m level on a tower near Fraserdale, Ontario, Canada, during intensive campaigns (1998-2000), the model has been used for several purposes: (i) to investigate the diurnal and seasonal variations in the disequilibrium in 13C fractionation between ecosystem respiration and photosynthesis, which is an important step in using 13C measurements to separate these carbon cycle components; (ii) to quantify the 13C rectification in the PBL, which differs significantly from CO2 rectification because of the diurnal and seasonal disequilibriums; and (iii) to model the 13C spatial and temporal variations over the global land surface for the purpose of CO2 inversion using 13C as an additional constraint.

  11. Solvent deuterium isotope effects in the catalysis of oxygen-18 exchange by human carbonic anhydrase II. (United States)

    Tu, C K; Silverman, D N


    By measuring the rate of exchange at chemical equilibrium of 18O between HCO3- and H2O catalyzed by human carbonic anhydrase II in the absence of buffers, we have determined the rate of release from the enzyme of water bearing substrate oxygen. The ratio of this rate measured in H2O to the rate measured in D2O, the solvent deuterium isotope effect, is between 4 and 9 in the range of pH(D) from 5.8 to 8.0, with a value of 8.0 +/- 0.7 at pH(D) 6.6 (uncorrected pH meter reading). The magnitude of this isotope effect at pH(D) 6.6 has an exponential dependence on the atom fraction of deuterium in solvent water. We conclude that an intramolecular proton transfer between a proton shuttle group on the enzyme and the active site is rate limiting for the release from the enzyme of water bearing substrate oxygen and involves a change in bonding of more than one proton. In contrast, the solvent deuterium isotope effect on the intermolecular proton transfer between the external buffer imidazole and the active site (or proton shuttle group) of the enzyme is small, 2.3 at pH(D) 7.0, as determined from initial velocity experiments. With a rate constant near 9 X 10(8) M-1 s-1, this intermolecular transfer is limited to a significant extent by diffusion processes.

  12. An Experimental Investigation of the Process of Isotope Exchange that Takes Place when Heavy Water Is Exposed to the Atmosphere (United States)

    Deeney, F. A.; O'Leary, J. P.


    We have used the recently developed method for rapid measurement of maximum density temperature to determine the rate at which hydrogen and deuterium isotope exchange takes place when a sample of heavy water is exposed to the atmosphere. We also provide a simple explanation for the observed linear rate of transition. (Contains 2 figures.)

  13. Enrichment of lithium isotope .sup.6./sup.Li by ion exchange resin with specific particle size

    Czech Academy of Sciences Publication Activity Database

    Mikeš, J.; Ďurišová, Jana; Jelínek, L.


    Roč. 312, č. 1 (2017), s. 13-18 ISSN 0236-5731 Institutional support: RVO:67985831 Keywords : lithium * isotope separation * elution chromatography * ion exchange chromatography Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.282, year: 2016

  14. Modelling non-steady-state isotope enrichment of leaf water in a gas-exchange cuvette environment. (United States)

    Song, Xin; Simonin, Kevin A; Loucos, Karen E; Barbour, Margaret M


    The combined use of a gas-exchange system and laser-based isotope measurement is a tool of growing interest in plant ecophysiological studies, owing to its relevance for assessing isotopic variability in leaf water and/or transpiration under non-steady-state (NSS) conditions. However, the current Farquhar & Cernusak (F&C) NSS leaf water model, originally developed for open-field scenarios, is unsuited for use in a gas-exchange cuvette environment where isotope composition of water vapour (δv ) is intrinsically linked to that of transpiration (δE ). Here, we modified the F&C model to make it directly compatible with the δv -δE dynamic characteristic of a typical cuvette setting. The resultant new model suggests a role of 'net-flux' (rather than 'gross-flux' as suggested by the original F&C model)-based leaf water turnover rate in controlling the time constant (τ) for the approach to steady sate. The validity of the new model was subsequently confirmed in a cuvette experiment involving cotton leaves, for which we demonstrated close agreement between τ values predicted from the model and those measured from NSS variations in isotope enrichment of transpiration. Hence, we recommend that our new model be incorporated into future isotope studies involving a cuvette condition where the transpiration flux directly influences δv . There is an increasing popularity among plant ecophysiologists to use a gas-exchange system coupled to laser-based isotope measurement for investigating non-steady state (NSS) isotopic variability in leaf water (and/or transpiration); however, the current Farquhar & Cernusak (F&C) NSS leaf water model is unsuited for use in a gas-exchange cuvette environment due to its implicit assumption of isotope composition of water vapor (δv ) being constant and independent of that of transpiration (δE ). In the present study, we modified the F&C model to make it compatible with the dynamic relationship between δv and δE as is typically associated

  15. QUDeX-MS: hydrogen/deuterium exchange calculation for mass spectra with resolved isotopic fine structure. (United States)

    Salisbury, Joseph P; Liu, Qian; Agar, Jeffrey N


    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry permits analysis of structure, dynamics, and molecular interactions of proteins. HDX mass spectrometry is confounded by deuterium exchange-associated peaks overlapping with peaks of heavy, natural abundance isotopes, such as carbon-13. Recent studies demonstrated that high-performance mass spectrometers could resolve isotopic fine structure and eliminate this peak overlap, allowing direct detection and quantification of deuterium incorporation. Here, we present a graphical tool that allows for a rapid and automated estimation of deuterium incorporation from a spectrum with isotopic fine structure. Given a peptide sequence (or elemental formula) and charge state, the mass-to-charge ratios of deuterium-associated peaks of the specified ion is determined. Intensities of peaks in an experimental mass spectrum within bins corresponding to these values are used to determine the distribution of deuterium incorporated. A theoretical spectrum can then be calculated based on the estimated distribution of deuterium exchange to confirm interpretation of the spectrum. Deuterium incorporation can also be detected for ion signals without a priori specification of an elemental formula, permitting detection of exchange in complex samples of unidentified material such as natural organic matter. A tool is also incorporated into QUDeX-MS to help in assigning ion signals from peptides arising from enzymatic digestion of proteins. MATLAB-deployable and standalone versions are available for academic use at and . Isotopic fine structure HDX-MS offers the potential to increase sequence coverage of proteins being analyzed through mass accuracy and deconvolution of overlapping ion signals. As previously demonstrated, however, the data analysis workflow for HDX-MS data with resolved isotopic fine structure is distinct. QUDeX-MS we hope will aid in the adoption of isotopic fine structure HDX

  16. Novel Hydrophobic Pt/Inorganic Catalyst Used in Hydrogen Isotope Exchange Reaction

    Directory of Open Access Journals (Sweden)

    JIA Qing-qing1;HU Shi-lin1;FENG Xiao-yan2;LIU Ya-ming1


    Full Text Available To improve the performance of hydrophobic catalyst and extend its using range, this research adopted the porous columnar inorganic carriers (ø=5 mm to prepare the hydrophobic catalyst used in hydrogen isotopes exchange reaction, the hydrophilic carriers became hydrophobic with the nanostructured CeO2 coating and the catalyst were then fabricated by convenient impregnation method. The samples were characterized by XRD、SEM、EDX、XPS and CO adsorption. The catalytic activity were tested through catalytic exchange reaction between hydrogen and saturated water vapor to investigate the effect of micro structured CeO2 on the catalyst properties. It turned out that the nano-CeO2 coating could build favorable hydrophobic environment for the catalysts and had almost no influence on the pore structure properties of carriers. Although the hydrophobic coating would lead to the decrease of Pt particle dispersion and metallic Pt content, it could make the Pt particles mostly deposit on the surface layer of the catalysts, which would make more Pt particle participate in the reaction at the same time. The catalytic activity of the novel Pt/inorganic catalyst could reach to 80% of the mature Pt/organic catalyst. After being flushed by water for 12 weeks, the catalytic activity of Pt/inorganic catalyst decreased less than 5%. The novel hydrophobic catalyst with good activity and stability was practical and had great application prospects.

  17. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution (United States)

    Rustad, James R.; Casey, William H.


    Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface.

  18. Quantifying the free living energy exchanges of Arctic ungulates with stable isotopes

    Directory of Open Access Journals (Sweden)

    Paul Haggarty


    thermoregulatory thermogenesis, in order to interpret the values for overall expenditure. For these reasons the most valuable use of the DLW method in the field may be to validate factorial models and other approaches so that they may be used with confidence. Additional important information on the energy exchanges of free ranging animals may be obtained from other stable isotope methodologies. In addition to the use of the isotopes 2H and lsO in the DLW method, natural variations in the abundance of "C and 15N in the arctic environment may be exploited to study diet selection in truly free living arctic ungulates.

  19. Experimental simulation of oxygen isotopic exchange in olivine and implication for the formation of metamorphosed carbonaceous chondrites (United States)

    Ivanova, Marina A.; Lorenz, Cyril A.; Franchi, Ian A.; Bychkov, Andrei Y.; Post, Jeffrey E.


    We have conducted hydration-dehydration experiments on terrestrial olivine to investigate the behavior of oxygen isotopic fractionation to test the hypothesis that multiple cycles of aqueous and thermal processing on a parent asteroid comprise a genetic relationship between CM2s and metamorphosed carbonaceous chondrites (MCCs). Two experiments were undertaken. In the first experiment, serpentine was obtained by hydrating terrestrial olivine (Fo90.9) in the laboratory. During this experiment, olivine was reacted with isotopically heavy water (δ18O 21.5‰) at T = 300 °C, PH2O = 300 bar, for 100 days. The oxygen isotopic composition of the experimental serpentine was enriched in 18O (by 10 ‰ in δ18O) due to exchange of oxygen isotopes between olivine and the 18O-rich water. Dehydrated serpentine was then produced during laboratory heating experiment in vacuum, at T = 930 °C, for 1 h. The oxygen isotopic composition of the dehydrated serpentine was enriched in 18O by a further 7 ‰. The net result of the hydration-dehydration process was an enrichment of 18O in the final material by approximately 17‰. The new experimental results suggest that the oxygen isotopic compositions of MCCs of the Belgica-like group, including Dhofar 225 and Dhofar 725, could be derived from those of typical CM2 chondrites via several cycles of hydration-dehydration caused by aqueous alteration and subsequent thermal metamorphism within their parent asteroids.

  20. Oxygen exchange with water alters the oxygen isotopic signature of nitrate in soil ecosystems.

    NARCIS (Netherlands)

    Kool, D.M.; Wrage, N.; Oenema, O.; Kessel, van C.; Groenigen, van J.W.


    Combined oxygen (O) and nitrogen (N) stable isotope analyses are commonly used in the source determination of nitrate . The source and fate of are studied based on distinct O and N isotopic signatures (d18O and d15N) of various sources and isotopic effects during transformation processes, which

  1. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange (United States)

    Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.


    Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

  2. Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time (United States)

    Lippold, Holger; Eidner, Sascha; Kumke, Michael U.; Lippmann-Pipke, Johanna


    Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of 160Tb as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable 159Tb or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of 160Tb was introduced prior to saturation with 159Tb, the expected partial desorption of 160Tb occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive

  3. Equilibrium isotope exchange kinetics of native and site-specific mutant forms of E. coli aspartate transcarbamoylase

    Energy Technology Data Exchange (ETDEWEB)

    Wedler, F.C.; Hsuanyu, Y.; Kantrowitz, E.R.


    Isotope exchange kinetics at equilibrium (EIEK) have been used to probe the kinetic and regulatory mechanisms of native aspartate transcarbamoylase (ATCase) from E. coli at pH 7.0, 30/sup 0/. Substrate saturation patterns were most consistent with a preferred order random kinetic mechanism: C-P prior to L-Asp, C-Asp released before Pi, with the Asp in equilibrium C-Asp exchange rate 5X faster than C-P in equilibrium Pi. Computer simulations allow one to fit the EIEK experimental data and to arrive at the best set of kinetic constants for a given enzyme state. These approaches have been applied to modified ATCase. Bound CTP and ATP were observed, respectively, to inhibit and activate differentially Asp in equilibrium C-Asp, but not C-P in equilibrium Pi, indicating that these modifiers alter the association-dissociation rates of L-Asp and C-Asp but not of C-P or Pi. Low levels of PALA activated both exchange rates (due to shifting the T-R equilibrium), but higher (PALA) completely blocked both exchanges. The effects of a site-specific mutation of Tyr240 Phe have been similarly probed by EIEK methods. The Phe240 mutant enzyme exhibited kinetic properties markedly different from native ATCase: the data indicate that Phe240 ATCase is much closer to an R-state enzyme than is native enzyme.

  4. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail:; Sboev, Mikhail N.; Chizhov, Yuri V.


    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  5. The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere. (United States)

    Johnson, Jennifer E; Berry, Joseph A


    The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics. © 2013 John Wiley & Sons Ltd.

  6. Hydrogen isotope exchange kinetics of single protons in bovine pancreatic trypsin inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Woodward, C.K.; Hilton, B.C.


    The exchange kinetics of the slowest exchanging BPTI ..beta..-sheet protons are complex compared to model peptides; the activation energy, E/sub a/, and the pH dependence are temperature dependent. We have measured the exchange kinetics in the range pH 1 to 11, 33 to 71/sup 0/C, particularly the temperature dependence. The data are fit to a model in which exchange of each proton is determined by two discrete dynamical processes, one with E/sub a/ approx. 65 kcal/mol and less than first order dependence on catalyst ion, and one with E/sub a/ 20 to 30 kcal/mol and approaching first order in catalyst ion. The low activation energy process is the mechanism of interest in the native conformation of globular proteins and involves low energy, small amplitude fluctuations; the high activation energy process involves major unfolding. The model is simple, has a precedent in the hydrogen exchange literature, and explains quantitatively the complex feature of the exchange kinetics of single protons in BPTI.

  7. Continuous, in situ Isotopic Carbon Dioxide Measurements of Ecosystem Exchange Processes and Soil Respiration Using a WS-CRDS Analyzer (United States)

    van Pelt, A. D.; Rahn, T. A.; Risk, D.; McDowell, N.; Powers, H.; Nickerson, N. R.; Bible, K.; Rella, C.; Wahl, E.


    Understanding the interdependencies of sources and sinks within ecosystems and validating models of such systems greatly benefits from fast, continuous, in situ measurements of not only CO2 concentration, but also isotopic carbon abundances in CO2. Such high frequency (influencing global atmospheric carbon budget. By utilizing high time resolution instrumentation based on Wavelength-Scanned Cavity Ring Down Spectroscopy (WS-CRDS) the biosphere-atmosphere CO2 exchange mechanisms can be more carefully examined. This measurement technique achieves precisions of approximately 0.3‰ with measurement drift that is sufficiently low so as to avoid frequent calibration and can be deployed in remote, unattended locations for long-term, continuous measurements, enabling the observation of diurnal and seasonal trends in the CO2 exchange processes. We present two sets of data from a recently commercialized WS-CRDS analyzer. The first is from Wind River Canopy Crane, WA, analyzing air within the canopy of an old growth forest. By combining this high-resolution isotopic CO2 data with existing models of the ecosystem carbon budget, these models can be further examined to test their sensitivities to currently held assumptions about the effect of environmental forcings (e.g. temperature, precipitation, VPD/RH, soil moisture, incident radiaition) on heterotrophic respiration. The second set of data is from a soil chamber in which δ13CO2 is continuously measured. Such monitoring of soil has been instrumental in validating recent modeling efforts that describe isotope dynamics in diffusive environments where equilibrium has not been established. We see that true isotopic equilibrium is likely rare because of the time it takes for all isotopologues to equilibrate. This results in a range of dynamic fractionations (frequently several permil) that in soil environments are a result of changes in the CO2 production rate, gas diffusivity, and air-filled porosity. This effect is seen to

  8. Influence of helium on hydrogen isotope exchange in tungsten at sequential exposures to deuterium and helium–protium plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Bobyr, N.P., E-mail: [NRC “Kurcharov Institute”, Ac. Kurcharov sq., 1/1, Moscow 123182 (Russian Federation); Alimov, V.Kh. [Max-Planck-Institut für Plasmaphysik, D-85748 Garching (Germany); Hydrogen Isotope Research Center, University of Toyama, Toyama 930-8555 (Japan); Khripunov, B.I.; Spitsyn, A.V. [NRC “Kurcharov Institute”, Ac. Kurcharov sq., 1/1, Moscow 123182 (Russian Federation); Mayer, M. [Max-Planck-Institut für Plasmaphysik, D-85748 Garching (Germany); Hatano, Y. [Hydrogen Isotope Research Center, University of Toyama, Toyama 930-8555 (Japan); Golubeva, A.V.; Petrov, V.B. [NRC “Kurcharov Institute”, Ac. Kurcharov sq., 1/1, Moscow 123182 (Russian Federation)


    Hydrogen isotopes exchange in tungsten was investigated after sequential exposures to low energy deuterium (D) and helium–seeded protium (He–seeded H) plasmas at sample temperatures of 403 and 533 K. Deuterium depth profiles were measured by the D({sup 3}He, p){sup 4}He nuclear reaction with {sup 3}He{sup +} energies between 0.69 and 4.5 MeV allowing determination of the D concentration up to a depth of 8 μm. It was found that a significant part of the deuterium initially retained in tungsten after D plasma exposure was released during sequential exposure to a protium plasma. However, exposure of the D-plasma-exposed W samples to the He–seeded H plasma reduces the amount of released deuterium as compared to pure H plasma exposure.

  9. Initial rate and equilibrium isotope exchange studies on the ATP-dependent activity of polyphosphate Glucokinase from Propionibacterium shermanii. (United States)

    Kowalczyk, T H; Horn, P J; Pan, W H; Phillips, N F


    Polyphosphate glucokinase [EC] catalyzes the phosphorylation of glucose using either inorganic polyphosphate [poly(P)] or ATP as the phosphoryl donor. Both activities purified from Propionibacterium shermanii are the functional properties of a single enzyme with separate binding sites for the two phosphoryl donor substrates. The enzyme was found to utilize poly(P) much more efficiently than it does ATP, with a kcat/Kpoly(P) to kcat/KATP ratio of 2800. The catalytic constant for poly(P) is about 2-fold higher than for ATP. Other nucleotides like GTP and dATP also served as substrates with good efficiencies. The ATP-dependent reaction was analyzed using steady-state kinetics and isotopic exchange kinetics at chemical equilibrium. Intersecting initial velocity patterns for both glucose and ATP indicate sequential addition of substrates. Product inhibition studies resulted in two competitive and two noncompetitive patterns, which is characteristic of a Theorell-Chance mechanism or a random mechanism with two dead-end complexes. Results of isotope exchange experiments, however, rule out a Theorell-Chance mechanism, as well as a truly random mechanism. They are not consistent with a partially random mechanism (although a kinetically compulsory order of substrate binding is not excluded), where glucose is preferentially bound to free enzyme before ATP, and ADP is preferentially released as the first product, followed by glucose 6-phosphate. Dead-end inhibition analysis confirms this order of substrate binding. Competitive inhibition of ADP vs ATP is explained as resulting primarily from binding as a dead-end inhibitor (E.Glc.ADP) and not as a product. Another weaker abortive complex, E.ATP.G6P, is also formed. The chemical transformation or the release of ADP is the rate-limiting step in ATP utilization.

  10. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry. (United States)

    Goswami, Devrishi; Tuske, Steve; Pascal, Bruce D; Bauman, Joseph D; Patel, Disha; Arnold, Eddy; Griffin, Patrick R


    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched ((15)N-labeled) p51 and unlabeled p66. To enable detection of (15)N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% (15)N model. Our results demonstrated that (15)N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but (15)N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the non-nucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV cocrystal structure.

  11. Isotopically exchangeable phosphate in freshwater sediments: Effects of u.v.-irradiation, formaldehyde, solid/solution ratio, and pH on its experimental determination

    NARCIS (Netherlands)

    Vaas, L.H.; Comans, R.N.J.; Reith, J.M.M.; Weijden, C.H. van der; Das, H.A.

    The influence of bioactivities, solid/solution ratio and the pH on the isotopic exchangeability of phosphate in a freshwater sediment was investigated. From the comparison of the results obtained for the same sample in the presence or absence of formaldehyde, it is concluded that microorganisms

  12. Studying biosphere-atmosphere exchange of CO2 through Carbon-13 stable isotopes

    NARCIS (Netherlands)

    Velde, van der I.R.


    Summary Thesis ‘Studying biosphere-atmosphere exchange of CO2 through carbon-13 stable isotopes’ Ivar van der Velde Making predictions of future climate is difficult, mainly due to large uncertainties in the carbon cycle. The rate at which carbon is stored in the oceans and terrestrial

  13. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect (United States)

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon


    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  14. Rapid carbon-carbon bond formation and cleavage revealed by carbon isotope exchange between the carboxyl carbon and inorganic carbon in hydrothermal fluids (United States)

    Glein, C. R.; Cody, G. D.


    The carbon isotopic composition of organic compounds in water-rock systems (e.g., hydrothermal vents, sedimentary basins, and carbonaceous meteorites) is generally interpreted in terms of the isotopic composition of the sources of such molecules, and the kinetic isotope effects of metabolic or abiotic reactions that generate or transform such molecules. This hinges on the expectation that the carbon isotopic composition of many organic compounds is conserved under geochemical conditions. This expectation is reasonable in light of the strength of carbon-carbon bonds (ca. 81 kcal/mol); in general, environmental conditions conducive to carbon-carbon bond cleavage typically lead to transformations of organic molecules (decarboxylation is a notable example). Geochemically relevant reactions that involve isotopic exchange between carbon atoms in organic molecules and inorganic forms of carbon with no change in molecular structure appear to be rare. Notwithstanding such rarity, there have been preliminary reports of relatively rapid carbon isotope exchange between the carboxyl group in carboxylic acids and carbon dioxide in hot water [1,2]. We have performed laboratory hydrothermal experiments to gain insights into the mechanism of this surprising reaction, using phenylacetate as a model structure. By mass spectrometry, we confirm that the carboxyl carbon undergoes facile isotopic exchange with 13C-labeled bicarbonate at moderate temperatures (i.e., 230 C). Detailed kinetic analysis reveals that the reaction rate is proportional to the concentrations of both reactants. Further experiments demonstrate that the exchange reaction only occurs if the carbon atom adjacent to the carboxyl carbon is bonded to a hydrogen atom. As an example, no carbon isotope exchange was observed for benzoate in experiments lasting up to one month. The requirement of an alpha C-H bond suggests that enolization (i.e., deprotonation of the H) is a critical step in the mechanism of the exchange

  15. Tritiated and deuterated alprazolam. The use of deuterium NMR to study isotope exchange in tritiated alprazolam

    Energy Technology Data Exchange (ETDEWEB)

    Banks, W.R.; Clore, L.S.; Dadey, E.J.; Digenis, G.A. (Kentucky Univ., Lexington, KY (United States). College of Pharmacy)


    Using labeled acetate, tritium was incorporated into the triazolomethyl group of alprazolam, a triazolobenzodiazepine. During chemical synthesis, purification and storage, a rapid loss of tritium into solvent media was noted. As a model reaction using tritiated sodium acetate (sp. act. 0.1 Ci/mmol), tritiated alprazolam was produced in 92% chemical yield (19% radiochemical yield) exhibiting a sp. act. of 0.02 Ci/mmol. Investigation of the lability of the [alpha]-methyl tritia utilized the synthesis of deuterated alprazolam and deuterium NMR. Deuterated alprazolam was found to exchange with all buffer systems employed over the pH range 1-11. The exchange was shown to be a rapid (t[sub 1/2] [approx] 2.5 min) process which appeared to proceed independently of pH. (author).

  16. Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope (United States)

    Hamuro, Yoshitomo


    A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification.

  17. A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O. (United States)

    Danon, Albert; Saig, Avraham; Finkelstein, Yacov; Koresh, Jacob E


    Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.

  18. Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model (United States)

    Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph


    Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

  19. Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries (United States)

    Longo, Edoardo; Rossetti, Fabrizio; Scampicchio, Matteo; Boselli, Emanuele


    Cyclic B-type proanthocyanidins in red wines and grapes have been discovered recently. However, proanthocyanidins of a different chemical structure (non-cyclic A-type proanthocyanidins) already known to be present in cranberries and wine possess an identical theoretical mass. As a matter of fact, the retention times and the MS/MS fragmentations found for the proposed novel cyclic B-type tetrameric proanthocyanidin in red wine and the known tetrameric proanthocyanidin in a cranberry extract are herein shown to be identical. Thus, hydrogen/deuterium (H/D) exchange was applied to HPLC-HRMS/MS to confirm the actual chemical structure of the new oligomeric proanthocyanidins. The comparison of the results in water and deuterium oxide and between wine and cranberry extract indicates that the cyclic B-type tetrameric proanthocyanidin is the actual constituent of the recently proposed novel tetrameric species ([C60H49O24]+, m/z 1153.2608). Surprisingly, the same compound was also identified as the main tetrameric proanthocyanidin in cranberries. Finally, a totally new cyclic B-type hexameric proanthocyanidin ([C90H73O36]+, m/z 1729.3876) belonging to this novel class was identified for the first time in red wine. [Figure not available: see fulltext.

  20. Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations (United States)

    Gregory, R.T.; Criss, R.E.; Taylor, H.P.


    The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and

  1. Assay of low deuterium enrichment of water by isotopic exchange with [U-13C3]acetone and gas chromatography-mass spectrometry. (United States)

    Yang, D; Diraison, F; Beylot, M; Brunengraber, D Z; Samols, M A; Anderson, V E; Brunengraber, H


    A sensitive assay of the 2H-enrichment of water based on the isotopic exchange between the hydrogens of water and of acetone in alkaline medium is described and validated. For low 2H-enrichments (0.008 to 0.5%), the sample is spiked with [U-13C3]acetone and NaOH. After exchange, 2H-enriched [U-13C3]acetone is extracted with chloroform and assayed by gas chromatography-mass spectrometry. With some instruments, ion-molecule reactions, resulting in increased baseline enrichment, are minimized by lowering the electron ionization energy from the usual 70 to 10 eV. The 2H-enrichment of water is amplified nearly sixfold in the M4/M3 ratio of [U-13C3]acetone. For high 2H-enrichments (0.25 to 100%), the use of unlabeled acetone suffices. After exchange, the mass isotopomer distribution of acetone is analyzed, yielding the 2H-enrichment of water. The assay with [U-13C3]acetone allows measuring the 2H-enrichment of water even in biological samples containing acetone. This technique is more rapid and economical than the classical isotope ratio mass spectrometric assay of the enrichment of hydrogen gas derived from the reduction of water.

  2. Comparison of acetate turnover in methanogenic and sulfate- reducing sediments by radiolabeling and stable isotope labeling and by use of specific inhibitors: Evidence for isotopic exchange

    NARCIS (Netherlands)

    De Graaf, W.; Wellsbury, P.; Parkes, R.J.; Cappenberg, T.E.


    Acetate turnover in the methanogenic freshwater anoxic sediments of Lake Vechten, The Netherlands, and in anoxic sediments from the Tamar Estuary, United Kingdom, and the Grosser Jasmunder Bodden, Germany, the latter two dominated by sulfate reduction, was determined, Stable isotopes and

  3. Oxygen and U-Th isotopes and the timescales of hydrothermal exchange and melting in granitoid wall rocks at Mount Mazama, Crater Lake, Oregon (United States)

    Ankney, Meagan E.; Bacon, Charles R.; Valley, John W.; Beard, Brian L.; Johnson, Clark M.


    We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0–50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an “outside in” perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1–5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000–63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10–200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others.Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the

  4. Oxygen and U-Th isotopes and the timescales of hydrothermal exchange and melting in granitoid wall rocks at Mount Mazama, Crater Lake, Oregon (United States)

    Ankney, Meagan E.; Bacon, Charles R.; Valley, John W.; Beard, Brian L.; Johnson, Clark M.


    We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0-50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an ;outside in; perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1-5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000-63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10-200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others. Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the highest U excess (≥5.8%) also

  5. Oxygen isotope exchange in rocks and minerals from the Cerro Prieto geothermal system: Indicators of temperature distribution and fluid flow

    Energy Technology Data Exchange (ETDEWEB)

    Williams, A.E.; Elders, W.A.


    Oxygen isotopic compositions have been measured in drill cuttings and core samples from more than 40 wells ranging in depth to more than 3.5 km in the Cerro Prieto geothermal field. Profiles of isotopic ratios versus sampling depths provide information on the three-dimensional distribution of temperature and fluid flow. These parameters also indicate variations in the history of hydrothermal processes in different areas of the geothermal field.

  6. Assessment of surface reactivity of thorium oxide in conditions close to chemical equilibrium by isotope exchange {sup 229}Th/{sup 232}Th method

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki-Muresan, Tomo; Perrigaud, Katy; Vandenborre, Johan; Ribet, Solange; Grambow, Bernd [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Takamasa, Inai [TOKAI Univ., Kanagawa (Japan)


    This work aims to assess the solubility and the surface reactivity of crystallized thorium at pH 3.0 in presence of three types of solids: synthesized powder at 1300 C, crushed kernel, and intact kernel. In this study, the kernel is composed by the core solid from high temperature reactors (HTR) sphere particles. The originality of this work consisted in following in a sequential order the kinetic of dissolution, the surface reactivity in presence of isotope tracer {sup 229}Th, and its desorption process. Long time experiments (634 days) allowed to get deeper understanding on the behavior of the surface reactivity in contact with the solution. Solubility values are ranging from 0.3 x 10{sup -7} mol.L{sup -1} to 3 x 10{sup -7} mol.L{sup -1} with a dissolution rate of 10{sup -6}-10{sup -4} g.m{sup -2} day{sup -1}. PHREEQC modeling showed that crystallized ThO{sub 2}(cr, 20 nm) phase controls the equilibrium in solution. Isotope exchange between {sup 229}Th and {sup 232}Th indicated that well-crystallized phase exist as an inert surface regarding to the absence of exchange between surface solid and solution.

  7. Synthesis and radioiodination of di-iodo-Evan's blue via isotopic exchange reaction in the molten state and evaluation of the kinetics

    Energy Technology Data Exchange (ETDEWEB)

    El-Azony, K.M. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry]|[Hot Lab. Center, Cairo (Egypt). Radioactive Isotopes and Generators Dept.; Bier, D.; Coenen, H.H. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry


    Many aryl halides were synthesized from aryl amines such as iodo-trypan, iodo-methylene blue and iodo-toluidine. Methylene blue and toludine blue are phenothiazinium dyes and were used to localize parathyroid glands visually during surgery. Radioiodination of these compounds by using iodine-123 analogues for scintgraphic localization of parathyroids was reported. Radiolabelled dyes administered may also localize in tumor tissues. Evan's blue dye was used to study altered sarcolemmal permeability in dystrophic muscle fibers, and in animals to study muscular dystrophy. In this work Diiodo-Evan's blue was synthesized via Sandmeyer reaction and characterized by mass spectrum analysis. A procedure for labelling DIEB with Na{sup 131}I via isotopic exchange in molten medium was developed. The labelling conditions studied for the isotopic exchange of {sup 131}I-for-I in DIEB included the effect of temperature and solvents (melt of acetamide, benzoic and pivalic acid). Kinetic studies were performed to obtain [{sup 131}I] DIEB with more reliable reaction conditions. Quality control for the final product ([{sup 131}I] DIEB) was performed by HPLC. (orig.)

  8. A global-scale simulation of the CO2 exchange between the atmosphere and the terrestrial biosphere with a mechanistic model including stable carbon isotopes, 1953 1999 (United States)

    Ito, Akihiko


    This paper presents the results of a simulation with a mechanistic terrestrial ecosystem model, focusing on the atmosphere-biosphere exchange and stable isotope composition of carbon. The simulation was performed from 1953 to 1999 on the basis of observed climate data and atmospheric carbon dioxide (CO2) concentration and stable carbon isotope ratio (δ13C). The model, termed Sim-CYCLE, captures carbon dynamics from photosynthetic assimilation to microbial decomposition, including seasonal and interannual variability. Photosynthetic discrimination effect on δ13C was considered at three levels: (1) leaf-level fractionation, (2) canopy-level CO2 recycling and (3) continent-level C3/C4 pattern. The 47-yr simulation estimated that the average gross CO2 flux was 121 Pg C yr-1, and that the average photosynthetic δ13C discrimination coefficient (Δ) was 18.2%. A sensitivity analysis indicated that the estimated Δ depends heavily on the parameterization of stomatal conductance and C3/C4 composition. In spite of their small biomass, C4 plants contributed considerably to the biospheric productivity and belowground carbon supply. The estimated net CO2 and isotopic exchange of the terrestrial ecosystems corresponded, at least qualitatively, with observed atmospheric CO2 and its δ13C seasonal patterns in the Northern Hemisphere. The gross CO2 fluxes of photosynthesis and respiration indicated a wide range of interannual variability, which was in a sufficient magnitude to induce anomalies in the atmospheric CO2 growth rate. The estimated Δ showed a wide range of latitudinal and longitudinal variations and seasonal oscillation, but little interannual change. However, during the 47-yr period, the estimated δ13C of carbon pools decreased by 0.3%, while the δ13C of atmospheric CO2 decreased by 0.7%. These results carry implications for the application of a top-down approach, i.e. the double-deconvolution method, to inferring the global terrestrial CO2 budget.

  9. Biology and air–sea gas exchange controls on the distribution of carbon isotope ratios (δ13C in the ocean

    Directory of Open Access Journals (Sweden)

    A. Schmittner


    Full Text Available Analysis of observations and sensitivity experiments with a new three-dimensional global model of stable carbon isotope cycling elucidate processes that control the distribution of δ13C of dissolved inorganic carbon (DIC in the contemporary and preindustrial ocean. Biological fractionation and the sinking of isotopically light δ13C organic matter from the surface into the interior ocean leads to low δ13CDIC values at depths and in high latitude surface waters and high values in the upper ocean at low latitudes with maxima in the subtropics. Air–sea gas exchange has two effects. First, it acts to reduce the spatial gradients created by biology. Second, the associated temperature-dependent fractionation tends to increase (decrease δ13CDIC values of colder (warmer water, which generates gradients that oppose those arising from biology. Our model results suggest that both effects are similarly important in influencing surface and interior δ13CDIC distributions. However, since air–sea gas exchange is slow in the modern ocean, the biological effect dominates spatial δ13CDIC gradients both in the interior and at the surface, in contrast to conclusions from some previous studies. Calcium carbonate cycling, pH dependency of fractionation during air–sea gas exchange, and kinetic fractionation have minor effects on δ13CDIC. Accumulation of isotopically light carbon from anthropogenic fossil fuel burning has decreased the spatial variability of surface and deep δ13CDIC since the industrial revolution in our model simulations. Analysis of a new synthesis of δ13CDIC measurements from years 1990 to 2005 is used to quantify preformed and remineralized contributions as well as the effects of biology and air–sea gas exchange. The model reproduces major features of the observed large-scale distribution of δ13CDIC as well as the individual contributions and effects. Residual misfits are documented and analyzed. Simulated surface and subsurface

  10. Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study. (United States)

    ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben


    In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short


    Spevack, J.S.


    An isotope concentration process is described which consists of exchanging, at two or more different temperature stages, two isotopes of an element between substances that are physically separate from each other and each of which is capable of containing either of the isotopes, and withdrawing from a point between at least two of the temperatare stages one of the substances containing an increased concentration of the desired isotope.

  12. Continuous In-situ Measurements of Carbonyl Sulfide (OCS) and Carbon Dioxide Isotopes to Constrain Ecosystem Carbon and Water Exchanges (United States)

    Rastogi, B.; Still, C. J.; Noone, D. C.; Berkelhammer, M. B.; Whelan, M.; Lai, C. T.; Hollinger, D. Y.; Gupta, M.; Leen, J. B.; Huang, Y. W.


    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf- level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from four heights as well as the soil to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere for the growing season. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings also seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  13. Iridium Cyclooctene Complex That Forms a Hyperpolarization Transfer Catalyst before Converting to a Binuclear C-H Bond Activation Product Responsible for Hydrogen Isotope Exchange. (United States)

    Iali, Wissam; Green, Gary G R; Hart, Sam J; Whitwood, Adrian C; Duckett, Simon B


    [IrCl(COE)2]2 (1) reacts with pyridine (py) and H2 to form crystallographically characterized IrCl(H)2(COE)(py)2 (2). 2 undergoes py loss to form 16-electron IrCl(H)2(COE)(py) (3), with equivalent hydride ligands. When this reaction is studied with parahydrogen, 1 efficiently achieves hyperpolarization of free py (and nicotinamide, nicotine, 5-aminopyrimidine, and 3,5-lutudine) via signal amplification by reversible exchange (SABRE) and hence reflects a simple and readily available precatayst for this process. 2 reacts further over 48 h at 298 K to form crystallographically characterized (Cl)(H)(py)(μ-Cl)(μ-H)(κ-μ-NC5H4)Ir(H)(py)2 (4). This dimer is active in the hydrogen isotope exchange process that is used in radiopharmaceutical preparations. Furthermore, while [Ir(H)2(COE)(py)3]PF6 (6) forms upon the addition of AgPF6 to 2, its stability precludes its efficient involvement in SABRE.

  14. Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide (United States)

    Mrozek, D. J.; van der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.


    This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from stratospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio mass spectrometry (IRMS). The 17O excess (Δ17O) is derived from isotope measurements on two different CO2 aliquots: unmodified CO2 and CO2 after complete oxygen isotope exchange with cerium oxide (CeO2) at 700 °C. Thus, a single measurement of Δ17O requires two injections of 1 mL of air with a CO2 mole fraction of 390 μmol mol-1 at 293 K and 1 bar pressure (corresponding to 16 nmol CO2 each). The required sample size (including flushing) is 2.7 mL of air. A single analysis (one pair of injections) takes 15 minutes. The analytical system is fully automated for unattended measurements over several days. The standard deviation of the 17O excess analysis is 1.7‰. Multiple measurements on an air sample reduce the measurement uncertainty, as expected for the statistical standard error. Thus, the uncertainty for a group of 10 measurements is 0.58‰ for Δ 17O in 2.5 h of analysis. 100 repeat analyses of one air sample decrease the standard error to 0.20‰. The instrument performance was demonstrated by measuring CO2 on stratospheric air samples obtained during the EU project RECONCILE with the high-altitude aircraft Geophysica. The precision for RECONCILE data is 0.03‰ (1σ) for δ13C, 0.07‰ (1σ) for δ18O and 0.55‰ (1σ) for δ17O for a sample of 10 measurements. This is sufficient to examine stratospheric enrichments, which at altitude 33 km go up to 12‰ for δ17O and up to 8‰ for δ18O with respect to tropospheric CO2 : δ17O ~ 21‰ Vienna Standard Mean Ocean Water (VSMOW), δ18O ~ 41‰ VSMOW (Lämmerzahl et al., 2002). The samples measured with our analytical technique agree with available data for

  15. A simulation code treating all twelve isotopic species of hydrogen gas and water for multistage chemical exchange column

    Energy Technology Data Exchange (ETDEWEB)

    Yamanishi, Toshihiko; Okuno, Kenji [Japan Atomic Energy Research Inst., Naka, Ibaraki (Japan). Naka Fusion Research Establishment


    A simulation code of the multistage chemical exchange column has been developed. The column has an electrolysis cell, a section for the liquid phase catalytic exchange, and a recombiner. The sieve trays and the catalyst beds are separated in the section for the liquid-vapor scrubbing steps and for the vapor-hydrogen gas exchange steps. This type of column is a promising system for the tritiated water processing. The code can deal with all the twelve molecular species of the hydrogen gas and the water. The equilibrium of atomic elements of H, D and T is also considered in the liquid phase. The Murphree-type factors are introduced in the code to evaluate the efficiencies for the sieve trays and catalyst beds. The solution of basic equations can be found out by the Newton-Raphson method. The atom fractions of D and T on the scrubbing trays are the independent variables of the equations: The order of the Jacobian matrix is only twice the number of sieve trays. The solution of the basic equations could be obtained for several example cases; and no difficulty was observed for the convergence of the calculations. Broyden`s method was quite effective to reduce computation time of the code. (author).

  16. Controls of Net Ecosystem Exchange at an Old Field, a Pine Plantation, and a Hardwood Forest under Identical Climatic and Edaphic Conditions-Isotopic Studies

    Energy Technology Data Exchange (ETDEWEB)

    Chanton, J. P.; Mortazavi, B.


    During the past year we have submitted two manuscripts. 1. Mortazavi, B., J. Chanton, J.L. Prater, A.C. Oishi, R. Oren and G. Katul. Temporal variability in 13C of respired CO2 in a pine and a hardwood forest subject to similar climatic conditions (in Press). Oecologia 2. Mortazavi, B. and J. P. Chanton. Use of Keeling plots for determining sources of dissolved organic carbon in nearshore and open ocean systems (Published in Limnology and Oceanography (2004) Vol 49 pages 102-108). 3. Mortazavi, B., J. L. Prater, and J. P. Chanton (2004). A field-based method for simultaneous measurements of the 18O and 13C of soil CO2 efflux. Biogeosciences Vol 1:1-16 Most recent products delivered: Mortazavi, B. and J. P. Chanton. Abiotic and biotic controls on the 13C of respired CO2 in the southeastern US forest mosaics and a new technique for measuring the of soil CO2 efflux. Joint Biosphere Stable Isotope Network (US) and Stable Isotopes in Biosphere Atmosphere Exchange (EU) 2004 Meeting, Interlaken, Switzerland, March 31-April 4, 2004. Mortazavi, B., J. Chanton, J.L. Prater, A.C. Oishi, R. Oren and G. Katul. Temporal variability in 13C of respired CO2 in a pine and a hardwood forest subject to similar climatic conditions. American Geophysical Union Fall Meeting, San Francisco, USA, December 8-12, 2003. Prater, J., Mortazavi, B. and J. P. Chanton. Measurement of discrimination against 13C during photosynthesis and quantification of the short-term variability of 13C over a diurnal cycle. American Geophysical Union Fall Meeting, San Francisco, USA, December 8-12, 2003.

  17. Sea-air exchange patterns along the central and outer East Siberian Arctic Shelf as inferred from continuous CO2, stable isotope, and bulk chemistry measurements (United States)

    Humborg, Christoph; Geibel, Marc C.; Anderson, Leif G.; Björk, Göran; Mörth, Carl-Magnus; Sundbom, Marcus; Thornton, Brett F.; Deutsch, Barbara; Gustafsson, Erik; Gustafsson, Bo; Ek, Jörgen; Semiletov, Igor


    This large-scale quasi-synoptic study gives a comprehensive picture of sea-air CO2 fluxes during the melt season in the central and outer Laptev Sea (LS) and East Siberian Sea (ESS). During a 7 week cruise we compiled a continuous record of both surface water and air CO2 concentrations, in total 76,892 measurements. Overall, the central and outer parts of the ESAS constituted a sink for CO2, and we estimate a median uptake of 9.4 g C m-2 yr-1 or 6.6 Tg C yr-1. Our results suggest that while the ESS and shelf break waters adjacent to the LS and ESS are net autotrophic systems, the LS is a net heterotrophic system. CO2 sea-air fluxes for the LS were 4.7 g C m-2 yr-1, and for the ESS we estimate an uptake of 7.2 g C m-2 yr-1. Isotopic composition of dissolved inorganic carbon (δ13CDIC and δ13CCO2) in the water column indicates that the LS is depleted in δ13CDIC compared to the Arctic Ocean (ArcO) and ESS with an offset of 0.5‰ which can be explained by mixing of δ13CDIC-depleted riverine waters and 4.0 Tg yr-1 respiration of OCter; only a minor part (0.72 Tg yr-1) of this respired OCter is exchanged with the atmosphere. Property-mixing diagrams of total organic carbon and isotope ratio (δ13CSPE-DOC) versus dissolved organic carbon (DOC) concentration diagram indicate conservative and nonconservative mixing in the LS and ESS, respectively. We suggest land-derived particulate organic carbon from coastal erosion as an additional significant source for the depleted δ13CDIC.

  18. Use of the isotope flux ratio approach to investigate the C18O16O and 13CO2 exchange near the floor of a temperate deciduous forest

    Directory of Open Access Journals (Sweden)

    P. Bartlett


    Full Text Available Stable isotopologues of CO2, such as 13CO2 and C18OO, have been used to study the CO2 exchange between land and atmosphere. The advent of new measuring techniques has allowed near-continuous measurements of stable isotopes in the air. These measurements can be used with micrometeorological techniques, providing new tools to investigate the isotope exchange in ecosystems. The objectives of this study were to evaluate the use of the isotope flux ratio method (IFR near the forest floor of a temperate deciduous forest and to study the temporal dynamics of δ18O of CO2 flux near the forest floor by comparing IFR estimates with estimates of δ18O of net soil CO2 flux provided by an analytical model. Mixing ratios of 12C16O2, 13CO2 and C16O18O were measured within and above a temperate deciduous forest, using the tunable diode laser spectroscopy technique. The half-hourly compositions of the CO2 flux near the forest floor (δ13CF and δ18OF were calculated by IFR and compared with estimates provided by a modified Keeling plot technique (mKP and by a Lagrangian dispersion analysis (WT analysis. The mKP and IFR δ18OF estimates showed good agreement (slope = 1.03 and correlation, R2 = 0.80. The δ13CF estimates from the two methods varied in a narrow range of −32.7 and −23‰; the mean (± SE mKP and IFR δ13CF values were −27.5‰ (±0.2 and −27.3‰ (±0.1, respectively, and were statistically identical (p>0.05. WT analysis and IFR δ18OF estimates showed better correlation (R2 = 0.37 when only turbulent periods (u*>0.6 m s−1 were included in the analysis. The large amount of data captured (~95 % of half-hour periods evaluated for the IFR in comparison with mKP (27 % shows that the former provides new opportunities for studying δ18OF dynamics within forest canopies. Values of δ18OF showed large temporal variation, with values ranging from −31.4‰ (DOY 208 to −11.2‰ (DOY 221. Precipitation events caused substantial variation (~8

  19. Additional Evidence That Transaldolase Exchange, Isotope Discrimination During the Triose-Isomerase Reaction, or Both Occur in Humans (United States)

    Basu, Rita; Chandramouli, Visvanthan; Schumann, William; Basu, Ananda; Landau, Bernard R.; Rizza, Robert A.


    OBJECTIVE To determine whether deuterium enrichment on carbons 5 and 3 (C5/C3) in plasma glucose is influenced by processes other than gluconeogenesis and, if so, whether these processes are altered by type 2 diabetes. RESEARCH DESIGN AND METHODS In this study, 10 obese diabetic and 10 obese nondiabetic subjects were infused intravenously with [3,5-2H2] galactose enriched at a C5-to-C3 ratio of 1.0 as well as the enrichment of deuterium on C5 and C3 of plasma glucose, measured with nuclear magnetic resonance using the acetaminophen glucuronide method. RESULTS The ratio of deuterium enrichment on C5 and C3 of glucose was deuterium at the level of the triose-isomerase reaction, or both occur in humans. This also indicates that the net effect of these processes on the C5-to-C3 ratio is the same in people with and without type 2 diabetes. The possible effects of transaldolase exchange or selective retention of deuterium (or tritium) at the level of the triose-isomerase reaction on tracee labeling and tracer metabolism should be considered when the deuterated water method is used to measure gluconeogenesis or [3-3H] glucose is used to measure glucose turnover in humans. PMID:19366865

  20. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling. (United States)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Donohoe, Gregory C; Valentine, Stephen J


    Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H](2-) ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H](3-) ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H](2-) ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H](3-) ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

  1. Stable-isotope geochemistry of the Pierina high-sulfidation Au-Ag deposit, Peru: Influence of hydrodynamics on SO42--H2S sulfur isotopic exchange in magmatic-steam and steam-heated environments (United States)

    Fifarek, R.H.; Rye, R.O.


    environment was unusually slow, which provided sufficient time for the uptake of groundwater and partial to complete SO42--H2S isotopic exchange. The slow steam velocities were likely related to the dispersal of the steam column as it entered the tuffs and possibly to intermediate exsolution rates from magmatic brine. The low ??D values may also partly reflect continuous degassing of the mineralizing magma. Similarly, data for steam-heated alunite (??34S=12.3??? to 27.2???; ??18OSO4=11.7??? to 13.0???; ??18OOH=6.6??? to 9.4???; ??D=-59??? to -42???) are unusual and indicate a strong magmatic influence, relatively high temperatures (140 to 180 ??C, based on ??18 OSO4-OH fractionations), and partial to complete sulfur isotopic exchange between steam-heated sulfate and H2S. Restricted lithologically controlled fluid flow in the host tuffs allowed magmatic condensate to supplant meteoric groundwater at the water table and create the high-temperature low-pH conditions that permitted unusually rapid SO42--H2S isotopic equilibration (50-300 days) and (or) long sulfate residence times for this environment. Late void-filling barite (??34S=7.4??? to 29.7???; ??18OSO4=-0.4??? to 15.1???) and later void-filling goethite (??18O=-11.8??? to 0.2???) document a transition from magmatic condensate to dominantly meteoric water in steam-heated fluids during cooling and collapse of the hydrothermal system. These steam-heated fluids oxidized the top ???300 m of the deposit by leaching sulfides, redistributing metals, and precipitating barite??acanthite??gold and goethite-hematite ??gold. Steam-heated oxidation, rather than weathering, was critical to forming the orebody in that it not only released encapsulated gold but likely enriched the deposit to ore-grade Au concentrations. ?? 2004 Elsevier B.V. All rights reserved.

  2. Magma mixing and crystal exchange at Yellowstone caldera revealed though sub-crystal-scale age, trace-element, and Hf-isotopic analyses of zircons (United States)

    Stelten, M. E.; Cooper, K. M.; Vazquez, J. A.; Wimpenny, J.; Yin, Q.


    We examine magma mixing and crystal exchange in a young magma reservoir by correlating sub-crystal-scale SIMS age, SIMS trace element, and LA-MC-ICPMS Hf-isotopic data from zircons in the coeval ca. 100ka, yet compositionally distinct rhyolites of the Solfatara Plateau flow (SPF) and Hayden Valley flow (HVF) at Yellowstone Caldera. The SPF and HVF lavas are part of the Central Plateau Member (CPM) of the Plateau Rhyolite that is composed of the youngest intracaldera rhyolite flows at Yellowstone, erupted between ca. 170-70ka. We compare these data to age and trace element data from zircons in 1) the Pitchstone Plateau Flow, West Yellowstone Flow, and Dry Creek Flow of the CPM as representative of main reservoir zircons, 2) the ca. 118ka extracaldera Gibbon River Flow rhyolite (GRF), and 3) the ca. 260ka Scaup Lake Flow of the Upper Basin Member rhyolites. Additionally, we compare the zircon data to new MC-ICPMS Hf-isotopic data from CPM glasses. Correlating age, trace element, and Hf-isotopic data from zircons in the HVF and SPF reveals the presence of four zircon populations. Main reservoir-like (MR-like) zircons have trace element compositions similar to main CPM reservoir zircons, young ages (Lastly, a population of zircons (which we interpret to be inherited) have cores with older ages (>350ka), a range in trace element compositions, and high ɛHf (-5.8 to -3.6) whereas the rims have restricted MR-like trace element compositions and ɛHf within error of CPM glasses. The sense of core to rim zoning specific to each population suggests that each population has its own unique history. The core to rim zoning in MR-like and inherited zircons, from cores with a range of Hf-isotopic compositions to rims similar to CPM glasses, suggests that MR-like and inherited zircons in the SPF and HVF came from distinct high ɛHf magmas and were incorporated into the CPM reservoir. For mixed zircons, the zoning from MR-like or EC-like cores to intermediate rim compositions

  3. Stable oxygen isotope and flux partitioning demonstrates understory of an oak savanna contributes up to half of ecosystem carbon and water exchange

    Directory of Open Access Journals (Sweden)

    Maren eDubbert


    Full Text Available Semi-arid ecosystems contribute about 40% to global net primary production (GPP even though water is a major factor limiting carbon uptake. Evapotranspiration (ET accounts for up to 95% of the water loss and in addition, vegetation can also mitigate drought effects by altering soil water distribution. Hence, partitioning of carbon and water fluxes between the soil and vegetation components is crucial to gain mechanistic understanding of vegetation effects on carbon and water cycling. However, the possible impact of herbaceous vegetation in savanna type ecosystems is often overlooked. Therefore, we aimed at quantifying understory vegetation effects on the water balance and productivity of a Mediterranean oak savanna. ET and net ecosystem CO2 exchange (NEE were partitioned based on flux and stable oxygen isotope measurements and also rain infiltration was estimated.The understory vegetation contributed importantly to total ecosystem ET and GPP with a maximum of 43% and 51%, respectively. It reached water-use efficiencies (WUE; ratio of carbon gain by water loss similar to cork-oak trees. The understory vegetation inhibited soil evaporation (E and, although E was large during wet periods, it did not diminish WUE during water-limited times. The understory strongly increased soil water infiltration, specifically following major rain events. At the same time, the understory itself was vulnerable to drought, which led to an earlier senescence of the understory growing under trees as compared to open areas, due to competition for water. Thus, beneficial understory effects are dominant and contribute to the resilience of this ecosystem. At the same time the vulnerability of the understory to drought suggests that future climate change scenarios for the Mediterranean basin threaten understory development. This in turn will very likely diminish beneficial understory effects like infiltration and ground water recharge and therefore ecosystem resilience to

  4. 15N Isotopic Crop Exchange Residue Studies Suggest that IPCC N Input Methodologies to Assess N2O-N Emissions Should be Reevaluated (United States)

    It is difficult to quantify nitrogen (N) losses from agricultural systems to the environment, however we can use 15N isotopic techniques to conduct site specific studies to increase our knowledge about N management and fate. This manuscript synthesizes the review of two selected 15N isotopic studies...

  5. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg


    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  6. Evolution of the isotope composition of C and O in the DIC in a water film during precipitation of calcite to the surface of a stalagmite in the presence of isotope exchange with the CO2 of the cave atmosphere and evaporation of the water (United States)

    Dreybrodt, Wolfgang; Romanov, Douchko


    In a thin water layer, super saturated with respect to calcite with pH of about 8, where the aqueous CO2 is in equilibrium with the pCO2 of the cave atmosphere, the following processes determine the temporal evolution of the isotope composition of carbon and oxygen in the dissolved inorganic carbon ( DIC). a) Precipitation of calcite driven by super saturation, whereby deposition rates Between the heavy and light isotopes are slightly different. b) Evaporation of water reducing the depth of the water layer and changing the isotope composition of oxygen in the water by Rayleigh-distillation. c) Isotope exchange between the CO2 in the cave atmosphere and the DIC for both carbon and oxygen. d) Isotope exchange between the oxygen in the water molecules and that in the DIC. All these processes can be described by a differential equation, which can be solved numerically. For small times a simple solution can be given. Δ_DIC(T_drip) = [ ( (⪉mbda + ɛ) C_eq/C0 - ɛ ) T_drip/τ + (δ^atm_eq - δ0 ) T_drip/τ^atm + (δ^water_eq-δ_0-ɛ_wT_drip/T_ev) T_drip/τ^water] Δ_DIC(T_drip) is the change of the δ13C and δ18O (given here as small numbers and not in the ‰ notation) after the drip time T_drip. ⪉mbda, ɛ are kinetic parameters of precipitation on the order of 10-2 and τ is the time scale of precipitation, typically about 1000 s. (δ^atm_eq - δ_0) and (δ^water_eq - δ_0) are the differences between the corresponding initial δ-value and that when DIC is in isotope equilibrium with the atmosphere or in the case of oxygen with the water. τ^atm and τ^water, both on the order of 10,000 s, are the time scales of the exchange reactions to approach isotope equilibrium. For carbon the last term (exchange with water) must be deleted. C_eq is the concentration of DIC in chemical equilibrium with the CO2 in the cave atmosphere and C0 is the initial concentration, when the water drips to the stalagmite. T_ev is the time needed to fully evaporate the water layer and

  7. Isotope geochemistry. Biological signatures in clumped isotopes of O₂. (United States)

    Yeung, Laurence Y; Ash, Jeanine L; Young, Edward D


    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in (18)O(18)O and (17)O(18)O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling. Copyright © 2015, American Association for the Advancement of Science.

  8. Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets (United States)

    Boering, Kristie A.; Connell, Peter; Rotman, Douglas


    Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

  9. Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

    NARCIS (Netherlands)

    Mrozek, D. J.; Van Der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.


    This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from atmospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses

  10. Isotopic exchange in the ethanol synthesis from CO + H/sub 2/. Comments on papers by A. Takeuchi and J. R. Katzer

    Energy Technology Data Exchange (ETDEWEB)

    Henrici-Olive, G.; Olive, S.


    Results of papers previously published by Takeuchi and Katzer suggesting mechanisms for the methanol and ethanol synthesis via CO hydrogenation without dissociation in the presence of supported Rh catalysts are not questioned. However, an alternate pathway for the oxygen scrambling at the C/sub 2/ level and an interpretation of the small, but significant, changes in the isotopic distribution of CO in the gas phase are presented.

  11. A Mn-54 Radiotracer Study of Mn Isotope Solid-Liquid Exchange during Reductive Transformation of Vernadite (δ-MnO₂) by Aqueous Mn(II)

    Energy Technology Data Exchange (ETDEWEB)

    Elzinga, Evert J.; Kustka, Adam B. [Rutgers


    We employed Mn-54 radiotracers to characterize the extent and dynamics of Mn atom exchange between aqueous Mn(II) and vernadite (δ-Mn(IV)O2) at pH 7.5 under anoxic conditions. Exchange of Mn atoms between the solid and liquid phase is rapid, reaching dynamic equilibrium in 2–4 days. We propose that during the initial stages of reaction, Mn atom exchange occurs through consecutive comproportionation-disproportionation reactions where interfacial electron transfer from adsorbed Mn(II) to lattice Mn(IV) generates labile Mn(III) cations that rapidly disproportionate to reform aqueous Mn(II) and solid-phase Mn(IV). Following nucleation of Mn(III)OOH phases, additional exchange likely occurs through electron transfer from aqueous Mn(II) to solid-phase Mn(III). Our results provide evidence for the fast and extensive production of transient Mn(III) species at the vernadite surface upon contact of this substrate with dissolved Mn(II). We further show that HEPES buffer is a reductant of lattice Mn(IV) in the vernadite structure in our experiments. The methods and results presented here introduce application of Mn-54 tracers as a facile tool to further investigate the formation kinetics of labile Mn(III) surface species and their impacts on Mn-oxide structure and reactivity over a range of environmentally relevant geochemical conditions.

  12. Determination of wine authenticity and geographical origin by measuring non-exchangeable hydrogen stable isotopes in wine ethanol with EIM-IRMS® methodology in combination with δ18O values obtained from wine water. (United States)

    Smajlovic, Ivan; Glavanovic, Mirko; Sparks, Kimberlee L.; Sparks, Jed P.; Jovic, Slobodan


    Wine consumption has grown significantly in the last two decades, with the United States being the leading consumer of wine in the world. It is also the second largest wine producer and importer after the European Union, which consists of 27 European countries. The world has seen a significant increase in production from new world countries, especially the United States, Australia and Chile, and wine imports have grown significantly with this globalization. The quality and authenticity of products have become critical concerns. With the amount of wine being imported the need for verifying wine authenticity and understanding procedures used in wine making has become more important than ever. Understanding the origin of consumed wine in rapidly expanding global economy has become fundamental in order to control quality and protect consumers. In our previous scientific work we have shown that EIM-IRMS®, Ethanol Isotope Measurement - Isotope Ratio Mass Spectrometry (EIM-IRMS®), is capable of providing unique molecular fingerprint that cannot be reproduced or counterfeited. Today we know that δ18O value from the wine water is one of the most important parameters which can give information about wine geographical origin. Earlier we have suggested that grape juice or grape pulp is a closed biochemical system in which all chemical compounds stand in dynamic equilibrium and are in direct connection with each other. Taking that into consideration we have concluded that if system is genuine and if no water, or no sugar has been added to the grape must or grape juice prior to alcoholic fermentation, then ethanol which is made in process of alcoholic fermentation will have specific δD value of non-exchangeable hydrogen stable isotopes which will be in range from -205 to -215 ‰ vs. V-SMOW. In this work we will show that this value, which we named δDn (non-exchangeable hydrogen stable isotopes in ethanol), is very important because it can support or refute conclusions

  13. Robust optical carbon dioxide isotope analyzer Project (United States)

    National Aeronautics and Space Administration — Isotopic analysis of carbon dioxide is an important tool for characterization of the exchange and transformation of carbon between the biosphere and the atmosphere....

  14. Wet chemical preparation and isotope exchange process of H/D-terminated Si(111) and Si(110) studied by adsorbate vibrational analysis (United States)

    Kawamoto, Erina; Kang, Jungmin; Matsuda, Takuya; Yamada, Taro; Suto, Shozo


    A convenient procedure for preparing D-terminated Si(111)-(1×1) and Si(110)-(1×1) by wet chemical etching was developed and applied to the vibrational analysis of these surfaces by high-resolution electron-energy loss spectroscopy (HREELS). Fully H-terminated Si(111)/(110) was first prepared in regular 40% NH4F/H2O solution, followed by immersion in saturated KF/D2O solution. HREELS revealed partially D-terminated H:Si(111)/(110) with the amount of deuterium termination depending on the immersion time. A series of various immersion times revealed the H/D exchange reaction kinetics, which are associated with the Si substrate etching processes on Si(111) (step-flow etching) and Si(110) (zipper reaction). The H-Si and D-Si stretching vibration frequencies as functions of the surface D fraction did not appear to change on Si(111), but on Si(110) the H-Si signal red shifted at a high D fraction. This is due to the adsorbate-adsorbate interaction, which is more intense on Si(110) because of the short nearest-neighbor distance of the adsorbates.

  15. Additional evidence that transaldolase exchange, isotope discrimination during the triose-isomerase reaction, or both occur in humans: effects of type 2 diabetes. (United States)

    Basu, Rita; Chandramouli, Visvanthan; Schumann, William; Basu, Ananda; Landau, Bernard R; Rizza, Robert A


    To determine whether deuterium enrichment on carbons 5 and 3 (C5/C3) in plasma glucose is influenced by processes other than gluconeogenesis and, if so, whether these processes are altered by type 2 diabetes. In this study, 10 obese diabetic and 10 obese nondiabetic subjects were infused intravenously with [3,5-(2)H(2)] galactose enriched at a C5-to-C3 ratio of 1.0 as well as the enrichment of deuterium on C5 and C3 of plasma glucose, measured with nuclear magnetic resonance using the acetaminophen glucuronide method. The ratio of deuterium enrichment on C5 and C3 of glucose was deuterium at the level of the triose-isomerase reaction, or both occur in humans. This also indicates that the net effect of these processes on the C5-to-C3 ratio is the same in people with and without type 2 diabetes. The possible effects of transaldolase exchange or selective retention of deuterium (or tritium) at the level of the triose-isomerase reaction on tracee labeling and tracer metabolism should be considered when the deuterated water method is used to measure gluconeogenesis or [3-(3)H] glucose is used to measure glucose turnover in humans.

  16. Fast analysis of quaternary ammonium pesticides in food and beverages using cation-exchange chromatography coupled with isotope-dilution high-resolution mass spectrometry. (United States)

    Nardin, Tiziana; Barnaba, Chiara; Abballe, Franco; Trenti, Gianmaria; Malacarne, Mario; Larcher, Roberto


    A fast separation based on cation-exchange liquid chromatography coupled with high-resolution mass spectrometry is proposed for simultaneous determination of chlormequat, difenzoquat, diquat, mepiquat and paraquat in several food and beverage commodities. Solid samples were extracted using a mixture of water/methanol/formic acid (69.6:30:0.4, v/v/v), while liquid samples were ten times diluted with the same solution. Separation was carried out on an experimental length-modified IonPac CS17 column (2 × 15 mm(2) ) that allowed the use of formic acid and acetonitrile as mobile phase. Detection limits for food and beverage matrices were established at 1.5 μg/L for chlormequat, difenzoquat and mepiquat, and 3 μg/L for diquat and paraquat, while for drinking water a pre-analytical sample concentration allowed detection limits of 9 and 20 ng/L, respectively. Precision, as repeatability (RSD%), ranged from 0.2 to 24%, with a median value of 6%, and trueness, as recovery, ranged from 64 to 118%, with a median value of 96%. The method developed was successfully applied to investigate the presence of herbicide residues in commercial commodities (mineral water, orange juice, beer, tea, green coffee bean, toasted coffee powder, cocoa bean, white corn flour, rice and sugar samples). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Redefining the utility of the three-isotope method (United States)

    Cao, Xiaobin; Bao, Huiming


    The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

  18. Carbon assimilation, translocation and respiration in Fagus sylvatica and Abies alba stands measured by gas exchange and isotopic techniques during two contrasting climatic years (United States)

    Gavrichkova, Olga; Scartazza, Andrea; Zampedri, Roberto; Cavagna, Mauro; Sottocornola, Matteo; Matteucci, Giorgio; Brugnoli, Enrico


    season each year. At the beech site the middle samplings corresponded to the peak of the drought season whereas the last samplings of each year - to recovery phase. Leaves were sampled with three replicates at three heights. Assimilation activity was monitored on the leaf level with a portable LiCor 6400 system. Leaf respiration was measured with the same instrument after keeping the leaves for 30 min in darkness. Recently assimilated soluble sugars as well as bulk leaf organic matter were analysed in the laboratory for their δ13C signature and for sugars quantity and composition. Trunk, root and soil respirations together with their δ13C signatures were measured with closed static chambers by the Keeling plot approach. Phloem was sampled with a bark core aiming to analyse the C isotopic signature and composition of assimilates translocate downward with the phloem flow. A sequence of climatically different growing seasons and detailed analyses of plant material allowed us to evaluate climatically-induced variations in different steps of the C cycle at a plant level and to derive some conclusions on the plasticity of European beech and Silver fir in response to changing climate.

  19. Isotope separation (United States)

    Bartlett, Rodney J.; Morrey, John R.


    A method and apparatus is described for separating gas molecules containing one isotope of an element from gas molecules containing other isotopes of the same element in which all of the molecules of the gas are at the same electronic state in their ground state. Gas molecules in a gas stream containing one of the isotopes are selectively excited to a different electronic state while leaving the other gas molecules in their original ground state. Gas molecules containing one of the isotopes are then deflected from the other gas molecules in the stream and thus physically separated.

  20. Isotopic exchange between molecular hydrogen and liquid ammonia catalysed by alkali amides; Echange isotopique entre l'hydrogene moleculaire et l'ammoniac liquide catalyse par les amidures alcalins

    Energy Technology Data Exchange (ETDEWEB)

    Delmas, R. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    The catalytic action of alkali amides on the isotopic exchange between hydrogen and liquid ammonia has been reinvestigated. It was clear before this work that the reaction is homogeneous and first order with respect to the concentration of dissolved hydrogen, but the nature of the catalytic species was still subject to discussion. On one hand new precise kinetic measurements have been made with sodium, potassium, rubidium and cesium amide. On the other hand, the dissociation of these salts has been calculated with the help of the FUOSS-ONSAGER equation. If the rate of exchange is plotted as a function of the concentration of the free amide ion, a linear relationship is obtained. In our experimental conditions, primary salt effects are negligible and the concentration has to be used in the rate equations. This shows that only the free amide ion is acting as a catalytic species. Experiments on common ion effects and secondary salt effects support this conclusion. The results are in agreement with an associative mechanism. (author) [French] Une nouvelle etude de l'echange isotopique entre l'hydrogene et l'ammoniac liquide catalyse par les amidures alcalins a ete effectuee. II etait bien etabli avant le present travail que la reaction etait homogene et que sa vitesse etait du premier ordre par rapport a la concentration d'hydrogene dissous, mais la nature de l'espece catalytique etait encore controversee. De nouvelles mesures cinetiques precises ont ete faites avec les amidures de sodium, de potassium, de rubidium et de cesium. D'autre part, la dissociation de ces sels a ete calculee a l'aide de l'equation de FUOSS-ONSAGER. On constate que la vitesse d'echange est proportionnelle a la concentration de l'ion amidure libre. Dans nos conditions experimentales, les effets de sel primaires sont negligeables, l'equation de vitesse doit s'exprimer simplement en fonction des concentrations. Ceci indique que l

  1. Leatherback Isotopes (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — SWFSC is currently working on a project identifying global marine isotopes using leatherback turtles (Dermochelys coriacea) as the indicator species. We currently...

  2. Isotope Identification

    Energy Technology Data Exchange (ETDEWEB)

    Karpius, Peter Joseph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The objective of this training modules is to examine the process of using gamma spectroscopy for radionuclide identification; apply pattern recognition to gamma spectra; identify methods of verifying energy calibration; and discuss potential causes of isotope misidentification.

  3. Barter exchanges

    DEFF Research Database (Denmark)

    Sudzina, Frantisek

    Although barter is often perceived as something that proceeded money, barter is still used. The focus of the paper is on barter exchanges. Barter exchanges are used both in developing countries as well as in developed countries (including the U.S.). They are used by both organizations...... and individuals. They usually allow to exchange good but some include also services. Some exchanges allow only for bi-directional barter, i.e. when only two parties are involved in the exchange. But probably most of the barter exchanges use barter money; this makes it easier to exchange goods and services...

  4. Transendothelial lipoprotein exchange and microalbuminuria

    DEFF Research Database (Denmark)

    Jensen, Jan Skov; Feldt-Rasmussen, Bo; Jensen, Kurt Svarre


    OBJECTIVE: Microalbuminuria associates with increased risk of atherosclerosis in individuals without diabetes. We hypothesized that transendothelial lipoprotein exchange is elevated among such individuals, possibly explaining increased intimal lipoprotein accumulation and thus atherosclerosis....... METHODS: Using an in vivo isotope technique, transendothelial exchange of low density lipoprotein (LDL) was measured in 77 non-diabetic individuals. Autologous 131-iodinated LDL was reinjected intravenously, and the 1-h fractional escape rate was calculated as index of transendothelial exchange. RESULTS......: There was no difference in transendothelial LDL exchange between subjects with microalbuminuria versus normoalbuminuria (mean (95% confidence interval) 3.8%/h (3.3-4.3%/h) versus 4.2%/h (3.7-4.7%/h); P=0.33). In contrast, there was a positive correlation between transendothelial LDL exchange and (logarithmically...

  5. ISOTOPE SEPARATORS (United States)

    Bacon, C.G.


    An improvement is presented in the structure of an isotope separation apparatus and, in particular, is concerned with a magnetically operated shutter associated with a window which is provided for the purpose of enabling the operator to view the processes going on within the interior of the apparatus. The shutier is mounted to close under the force of gravity in the absence of any other force. By closing an electrical circuit to a coil mouated on the shutter the magnetic field of the isotope separating apparatus coacts with the magnetic field of the coil to force the shutter to the open position.

  6. Stable isotope

    African Journals Online (AJOL)

    Results of the study suggest that there are two main carbon pathways for plankton and nekton in the Kariega estuary, carbon derived from the eelgrass and its associated epiphytes and carbon which has its origins in the salt marsh riparian vegetation and zooplankton. Keywords: stable isotope analysis; temperate estuary; ...

  7. Biological signatures in clumped isotopes of O2 (United States)

    Yeung, Laurence Y.; Ash, Jeanine L.; Young, Edward D.


    The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of “clumped” isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2—and not formation temperatures. Photosynthetic O2 is depleted in 18O18O and 17O18O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling.

  8. Novel PEFC Application for Deuterium Isotope Separation

    Directory of Open Access Journals (Sweden)

    Hisayoshi Matsushima


    Full Text Available The use of a polymer electrolyte fuel cell (PEFC with a Nafion membrane for isotopic separation of deuterium (D was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange of D with protium (H in H2O was facilitated by a Pt catalyst. The anodic data showed that the separation efficiency was dependent on the D concentration in the source gas, whereby the water produced during the operation of the PEFC was more enriched in D as the D concentration of the source gas was increased.

  9. Oxygen isotope fractionation in stratospheric CO2 (United States)

    Thiemens, M. H.; Jackson, T.; Mauersberger, K.; Schueler, B.; Morton, J.


    A new cryogenic collection system has been flown on board a balloon gondola to obtain separate samples of ozone and carbon dioxide without entrapping major atmospheric gases. Precision laboratory isotopic analysis of CO2 samples collected between 26 and 35.5 km show a mass-independent enrichment in both O-17 and O-18 of about 11 per mil above tropospheric values. Ozone enrichment in its heavy isotopes was 9 to 16 percent in O3-50 and 8 to 11 percent in O3-49, respectively (Schueler et al., 1990). A mechanism to explain the isotope enrichment in CO2 has been recently proposed by Yung et al. (1991). The model is based on the isotope exchange between CO2 and O3 via O(1D), resulting in a transfer of the ozone isotope enrichment to carbon dioxide. Predicted enrichment and measured values agree well.

  10. A dynamic leaf gas-exchange strategy is conserved in woody plants under changing ambient CO2: evidence from carbon isotope discrimination in paleo and CO2 enrichment studies (United States)

    Rising atmospheric [CO2], ca, is expected to affect stomatal regulation of leaf gas-exchange of woody plants, thus influencing energy fluxes as well as carbon (C), water and nutrient cycling of forests. Researchers have reported that stomata regulate leaf gas-exchange around “set...

  11. A dynamic leaf gas-exchange strategy is conserved in woody plants under changing ambient CO2: evidence from carbon isotope discrimination in paleo and CO2 enrichment studies (United States)

    Rising atmospheric [CO2], ca, is expected to affect stomatal regulation of leaf gas-exchange of woody plants, thus influencing energy fluxes as well as carbon (C), water and nutrient cycling of forests. Researchers have reported that stomata regulate leaf gas-exchange around &ldq...

  12. Carbon isotopes of graphite: Implications on fluid history


    F.J. Luque; E. Crespo-Feo; J.F. Barrenechea; L. Ortega


    Stable carbon isotope geochemistry provides important information for the recognition of fundamental isotope exchange processes related to the movement of carbon in the lithosphere and permits the elaboration of models for the global carbon cycle. Carbon isotope ratios in fluid-deposited graphite are powerful tools for unravelling the ultimate origin of carbon (organic matter, mantle, or carbonates) and help to constrain the fluid history and the mechanisms involved in graphite deposition. Gr...

  13. Anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma-isotope dilution-time-of-flight mass spectrometry for speciation analysis of metal complexes with metallothionein isoforms in gibel carp (Carassius auratus gibelio) exposed to environmental metal pollution. (United States)

    Infante, Heidi Goenaga; Van Campenhout, Karen; Blust, Ronny; Adams, Freddy C


    The capability of post-column isotope dilution (ID) combined with anion-exchange HPLC-ICP-time-of-flight (TOF)-MS was for the first time investigated for environmental quality assessment through metal speciation analysis of metallothionein (MT) isoforms in cytosols of gibel carp (Carassius auratus gibelio), used as biomarkers for environmental metal exposure. A full spectral scanning of the biological sample (with 50 microl injection volume) using ICP-TOF-MS in transient mode allowed fast multi-isotope screening of cytosolic metal-containing fractions and to investigate the presence of matrix-induced interferences. The MT cytosolic fraction of liver and kidney of the carp, sampled at three different sampling sites in Belgium, was partially purified using size-exclusion (SE) HPLC. Quantification of the elements Cd (toxic) and Zn and Cu (essential) associated with MT isoforms in this fraction was addressed using an hybrid approach based on post-column addition of the enriched isotopes 65Cu, 67Zn, 106Cd and monitoring on-line the isotope ratios 63Cu/65Cu, 64Zn/67Zn and 114Cd/106Cd by ICP-MS with a time of flight instrument, which was coupled to anion-exchange HPLC. With this separation method, baseline separation of up to five MT isoforms, which is required for quantitative metal speciation by HPLC-ICP-IDMS, was achieved within a run of 15 min. The MT fraction of the cytosols was also analysed for the total metal content using IDMS with size-exclusion HPLC-ICP-MS and species-unspecific calibration. Results showed significant differences between speciation results and total MT concentrations of control fish and fish from the most contaminated sampling sites, revealing the potential of gibel carp MT for sequestering excess intracellular free-ions (essential and toxic elements) and for its protection against metal toxicity. Preferences for metal sequestration of metal complexes with MT isoforms were also found to be tissue-specific: excess of Cd was found preferably

  14. Calculation of individual isotope equilibrium constants for geochemical reactions (United States)

    Thorstenson, D.C.; Parkhurst, D.L.


    Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation

  15. Relationships between tree height and carbon isotope discrimination (United States)

    Nate G. McDowell; Barbara J. Bond; Lee T. Dickman; Michael G. Ryan; David Whitehead


    Understanding how tree size impacts leaf- and crown-level gas exchange is essential to predicting forest yields and carbon and water budgets. The stable carbon isotope ratio of organic matter has been used to examine the relationship of gas exchange to tree size for a host of species because it carries a temporally integrated signature of foliar photosynthesis and...

  16. The production of stable isotopes in Spain

    Energy Technology Data Exchange (ETDEWEB)

    Urgel, M.; Iglesias, J.; Casas, J.; Saviron, J. M.; Quintanilla, M.


    The activities developed in the field of the production of stable isotopes by means of ion-exchange chromatography and thermal diffusion techniques are reported. The first method was used to study the separation of the nitrogen and boron isotopes, whereby the separation factor was determined by the break through method. Values ranging from 1,028 to 1,022 were obtained for the separation factor of nitrogen by using ammonium hydroxide solutions while the corresponding values as obtained for boron amounted to 1,035-1,027 using boric acid solutions. Using ammonium chloride or acetate and sodium borate, respectively, resulted in the obtention of values for the separation factor approaching unity. The isotopic separation has been carried out according to the method of development by displacement. The separation of the isotopes of the noble gases, oxygen, nitrogen and carbon has been accomplished resorting to the method of thermal diffusion. (Author) 16 refs.

  17. Exchange Network (United States)

    The Environmental Information Exchange Network (EIEN) is an Internet-based system used by state, tribal and territorial partners to securely share environmental and health information with one another and EPA.

  18. The labeling of unsaturated gamma-hydroxybutyric acid by heavy isotopes of hydrogen: iridium complex-mediated H/D exchange by C-H bond activation vs reduction by boro-deuterides/tritides

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Pedersen, M. H. F.; Vogensen, S. B.; Clausen, R. P.; Frolund, B.; Elbert, Tomáš


    Roč. 59, č. 12 (2016), s. 476-483 ISSN 0362-4803 Institutional support: RVO:61388963 Keywords : C-H activation * borotritides * hydrogen/deuterium exchange * iridium catalyst * tritium-labeled gamma-hydroxybutyric acid Subject RIV: CC - Organic Chemistry Impact factor: 1.745, year: 2016

  19. Seafloor alteration, oxygen isotopes and climate (United States)

    Kanzaki, Y.; Kump, L. R.; Kasting, J. F.


    Seafloor alteration can be related to climate in two ways: through storage of carbon dioxide as carbonates and indirectly through its influence on the oxygen isotopic composition of seawater. Low temperature alteration of the seafloor, or seafloor weathering, can store carbon dioxide as carbonates formed as the result of dissolution of cations from silicate rocks, and since this process is temperature dependent, can serve as a climate regulator. On the other hand, the oxygen isotopic composition of seawater is determined by the balance between low temperature crustal alteration (including continental weathering) and high temperature seafloor alteration, because the heavy isotope is depleted from and added to seawater in low and high temperature alteration, respectively. The oxygen isotopic composition of seawater is a parameter necessary to estimate surface temperature of the Earth from the oxygen isotopic composition of authigenic sedimentary rocks. Thus seafloor alteration is related to reconstruction of Earth's climate. We have developed a comprehensive model of seafloor alteration that captures both seafloor weathering and oxygen isotope exchange, and use it to reconcile observations of long-term stability in both climate and altered ocean crust δ18O with secular changes in the oxygen isotopic composition of marine sediments.

  20. Titanium Isotopes Provide Clues to Lunar Origin (United States)

    Taylor, G. J.


    The idea that the Moon formed as the result of the giant impact of a Mars-sized impactor with the still-growing Earth explains two central facts about the Earth-Moon system: its total angular momentum (Earth's spin and the Moon's orbital motion), and the sizes of the metallic cores of the Earth (large) and Moon (tiny). This gives cosmochemists some confidence in the hypothesis, but they would greatly appreciate additional compositional tests. One undisputed point is the identical abundance of the three oxygen isotopes in Earth and Moon. Junjun Zhang and colleagues at the University of Chicago (USA) and the University of Bern (Switzerland) have added another isotopic system to the cosmochemical testing tool kit, titanium isotopes. They find that the ratio of titanium-50 to titanium-47 is identical in Earth and Moon to within four parts per million. In contrast, other solar system materials, such as carbonaceous chondrites, vary by considerably more than this-- up to 150 times as much. The identical oxygen and titanium isotopic compositions in Earth and Moon are surprising in light of what we think we know about planet formation and formation of the Moon after a giant impact. The variations in oxygen and titanium isotopes among meteorite types suggest that it is unlikely that the Moon-forming giant impactor would have had the same isotopic composition as the Earth. Simulations show that the Moon ends up constructed mostly (40-75%) from the impactor materials. Thus, the Moon ought to have different isotopic composition than does Earth. The isotopes might have exchanged in the complicated, messy proto-lunar disk (as has been suggested for oxygen isotopes), making them the same. However, Zhang and colleagues suggest that this exchange is unlikely for a refractory element like titanium. Could the impact simulations be greatly overestimating the contributions from the impactor? Was the mixing of building-block materials throughout the inner solar system much less than

  1. Carbon isotopes in mollusk shell carbonates (United States)

    McConnaughey, Ted A.; Gillikin, David Paul


    Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

  2. Global Cr-isotope distributions in surface seawater and incorporation of Cr isotopes into carbonate shells

    DEFF Research Database (Denmark)

    Paulukat, Cora Stefanie; Frei, Robert; Vögelin, Andrea Regula

    In this study we present the Cr-isotope composition of surface seawater from several locations worldwide. In addition to the samples from the oceans (Atlantic Ocean, Pacific Ocean, Southern Ocean and Artic Ocean) we analysed water samples from areas with a more limited water exchange (Mediterrane...

  3. Isotopic fractionation of tritium in biological systems. (United States)

    Le Goff, Pierre; Fromm, Michel; Vichot, Laurent; Badot, Pierre-Marie; Guétat, Philippe


    Isotopic fractionation of tritium is a highly relevant issue in radiation protection and requires certain radioecological considerations. Sound evaluation of this factor is indeed necessary to determine whether environmental compartments are enriched/depleted in tritium or if tritium is, on the contrary, isotopically well-distributed in a given system. The ubiquity of tritium and the standard analytical methods used to assay it may induce biases in both the measurement and the signification that is accorded to the so-called fractionation: based on an exhaustive review of the literature, we show how, sometimes large deviations may appear. It is shown that when comparing the non-exchangeable fraction of organically bound tritium (neOBT) to another fraction of tritium (e.g. tritiated water) the preparation of samples and the measurement of neOBT reported frequently led to underestimation of the ratio of tritium to hydrogen (T/H) in the non-exchangeable compartment by a factor of 5% to 50%. In the present study, corrections are proposed for most of the biological matrices studied so far. Nevertheless, the values of isotopic fractionation reported in the literature remain difficult to compare with each other, especially since the physical quantities and units often vary between authors. Some improvements are proposed to better define what should encompass the concepts of exchangeable and non-exchangeable fractions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Exchange Options

    NARCIS (Netherlands)

    Jamshidian, F.


    The contract is described and market examples given. Essential theoretical developments are introduced and cited chronologically. The principles and techniques of hedging and unique pricing are illustrated for the two simplest nontrivial examples: the classical Black-Scholes/Merton/Margrabe exchange

  5. In Situ Raman Spectroscopy of Supported Chromium Oxide Catalysts: ^18 O2- ^16 O2 Isotopic Labeling Studies

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.


    The isothermal isotopic exchange reaction of 18 O2 with 16 O of chromium(VI) oxide supported on zirconia, alumina, and titania has been investigated with in situ laser Raman spectroscopy. The isotopic exchange reaction is dependent on the support type, the Cr loading, and the reaction temperature.

  6. In Situ Raman Spectroscopy of Supported Chromium Oxide Catalysts: 18O2-16O2 Isotopic Labeling Studies

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.


    The isothermal isotopic exchange reaction of 18O2 with 16O of chromium(VI) oxide supported on zirconia, alumina, and titania has been investigated with in situ laser Raman spectroscopy. The isotopic exchange reaction is dependent on the support type, the Cr loading, and the reaction temperature.

  7. Oxygen isotope geochemistry of the amphiboles: Isotope effects of cation substitutions in minerals

    Energy Technology Data Exchange (ETDEWEB)

    Kohn, M.J. [Lawrence Livermore National Lab., CA (United States); Valley, J.W. [Univ. of Wisconsin, Madison, WI (United States). Dept. of Geology and Geophysics


    The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition {sup 18}O in the order: hornblende {much_lt} gedrite < cummingtonite {le} anthophyllite. The observed fractionations at {approximately}575 C are: {Delta}(Ged-Hbl) = 0.8%, {Delta}(Cum-Hbl) = 0.9, {Delta}(Cum-Ged) = 0.2, {Delta}(Ath-Ged) = 0.3, and {Delta}(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that {Delta}(Act-Hbl) {approximately} 0.2, {Delta}(Gin-Grt) {much_gt} 1, and {Delta}(Hbl-Grt) {approximately} 0. Thus, glaucophane strongly partitions {sup 18}O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components. Applications of the exchange component method reproduce measured amphibole fractionations to within {+-}0.1 to {+-}0.2%, whereas other predictive methods cause misfit for typical metamorphic hornblende of {ge}0.5% at 575 C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium {delta}{sup 18}O differences of 2--9%. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

  8. In-situ Nd isotope measurements on accessory minerals: Insights into isotope equilibration during metamorphism (United States)

    Hammerli, Johannes; Spandler, Carl; Kemp, Tony; Pirard, Cassian


    differences cannot be simply explained with retrogressive processes and the partial resetting of the isotope system. The results rather suggest that isotopic exchange between different REE-phases in such systems might be limited, and hence heterogeneous isotope signatures of protolithic sedimentary rocks can survive to great depths in subduction-zone environments. These results may have bearing on the reliability of isotopic tracking of the subducted slab component of arc magmas.

  9. Stable isotope ratios of rain and vapor in 1995 hurricanes (United States)

    Lawrence, James Robert; Gedzelman, Stanley David; Zhang, Xiaoping; Arnold, Robert


    Isotope ratios of rain and vapor samples collected at the surface from four tropical cyclones during the active 1995 Atlantic hurricane season were determined. A two-dimensional bulk microphysics isotope model was applied to steady symmetric tropical cyclones to explain the observed low mean values and inward decrease of isotope ratios of the rain and vapor. The low mean value is caused by the tropical cyclone's relatively large size, longevity, and deep clouds. The inward decrease is due to diffusive isotope exchange between falling rain and converging vapor in the atmospheric boundary layer. Dean, a minimal tropical storm, produced relatively high isotope ratios because of its small size and youth. Rains from the extreme outer edge of Felix, a category 3 hurricane, exhibited high isotope ratios similar to normal summer rain. Isotope ratios of rains and vapors from Hurricane Luis in Puerto Rico decreased as the storm approached. Isotope ratios of rain exhibited an abrupt jump from low values in the eastern half of Puerto Rico to high values farther west which is linked to the storm's rainbands. Isotope ratios of Hurricane Opal's rains reflected the storm's asymmetric structure, with lowest values west of the point of landfall. Record low isotope ratios from a squall line that struck eastern Texas two days before landfall are linked to low-level outflow from Opal and demonstrate that hurricanes can vent enormous quantities of vapor to the surroundings.

  10. Ion exchange equilibrium constants

    CERN Document Server

    Marcus, Y


    Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

  11. A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Boschker, H.T.S.; Moerdijk-Poortvliet, T.C.W.; Van Breugel, P.; Houtekamer, M.J.; Middelburg, J.J.


    We have developed a method to analyze stable carbon isotope (13C/12C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent

  12. Statistical clumped isotope signatures

    NARCIS (Netherlands)

    Röckmann, T.; Popa, M.E.; Krol, M.C.; Hofmann, M.E.G.


    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of

  13. Statistical clumped isotope signatures

    NARCIS (Netherlands)

    Röckmann, T.|info:eu-repo/dai/nl/304838233; Popa, M. E.|info:eu-repo/dai/nl/375806407; Krol, M. C.|info:eu-repo/dai/nl/078760410; Hofmann, M. E. G.|info:eu-repo/dai/nl/374642907


    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a

  14. Statistical clumped isotope signatures (United States)

    Röckmann, T.; Popa, M. E.; Krol, M. C.; Hofmann, M. E. G.


    High precision measurements of molecules containing more than one heavy isotope may provide novel constraints on element cycles in nature. These so-called clumped isotope signatures are reported relative to the random (stochastic) distribution of heavy isotopes over all available isotopocules of a molecule, which is the conventional reference. When multiple indistinguishable atoms of the same element are present in a molecule, this reference is calculated from the bulk (≈average) isotopic composition of the involved atoms. We show here that this referencing convention leads to apparent negative clumped isotope anomalies (anti-clumping) when the indistinguishable atoms originate from isotopically different populations. Such statistical clumped isotope anomalies must occur in any system where two or more indistinguishable atoms of the same element, but with different isotopic composition, combine in a molecule. The size of the anti-clumping signal is closely related to the difference of the initial isotope ratios of the indistinguishable atoms that have combined. Therefore, a measured statistical clumped isotope anomaly, relative to an expected (e.g. thermodynamical) clumped isotope composition, may allow assessment of the heterogeneity of the isotopic pools of atoms that are the substrate for formation of molecules. PMID:27535168

  15. Calculation of individual isotope equilibrium constants for implementation in geochemical models (United States)

    Thorstenson, Donald C.; Parkhurst, David L.


    Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

  16. Biochemical effects of salinity on oxygen isotope fractionation during cellulose synthesis. (United States)

    Ellsworth, Patricia V; Sternberg, Leonel S L


    The current isotope tree ring model assumes that 42% of the sucrose oxygen exchanges with stem water during cellulose synthesis and that the oxygen isotope biochemical fractionation is c. 27‰. However, previous studies have indicated that this model can overestimate the cellulose oxygen isotope ratio of plants under salinity or water stress. Saline stress increases soluble carbohydrates and osmolytes, which can alter exchange and biochemical fractionation during cellulose synthesis. To test the effect of salinity as well as the synthesis of osmolytes on exchange and biochemical fractionation, we grew wild-type and a transgenic mannitol synthesizer Arabidopsis thaliana hydroponically with fresh and saline water. We then measured the oxygen isotope ratios of leaf water, stem water and stem cellulose to determine the effects on exchange and biochemical fractionation. Biochemical fractionation did not change, but oxygen isotope exchange was twice as high for plants grown in saline water relative to freshwater-treated plants (0.64 and 0.3, respectively). Mannitol (osmolyte) synthesis did not affect exchange or biochemical fractionation regardless of salinity. Increases in salinity increased oxygen isotope exchange during cellulose synthesis, which may explain the overestimation of cellulose δ(18) O values under saline conditions. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  17. Molecular Exchange in Ordered Diblock Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Previously, molecular exchange between spherical micelles in dilute solution (1 vol% polymer) was investigated using time-resolved small-angle neutron scattering (TR-SANS). As the concentration of spherical micelles formed by the diblock copolymers increases, the micelles begin to overlap and eventually pack onto body-centered cubic (BCC) lattice. In this study, concentrated, ordered micelles (15 vol% polymers) prepared by dispersing isotopically labeled poly(styrene- b -ethylene-alt-propylene) in an isotopic squalane mixture was investigated to understand the micellar concentration dependence of the molecular exchange. Perfectly random mixing of isotopically labeled micelles on the BCC lattice was confirmed by SANS patterns where the interparticle contribution vanishes, resulting in an intensity that directly relates to the exchange kinetics. The measured molecular exchange process for the concentrated, ordered system is qualitatively consistent with the previous observations, but the rate is more than an order of magnitude slower than that for the dilute, disordered system. Infineum(IPrime), MRSEC(NSF), NIST.

  18. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ


    The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

  19. Carbon Isotopes in an Earth System Model (United States)

    Cuntz, M.; Reick, C. H.; Maier-Reimer, E.; Heimann, M.; Scholze, M.; Naegler, T.


    We present first calculations of the carbon isotopic composition of carbon dioxide in the Earth System Model (ESM) COSMOS. Earth System models consist of coupled models of the ocean, the atmosphere, the land surface, the biosphere (marine and terrestrial, plants and soils), and the cryosphere (snow and ice). In COSMOS from the Max Planck Institute for Meteorology, Hamburg, Germany, these components are the model of the atmospheric circulation ECHAM, the physical ocean model MPI-OM, the land surface parameterisation JSBACH and the oceanic carbon cycle model HAMOCC. The ESM COSMOS therefore calculates its own climate and CO2 concentrations during the diel course with a few degrees resolution, driven only by solar activity and human perturbations. The new model version now computes the multiple fractionation processes occurring during uptake of CO2 from the atmosphere by the terrestrial and marine biosphere. The model then redistributes the isotopic compositions in the land and ocean biospheres, including respiration, phenology, fire, land-use change and carbon export. This means that it includes a full isotopic carbon cycle, in the atmosphere, the ocean and on land. The model calculates not only the stable carbon isotope signatures but also radiocarbon activities in the Earth System. It will include in future the radiocarbon perturbation due to nuclear bomb tests. We compare first results of the ESM with other global estimates of terrestrial discrimination. We also compare predicted zonal and seasonal variations of isotope ratios in atmospheric CO2 with measurements from the GLOBALVIEW flask network. The stable and radioactive carbon isotopes are excellent tests for the overall model performance but also for individual model components. For example radiocarbon will be used to test stratosphere-troposphere exchange, ocean circulation and air-sea gas exchange. The isotope-enabled model can be used in future for example to predict carbon isotope ratios of terrestrial

  20. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    Chromium (Cr) stable isotopes are a useful tracer of changes in redox conditions because changes in its oxidation state are accompanied by an isotopic fractionation. For this reason the Cr isotope system is being developed as a potential tool for paleo-redox reconstruction. Dissolved Cr in seawater...... is incorporated into carbonates. Hence, ancient carbonates can potentially record the Cr isotopic composition (δ53Cr ‰) of seawater in the geological past. Reliable application and interpretation of this proxy requires a detailed knowledge about processes that fractionate Cr on the Earth’s surface......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify...

  1. The effect of dipolar interaction on the magnetic isotope effect

    DEFF Research Database (Denmark)

    Mojaza, Matin; Pedersen, Jørgen Boiden; Lukzen, Nikita


    A multi-channel kinetic description is used to study the magnetic isotope effect (MIE) in zero magnetic field. The maximal isotope effect is equal to the number of channels, two for the hyperfine interaction but four for the electron spin dipole–dipole interaction of the intermediate radical pair....... Quantum mechanical calculations agree with these conclusion and show that large MIE may be obtained even in the presence of a strong exchange interaction. The observed magnesium isotope effect on the rate of enzymatic synthesis of adenosine triphosphate (ATP) is approximately 3 implying that the dipolar...... interaction is responsible for the effect. Our calculations provide support for the proposed mechanism....

  2. On the synthesis of radiofluorinated amino acids by isotope exchange based on the example of 6-[{sup 18}F]Fluor-L-DOPA; Zur Synthese radiofluorierter aromatischer Aminosaeuren mittels Isotopenaustausch am Beispiel von 6-[{sup 18}F]Fluor-L-DOPA

    Energy Technology Data Exchange (ETDEWEB)

    Wagner, F.M.


    In nuclear medical diagnosis, 6-[{sup 18}F]fluoro-L-3,4-dihydroxyphenylalanine (6-[{sup 18}F]fluoro-LDOPA), an analogue of L-DOPA, is one of the few established radiopharmaceuticals used for the in vivo investigation of the presynaptic dopaminergic metabolism and of some kind of tumours via Positron Emission Tomography (PET). The presently used method of preparation of the radiotracer by electrophilic labelling is limited to low amounts of activity at high costs. Known nucleophilic syntheses, however, result either in insufficient enantiomeric purity or the known multi-step syntheses are hard to automate, due to their complexity. During this work a novel, easy to automate alternative for the preparation of 6-[{sup 18}F]fluoro-L-DOPA, was developed and evaluated, using a direct nucleophilic {sup 18}F-fluorination of a protected amino acid derivative. The resulting product has a very high enantiomeric purity. At first, the general suitability of the (S)-BOC-BMI-derivatives for the synthesis of {sup 18}F-labelled amino acids, used in this work, was investigated using a less complex precursor, which resulted in the amino acid 6-[{sup 18}F]fluoro-L-m-tyrosin via acidic hydrolysis. The preparation of a useful precursor for the nucleophilic {sup 18}F-isotope substitution, namely the (2S,5S)-tert.-butyl- 5-(2-fluoro-5-formylbenzyl)-2-tert.-butyl-3-methyl-4-oxoimidazolidine-1-carboxylate, was investigated in three general different ways. At first it was tried to obtain this product via formylation after coupling with the BOC-BMI, secondly via {alpha},{beta}-dehydro amino acid derivatives and finally via a systematic multi-step synthesis. Only the last mentioned way resulted in a precursor with sufficient purity that could be labelled. The radiochemical yield of the isotopic exchange was about 60 %. In the next step, the presented concept was modified to synthesize a precursor for the preparation of 6-[{sup 18}F]fluoro-L-DOPA. Only a combination of the protecting groups

  3. Electron spray ionization mass spectrometry and 2D {sup 31}P NMR for monitoring {sup 18}O/{sup 16}O isotope exchange and turnover rates of metabolic oligophosphates

    Energy Technology Data Exchange (ETDEWEB)

    Nemutlu, Emirhan [Mayo Clinic, Division of Cardiovascular Diseases, Department of Medicine, Rochester, MN (United States); University of Hacettepe, Department of Analytical Chemistry, Faculty of Pharmacy, Ankara (Turkey); Juranic, Nenad; Macura, Slobodan [Mayo Clinic, Department of Biochemistry and Molecular Biology, Rochester, MN (United States); Mayo Clinic, Analytical NMR Core Facility, Rochester, MN (United States); Zhang, Song; Terzic, Andre; Dzeja, Petras P. [Mayo Clinic, Division of Cardiovascular Diseases, Department of Medicine, Rochester, MN (United States); Ward, Lawrence E. [Mayo Clinic, CTSA Metabolomic Core Facility, Rochester, MN (United States); Dutta, Tumpa; Nair, K.S. [Mayo Clinic, CTSA Metabolomic Core Facility, Rochester, MN (United States); Mayo Clinic, Division of Endocrinology and Endocrine Research Unit, Rochester, MN (United States)


    A new method was here developed for the determination of {sup 18}O-labeling ratios in metabolic oligophosphates, such as ATP, at different phosphoryl moieties ({alpha}-, {beta}-, and {gamma}-ATP) using sensitive and rapid electrospray ionization mass spectrometry (ESI-MS). The ESI-MS-based method for monitoring of {sup 18}O/{sup 16}O exchange was validated with gas chromatography-mass spectrometry and 2D {sup 31}P NMR correlation spectroscopy, the current standard methods in labeling studies. Significant correlation was found between isotopomer selective 2D {sup 31}P NMR spectroscopy and isotopomer less selective ESI-MS method. Results demonstrate that ESI-MS provides a robust analytical platform for simultaneous determination of levels, {sup 18}O-labeling kinetics and turnover rates of {alpha}-, {beta}-, and {gamma}-phosphoryls in ATP molecule. Such method is advantageous for large scale dynamic phosphometabolomic profiling of metabolic networks and acquiring information on the status of probed cellular energetic system. (orig.)

  4. BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the...

  5. BASIN TCP Stable Isotope Composition of CO2 in Terrestrial Ecosystems (United States)

    National Aeronautics and Space Administration — This data set reports stable isotope ratio data of CO2 (13C/12C and 18O/16O) associated with photosynthetic and respiratory exchanges across the biosphere-atmosphere...

  6. Oxygen isotope fractionation in double carbonates. (United States)

    Zheng, Yong-Fei; Böttcher, Michael E


    Oxygen isotope fractionations in double carbonates of different crystal structures were calculated by the increment method. Synthesis experiments were performed at 60 °C and 100 °C to determine oxygen and carbon isotope fractionations involving PbMg[CO3]2. The calculations suggest that the double carbonates of calcite structure are systematically enriched in (18)O relative to those of aragonite and mixture structures. Internally consistent oxygen isotope fractionation factors are obtained for these minerals with respect to quartz, calcite and water at a temperature range of 0-1200 °C. The calculated fractionation factors for double carbonate-water systems are generally consistent with the data available from laboratory experiments. The experimentally determined fractionation factors for PbMg[CO3]2, BaMg[CO3]2 and CaMg[CO3]2 against H2O not only fall between fractionation factors involving pure carbonate end-members but are also close to the calculated fractionation factors. In contrast, experimentally determined carbon isotope fractionation factors between PbMg[CO3]2 and CO2 are much closer to theoretical predictions for the cerussite-CO2 system than for the magnesite-CO2 system, similar to the fractionation behavior for BaMg[CO3]2. Therefore, the combined theoretical and experimental results provide insights into the effects of crystal structure and exchange kinetics on oxygen isotope partitioning in double carbonates.

  7. Fusion and the Discovery of Isotopes (United States)

    Thoennessen, M.


    Heavy-ion fusion-evaporation has been the most productive method to form and identify new isotopes. Of the presently known over 3200 isotopes, almost 25% were discovered with heavy-ion induced reactions. Since the development of the first heavy-ion beam at Berkeley in 1950 most of the nuclides on the neutron-deficient side of the line of stability and all isotopes of the superheavy elements were discovered utilizing fusion reactions. In addition, some isotopes were first produced in heavy-ion transfer, charge-exchange, incomplete fusion or deep inelastic reactions. The discovery of isotopes relies on new advances in accelerator and detector technology. The continuous development of pioneering and innovative separation and detection techniques have pushed the limit towards ‒ and in many cases beyond ‒ the proton-dripline. A review of the discovery of neutron-deficient and super-heavy nuclides in heavy-ion induced reactions as well as an outlook for the discovery potential in the future is presented.

  8. Zn Isotope Fractionation during Sorption onto Kaolinite. (United States)

    Guinoiseau, Damien; Gélabert, Alexandre; Moureau, Julien; Louvat, Pascale; Benedetti, Marc F


    In this study, we quantify zinc isotope fractionation during its sorption onto kaolinite, by performing experiments under various pH, ionic strength, and total Zn concentrations. A systematic enrichment in heavy Zn isotopes on the surface of kaolinite was measured, with Δ(66)Znadsorbed-solution ranging from 0.11‰ at low pH and low ionic strength to 0.49‰ at high pH and high ionic strength. Both the measured Zn concentration and its isotopic ratio are correctly described using a thermodynamic sorption model that considers two binding sites: external basal surfaces and edge sites. Based on this modeling approach, two distinct Zn isotopic fractionation factors were calculated: Δ(66)Znadsorbed-solution = 0.18 ± 0.06‰ for ion exchange onto basal sites, and Δ(66)Znadsorbed-solution = 0.49 ± 0.06‰ for specific complexation onto edge sites. These two distinct factors indicate that Zn isotope fractionation is dominantly controlled by the chemical composition of the solution (pH, ionic strength).

  9. Isotopic Evidence of Unaccounted for Fe and Cu Erythropoietic Pathways (United States)

    Albarede, F.; Telouk, P.; Lamboux, A.; Jaouen, K.; Balter, V.


    Despite its potential importance for understanding perturbations in the Fe-Cu homeostatic pathways, the natural isotopic variability of these metals in the human body remains unexplored. We measured the Fe, Cu, and Zn isotope compositions of total blood, serum, and red blood cells of ~50 young blood donors by multiple-collector ICP-MS after separation and purification by anion exchange chromatography. Zn is on average 0.2 permil heavier in erythrocytes (δ 66Zn=0.44±0.33 permil) with respect to serum but shows much less overall isotopic variability than Fe and Cu, which indicates that isotope fractionation depends more on redox conditions than on ligand coordination. On average, Fe in erythrocytes (δ 56Fe=-2.59±0.47 permil) is isotopically light by 1-2 permil with respect to serum, whereas Cu in erythrocytes (δ 65Cu=0.56±0.50 permil) is 0.8 percent heavier. Fe and Cu isotope compositions clearly separate erythrocytes of men and women. Fe and Cu from B-type men erythrocytes are visibly more fractionated than all the other blood types. Isotope compositions provide an original method for evaluating metal mass balance and homeostasis. Natural isotope variability shows that the current models of Fe and Cu erythropoiesis, which assume that erythropoiesis is restricted to bone marrow, violate mass balance requirements. It unveils unsuspected major pathways for Fe, with erythropoietic production of isotopically heavy ferritin and hemosiderin, and for Cu, with isotopically light Cu being largely channeled into blood and lymphatic circulation rather than into superoxide dismutase-laden erythrocytes. Iron isotopes provide an intrinsic measuring rod of the erythropoietic yield, while Cu isotopes seem to gauge the relative activity of erythropoiesis and lymphatics.

  10. Determination of porphyrin carbon isotopic composition using gas chromatography-isotope ratio monitoring mass spectrometry. (United States)

    Yu, Z; Sheng, G; Fu, J; Peng, P


    Carbon isotopic compositions of aetio I occurring in the form of free-base, nickel, demetallation, dihydroxysilicon(IV) and bis(tert.-butyldimethylsiloxy)silicon(IV) [(tBDMSO)2Si(IV)] have shown that it has experienced no obvious isotope fractionation during the synthesis of [(tBDMSO)2Si(IV)] porphyrin from aetio I. Here, aetio I porphyrin species such as free-base, nickel, demetallated and dihydroxysilicon were analyzed by the conventional method, namely it is combusted in sealed system, and followed by isotope ratio monitoring mass spectrometric analysis. [(tBDMSO)2Si(IV)] aetio I was assayed by gas chromatography-isotope ratio monitoring mass spectrometry (GC-IRMS). A porphyrin mixture of [(tBDMSO)2Si(IV)] aetio I and octaethylporphyrin was also prepared. Their carbon isotopic compositions measured by GC-IRMS indicate that no isotope exchange took place between the porphyrins during the synthesis of [(tBDMSO)2Si(IV)] porphyrins. This method is employed for delta13C determination of geoporphyrins from the Maoming and Jianghan oil shales.

  11. Segmented heat exchanger (United States)

    Baldwin, Darryl Dean; Willi, Martin Leo; Fiveland, Scott Byron; Timmons, Kristine Ann


    A segmented heat exchanger system for transferring heat energy from an exhaust fluid to a working fluid. The heat exchanger system may include a first heat exchanger for receiving incoming working fluid and the exhaust fluid. The working fluid and exhaust fluid may travel through at least a portion of the first heat exchanger in a parallel flow configuration. In addition, the heat exchanger system may include a second heat exchanger for receiving working fluid from the first heat exchanger and exhaust fluid from a third heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the second heat exchanger in a counter flow configuration. Furthermore, the heat exchanger system may include a third heat exchanger for receiving working fluid from the second heat exchanger and exhaust fluid from the first heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the third heat exchanger in a parallel flow configuration.

  12. Mechanism of Molecular Exchange in Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Compared to thermodynamic structure, much less has been known about the kinetics of block copolymer micelles which should underlay the attainment of thermodynamic equilibrium. In this presentation, molecular exchange between spherical micelles formed by isotopically labeled diblock copolymers was investigated using time-resolved small-angle neutron scattering. Two pairs of structurally matched poly(styrene-b-ethylene-alt-propylene) (PS-PEP) were synthesized and dispersed in isotopic mixture of squalane, highly selective to PEP block. Each pair includes polymers with fully deuterated (dPS-PEP) and a normal (hPS-PEP) PS blocks. Temperature dependence of the micelle exchange rate R(t) is consistent with melt dynamics for the core polymer. Furthermore, R(t) is significantly sensitive to the core block length N due to the thermodynamic penalty associated with ejecting a core block into the solvent. This hypersensitivity, combined with modest polydispersity in N, leads to an approximately logarithmic decay in R(t).

  13. Sources of Holocene variability of oxygen isotopes in paleoclimate archives

    Directory of Open Access Journals (Sweden)

    A. N. LeGrande


    Full Text Available Variability in water isotopes has been captured in numerous archives and used to infer past climate changes. Here we examine water isotope variability over the course of the Holocene using the water-isotope enabled, coupled atmosphere-ocean general circulation model, GISS ModelE-R. Eight Holocene time slices, ~1000 years apart are simulated and driven by estimated changes in orbital configuration, greenhouse gases, and ice sheet extent. We find that simulated water isotope archives match well with those seen in ice cores, ocean sediment cores, and speleothems. The climate changes associated with the water isotope changes, however, are more complex than simple modern spatial slope interpretations might suggest. In particular, water isotope variability in Asian speleothems is linked to alterations in landward water vapor transport, not local precipitation, and ice sheet changes over North America lead to the masking of temperature signals in Summit, Greenland. Salinity-seawater isotope variability is complicated by inter-ocean basin exchanges of water vapor. Water isotopes do reflect variability in the hydrology, but are better interpreted in terms of regional hydrological cycle changes rather than as indicators of local climate.

  14. Deuterium exchange during acid-demineralisation. [of Murchison meteorite (United States)

    Kerridge, John F.; Chang, Sherwood; Shipp, Ruth


    Isotopic analyses of residues prepared by demineralization of the Murchison meteorite using D-labelled reagents provide evidence for measurable exchange of H-isotopes between residue and reagents. Precise quantification of this effect is precluded by substantial inhomogeneity of the meteoritic organic matter. A conservative estimate of the degree of exchange is 3-5 percent of the H pyrolyzable as H2O. This could affect the shape of the curve defining D release as a function of temperature, but does not change conclusions previously drawn concerning the nature of the bulk D enrichment of insoluble organic matter in meteorites.

  15. Fishing for isotopes in the Brookhaven Lab Isotope Producer (BLIP) cooling water

    Energy Technology Data Exchange (ETDEWEB)

    Fitzsimmons, Jonathan [Brookhaven National Lab. (BNL), Upton, NY (United States). Collider Accelerator Dept.


    Be-7 has been used in environmental studies; the isotope is produced during BLIP irradiations and accumulates in the 320 gallons of cooling water. Be-7 has a 53.24 day half-life, so the optimal production/purification time is at the end of the BLIP run season. To purify Be-7 fifteen to twenty gallons of BLIP cooling water are removed and pumped through ion exchange columns that retain Be-7. This labor intensive approach captures ~15 mCi of Be-7, but the solution requires further purification. The method can lead to increased radiation exposure to staff. The ideal way to capture isotopes from large volumes is to reach in to the solution and selectively pull out the desired isotope. It is a lot like fishing.

  16. NOx cycle and tropospheric ozone isotope anomaly: an experimental investigation (United States)

    Michalski, G.; Bhattacharya, S. K.; Girsch, G.


    The oxygen isotope composition of nitrogen oxides (NOx) in the atmosphere may be a useful tool for understanding the oxidation of NOx into nitric acid/nitrate in the atmosphere. A set of experiments were conducted to examine changes in isotopic composition of NOx due to O3-NOx photochemical cycling. At low NO2/O2 mixing ratios, NO2 becomes progressively and nearly equally enriched in 17O and 18O over time until it reaches a steady state with Δ17O values of 40.6 ± 1.9‰ and δ18O values of 84.2 ± 4‰, relative to the isotopic composition of the O2 gas. As the mixing ratio increases, isotopic exchange between O atoms and O2 and NOx suppresses the isotopic enrichments. A kinetic model simulating the observed data shows that the isotope effects during ozone formation play a more dominant role compared to kinetic isotope effects during NO oxidation or exchange of NO2. The model results are consistent with the data when the NO + O3 reaction occurs mainly via the transfer of the terminal atom of O3. The model predicts that under tropospheric concentrations of the three reactants, the timescale of NOx isotopic equilibrium ranges from hours (ppbv mixing ratios) to days/weeks (pptv) and yields steady state Δ17O and δ18O values of 46‰ and 115‰ respectively with respect to Vienna Standard Mean Ocean Water. Interpretation of tropospheric nitrate isotope data can now be done with the derived rate coefficients of the major isotopologue reactions at various pressures.

  17. The process of glauconitization: chemical and isotopic evidence (United States)

    Stille, Peter; Clauer, Norbert


    liberation of these elements. Consequently, the phosphate-rich phase with sea water Sr and Nd isotopic signatures becomes increasingly important for the isotopic characteristics of the maturing glauconite grains, and sea water isotopic signatures can be reached during the stage of mature glauconite (K2O>6.5%), without chemical exchange with the depositional environment.

  18. Measurements of Isotopic Composition of Vapour on the Antarctic Plateau (United States)

    Casado, M.; Landais, A.; Masson-Delmotte, V.; Genthon, C.; Prie, F.; Kerstel, E.; Kassi, S.; Arnaud, L.; Steen-Larsen, H. C.; Vignon, E.


    The oldest ice core records are obtained on the East Antarctic plateau. The composition in stable isotopes of water (δ18O, δD, δ17O) permits to reconstruct the past climatic conditions over the ice sheet and also at the evaporation source. Paleothermometer accuracy relies on good knowledge of processes affecting the isotopic composition of surface snow in Polar Regions. Both simple models such as Rayleigh distillation and global atmospheric models with isotopes provide good prediction of precipitation isotopic composition in East Antarctica but post deposition processes can alter isotopic composition on site, in particular exchanges with local vapour. To quantitatively interpret the isotopic composition of water archived in ice cores, it is thus essential to study the continuum water vapour - precipitation - surface snow - buried snow. While precipitation and snow sampling are routinely performed in Antarctica, climatic conditions in Concordia, very cold (-55°C in average) and very dry (less than 1000ppmv), impose difficult conditions to measure the water vapour isotopic composition. New developments in infrared spectroscopy enable now the measurement of isotopic composition in water vapour traces (down to 20ppmv). Here we present the results of a campaign of measurement of isotopic composition in Concordia in 2014/2015. Two infrared spectrometers have been deployed or the first time on top of the East Antarctic Plateau allowing a continuous vapour measurement for a month. Comparison of the results from infrared spectroscopy with cryogenic trapping validates the relevance of the method to measure isotopic composition in dry conditions. Identification of different behaviour of isotopic composition in the water vapour associated to turbulent or stratified regime indicates a strong impact of meteorological processes in local vapour/snow interaction.

  19. Oxygen isotope fractionation between analcime and water - An experimental study (United States)

    Karlsson, Haraldur R.; Clayton, Robert N.


    The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

  20. Discovery of the Indium Isotopes

    CERN Document Server

    Amos, S


    Thirty-eight indium isotopes (A = 98-135) have so far been observed; the discovery of these isotopes is discussed. For each isotope a brief summary of the first refereed publication, including the production and identification method, is presented.

  1. Iron Isotope Constraints on Planetesimal Core Formation (United States)

    Jordan, M.; Young, E. D.


    The prevalence of iron in both planetary cores and silicate mantles renders the element a valuable tool for understanding core formation. Magmatic iron meteorites exhibit an enrichment in 57Fe/54Fe relative to chondrites and HED meteorites. This is suggestive of heavy Fe partitioning into the cores of differentiated bodies. If iron isotope fractionation accompanies core formation, we can elucidate details about the history of accretion for planetary bodies as well as their compositions and relative core sizes. The equilibrium 57Fe/54Fe between metal and silicate is necessary for understanding observed iron isotope compositions and placing constraints on core formation. We measure this fractionation in two Aubrite meteorites, Norton County and Mount Egerton, which have known temperatures of equilibration and equilibrated silicon isotopes. Iron was purified using ion-exchange chromatography. Data were collected on a ThermoFinnigan NeptuneTM multiple-collector inductively coupled plasma-source mass spectrometer (MC-ICP-MS) run in wet plasma mode. The measured fractionation Δ57Femetal-silicate is 0.08‰ ± 0.039 (2 SE) for Norton County and 0.09‰ ± 0.019 (2 SE) for Mount Egerton, indicating that the heavy isotopes of Fe partition into the metallic phase. These rocks are in isotopic equilibrium at a temperature of 1130 K and 1200 K ± 80 K, respectively. The concentration of the heavy isotopes of iron in the metallic phase is consistent with recent experimental studies. Using our measured metal-silicate Fe isotope fractionation and the resulting temperature calibration, while taking into account impurities in the metallic phase and temperatures of equilibration, determine that core formation could explain the observed difference between magmatic iron meteorites and chondrites if parent bodies have small cores. In order to verify that Rayleigh distillation during fractional crystallization was not a cause of iron isotope fractionation in iron meteorites, we measured

  2. Site-Specific Carbon Isotopes in Organics (United States)

    Piasecki, A.; Eiler, J. M.


    propane and labeled propane (13CH3-12CH2-12CH3). Results are consistent with the expected relative fractionations between the two fragments, indicating limited 'scrambling' of carbon positions of less than 2% in the source. The limits of precision of this method are currently ~0.5 ‰, sufficient to resolve known or suspected position-specific isotope effects in propane. We have explored the expected temperature-dependent equilibrium isotopic distributions of propane using density functional theory and quantum mechanical models of vibrational isotope effects. These models predict the homogeneous isotope exchange equilibria among the various isotopologues of propane, which include several of a wide range of effects that should be measurable by our methods. At 300 K we predict that the central carbon site is 15‰ higher in δ13C and 95 ‰ higher in δD than the terminal carbon site; similarly the molecule containing both a 13C and D in the central site is enriched by ~120 ‰ relative to a random isotopic distribution at 300 K. These predictions present targets for future experimental and empirical studies of the temperature dependence of isotopic ordering in propane. More generally, the methods we are developing for the study of intramolecular isotopic distributions in propane will serve as a model for future study of similar effects in other organic compounds. [1]DeNiro, Epstein (1977) Science Volume 197, 261-263.


    African Journals Online (AJOL)

    Valley. Although fossil specimens of this subspecies have been used in palaeoclimatic reconstruction, there have been no previous reports of living examples. Here We describe the local habitat, climate and some aspects of ecology and isotopic variation within the snail shell. If isotope data can be obtained for fossil shells, ...

  4. ICT: isotope correction toolbox. (United States)

    Jungreuthmayer, Christian; Neubauer, Stefan; Mairinger, Teresa; Zanghellini, Jürgen; Hann, Stephan


    Isotope tracer experiments are an invaluable technique to analyze and study the metabolism of biological systems. However, isotope labeling experiments are often affected by naturally abundant isotopes especially in cases where mass spectrometric methods make use of derivatization. The correction of these additive interferences--in particular for complex isotopic systems--is numerically challenging and still an emerging field of research. When positional information is generated via collision-induced dissociation, even more complex calculations for isotopic interference correction are necessary. So far, no freely available tools can handle tandem mass spectrometry data. We present isotope correction toolbox, a program that corrects tandem mass isotopomer data from tandem mass spectrometry experiments. Isotope correction toolbox is written in the multi-platform programming language Perl and, therefore, can be used on all commonly available computer platforms. Source code and documentation can be freely obtained under the Artistic License or the GNU General Public License from: {,} Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail:

  5. Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O (United States)

    Anicich, V. G.; Sen, A. D.


    Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

  6. Radiotracer application for characterization of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC

    Energy Technology Data Exchange (ETDEWEB)

    Singare, P.U. [Bhavan' s College, Mumbai (India). Dept. of Chemistry


    Radio isotopic tracer technique as one of the versatile nondestructive technique is employed to evaluate the performance of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC. The evaluation was made on the basis of ion-isotopic exchange reaction kinetics by using {sup 131}I and {sup 82}Br radioactive tracer isotopes. It was observed that for both the resins, the values of specific reaction rate (min{sup -1}), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) were calculated to be lower for bromide ion-isotopic exchange reaction than that for iodide ion-isotopic exchange reaction. It was observed that for iodide ion-isotopic exchange reaction under identical experimental conditions of 30.0 C, 1.000 g of ion exchange resins and 0.001 mol/L labeled iodide ion solution, the values of specific reaction rate (min{sup -1}), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K{sub d} were calculated as 0.377, 0.212, 0.080 and 15.5 respectively for Dowex SBR LC resin, which was higher than 0.215, 0.144, 0.031 and 14.1 respectively as that obtained for Tulsion A23 resins. Also at a constant temperature of 30.0 C, as the concentration of labeled iodide ion solution increases from 0.001 mol/L to 0.004 mol/L, the percentage of iodide ions exchanged increases from 84.75 % to 90.20 % for Dowex SBR LC resins which was higher than increases from 57.66 % to 62.38 % obtained for Tulsion A23 resins. The identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate superior performance of Dowex SBR LC over Tulsion A23 resins under identical experimental conditions.

  7. Totalization Data Exchange (TDEX) (United States)

    Social Security Administration — The Totalization Data Exchange (TDEX) process is an exchange between SSA and its foreign country partners to identify deaths of beneficiaries residing abroad. The...

  8. Significance of Isotopically Labile Organic Hydrogen in Thermal Maturation of Organic Matter

    Energy Technology Data Exchange (ETDEWEB)

    Arndt Schimmelmann; Maria Mastalerz


    Isotopically labile organic hydrogen in fossil fuels occupies chemical positions that participate in isotopic exchange and in chemical reactions during thermal maturation from kerogen to bitumen, oil and gas. Carbon-bound organic hydrogen is isotopically far less exchangeable than hydrogen bound to nitrogen, oxygen, or sulfur. We explore why organic hydrogen isotope ratios express a relationship with organic nitrogen isotope ratios in kerogen at low to moderate maturity. We develop and apply new techniques to utilize organic D/H ratios in organic matter fractions and on a molecular level as tools for exploration for fossil fuels and for paleoenvironmental research. The scope of our samples includes naturally and artificially matured substrates, such as coal, shale, oil and gas.

  9. Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems (United States)

    Ni, Y.; Ma, Q.; Ellis, G.S.; Dai, J.; Katz, B.; Zhang, S.; Tang, Y.


    Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using ??D values in ethane from several basins in the world are in close agreement with similar predictions based on the ??13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that ??D values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that ??D values in ethane might be more suitable for modeling than comparable values in methane and propane. ?? 2011 Elsevier Ltd.

  10. Lithium Isotopic Fractionation in Subduction Zones: Clues From Clays (United States)

    Williams, L. B.; Hervig, R. L.


    Lithium isotope ratios show such large variations in nature (>30 per mil), that many areas of geosciences are exploring the usefulness of this system in explaining the evolution of particular rocks. Here we show how the lithium isotope ratios change during the transformation of smectite clay minerals to illite during burial metamorphism. Such a transition may be a common feature in the shallow regions of subduction zones and may ultimately affect the Li isotope compositions of fluids contributing to arc magmatism. Lithium is a ubiquitous trace element in natural formation waters that, like B, shows large isotopic fractionation especially during interactions with clay minerals. Lithium is adsorbed in the interlayer region of expandable clay minerals but is easily exchanged. Lithium is also incorporated into the octahedral sites. The substitutions of Li in two crystallographic sites of clay minerals may complicate interpretations of bulk Li-isotope ratios. We suggest that the magnitude of the isotopic fractionation of Li between fluid and clay is different in the interlayer sites of clay minerals than in the octahedral sites of clay minerals. Examination of Li contents and isotope variations in experimental reactions of smectite to illite (300C, 100MPa) shows changes with structural re-arrangement of the clay layers. The Li-isotope trend declines (from ~+6 to -13 per mil, expressed as ratios of 7/6) throughout R1-ordering of the mixed-layered illite smectite (I/S). However, the equilibrium end products of the reaction have R3-ordering and show a heavier isotope ratio (~0 per mil). This observation is very similar to the trends we observed for B-isotopes, where the interlayer B initially overprinted the tetrahedral-layer B isotope composition, but as the interlayer sites were collapsed during illitization, the equilibrium isotope composition was approached. The significant Li and B isotopic changes that occur during ordering of I/S coincides with the temperatures

  11. Iron isotope systematics in planetary reservoirs (United States)

    Sossi, Paolo A.; Nebel, Oliver; Foden, John


    Iron is the only polyvalent major element, and controls reduction-oxidation (redox) reactions in a host of geologic processes and reservoirs, from the mineral- to planetary-scale, on Earth and in space. Mass transfer of Fe is often accompanied by changes in bonding environment, meaning the resultant variation in bond-strength in crystals, liquids and gases induces stable isotope fractionation, even at high temperatures. In the absence of iron exchange, electron transfer can also affect iron's valence state and calculated oxygen fugacity (fO2), however its isotope composition remains unchanged. Thus, iron isotopes are a powerful tool to investigate processes that involve mass transfer, redox reactions and changes in bonding environment in planetary systems. Primitive chondritic meteorites show remarkable isotopic homogeneity, δ57 Fe = - 0.01 ± 0.01 ‰ (2SE), over a wide range of Fe/Mg vs Ni/Mg, a proxy for fO2 in the solar nebula. In chondrites, there are iron isotope differences between metal and silicates that become more pronounced at higher metamorphic grades. However, on a planetary scale, Mars and Vesta overlap with chondrites, preserving no trace of core formation or volatile depletion on these bodies. Upon assessment of pristine lherzolites, the Bulk Silicate Earth is heavier than chondrites (δ57 Fe = + 0.05 ± 0.01 ‰; 2SE), and similar to or slightly lighter than the Moon. That the mantles of some differentiated inner solar system bodies extend to heavier compositions (+ 0.2 ‰) than chondrites may principally result from volatile depletion either at a nebular or late accretion stage. Within terrestrial silicate reservoirs, iron isotopes provide insight into petrogenetic and geodynamic processes. Partial melting of the upper mantle produces basalts that are heavier than their sources, scaling with degree of melting and driving the increasingly refractory peridotite to lighter compositions. Mid-Ocean Ridge Basalts (MORBs) are homogeneous to δ57 Fe

  12. Isotopes through the looking glass (United States)

    Mårtensson Pendrill, Ann Marie


    Nuclear distributions affect many aspects of atomic spectra. As an example, recent experimental results for the hyperfine anomaly in Fr isotopes are considered. These depend on nuclear charge and magnetization distributions. The variations in charge radii for these isotopes were studied earlier by measuring optical isotope shifts. The hyperfine anomalies for the odd-odd isotopes involve the neutron distributions, of interest for studies of parity nonconserving effects along a chain of isotopes.

  13. Calcium stable isotope geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gausonne, Nikolaus [Muenster Univ. (Germany). Inst. fuer Mineralogie; Schmitt, Anne-Desiree [Strasbourg Univ. (France). LHyGeS/EOST; Heuser, Alexander [Bonn Univ. (Germany). Steinmann-Inst. fuer Geologie, Mineralogie und Palaeontologie; Wombacher, Frank [Koeln Univ. (Germany). Inst. fuer Geologie und Mineralogie; Dietzel, Martin [Technische Univ. Graz (Austria). Inst. fuer Angewandte Geowissenschaften; Tipper, Edward [Cambridge Univ. (United Kingdom). Dept. of Earth Sciences; Schiller, Martin [Copenhagen Univ. (Denmark). Natural History Museum of Denmark


    This book provides an overview of the fundamentals and reference values for Ca stable isotope research, as well as current analytical methodologies including detailed instructions for sample preparation and isotope analysis. As such, it introduces readers to the different fields of application, including low-temperature mineral precipitation and biomineralisation, Earth surface processes and global cycling, high-temperature processes and cosmochemistry, and lastly human studies and biomedical applications. The current state of the art in these major areas is discussed, and open questions and possible future directions are identified. In terms of its depth and coverage, the current work extends and complements the previous reviews of Ca stable isotope geochemistry, addressing the needs of graduate students and advanced researchers who want to familiarize themselves with Ca stable isotope research.

  14. Isotope Production Facility (IPF) (United States)

    Federal Laboratory Consortium — The Los Alamos National Laboratory has produced radioactive isotopes for medicine and research since the mid 1970s, when targets were first irradiated using the 800...

  15. Isotopes in Greenland Precipitation

    DEFF Research Database (Denmark)

    Faber, Anne-Katrine

    ) Constructing a new Greenland database of observations and present-day ice core measurements, and (3) Performance test of isotope-enabled CAM5 for Greenland. The recent decades of rapid Arctic sea ice decline are used as a basis for an observational-based model experiment using the isotope-enabled CAM model 3....... The simulation of Greenland isotopes is tested for the isotope-enabled model CAM5. Here the importance of model resolution is investigated. A positive bias of 6-10 ‰ is found for the annual mean δ18O on the central part of the Greenland Ice Sheet. The amplitude of the seasonal cycle of Greenland δ18O is highly...

  16. Spontaneous oxygen isotope exchange between carbon dioxide and\

    Czech Academy of Sciences Publication Activity Database

    Knížek, Antonín; Zukalová, Markéta; Kavan, Ladislav; Zukal, Arnošt; Kubelík, Petr; Rojík, P.; Skřehot, P.; Ferus, Martin; Civiš, Svatopluk


    Roč. 137, MAR 2017 (2017), s. 6-10 ISSN 0169-1317 R&D Projects: GA MŠk LD14115; GA ČR(CZ) GA14-12010S; GA ČR GA13-07724S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388955 Keywords : clay * carbon dioxide * FTIR spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.101, year: 2016

  17. 10 CFR Appendix E to Part 110 - Illustrative List of Chemical Exchange or Ion Exchange Enrichment Plant Equipment and Components... (United States)


    ... (exchange rate half-time of less than 10 seconds) and are capable of operating at a temperature in the range... between the isotopes of uranium causes small changes in chemical reaction equilibria that can be used as a..., immiscible liquid phases (aqueous and organic) are countercurrently contacted to give the cascading effect of...

  18. Isotope toolbox turns 10

    DEFF Research Database (Denmark)

    Wenander, Fredrik; Riisager, Karsten


    REX-ISOLDE, one of CERN’s most compact accelerators, has just celebrated its 10th anniversary. The machine’s versatility provides radioactive ion beams across the range of nuclear isotopes.......REX-ISOLDE, one of CERN’s most compact accelerators, has just celebrated its 10th anniversary. The machine’s versatility provides radioactive ion beams across the range of nuclear isotopes....

  19. Isotope research materials

    Energy Technology Data Exchange (ETDEWEB)

    Wilkinson, M. K.; Young, Jr, F. W.


    Preparation of research isotope materials is described. Topics covered include: separation of tritium from aqueous effluents by bipolar electrolysis; stable isotope targets and research materials; radioisotope targets and research materials; preparation of an 241Am metallurgical specimen; reactor dosimeters; ceramic and cermet development; fission-fragment-generating targets of 235UO2; and wire dosimeters for Westinghouse--Bettis. (GHT)

  20. Free Air Respiratory Carbon Isotope Enrichment Experiment (United States)

    Sternberg, L. D.; Greaver, T.; Schaffer, B.; Moreno, T.


    Recycling of respiratory carbon in canopies is difficult to measure. Other than a steady state model, there are currently no direct methods of measuring recycling. Respiratory carbon recycling not only will affect the carbon isotope ratio signature of the canopy, but is also important in partitioning gross photosynthesis and respiration from net ecosystem exchange (NEE). In order to better understand recycling, we empirically derived an integrated measure of recycling in a cover crop (Crotalaria juncea L.) and compared it with that derived by the steady state model. A measured dose of nitrogen gas having CO2 with a high Carbon-13 abundance (41%) was applied at ground level ( ˜10 cm above the soil surface) with a system of hoses in a 10 by 10 m plot embedded in a 30 by 30 m plot. We adjusted the flux rate of this enriched gas weekly to correspond to weekly measurements of soil respiration rates. The gas application rates at ground level were sufficiently low so as to not affect the carbon dynamics of the treatment plot relative to that of a control plot with only nitrogen (no CO2) applied. The isotopic composition of the applied gas, however, was high enough to significantly increase the isotopic composition of respired CO2. Using the carbon isotopic composition of respiration and biomass from the control and treatment plots and mass balance principles we calculated that 45% of the total respired CO2 is recycled by this crop, which compares well with that derived by the steady state model (48%). Partitioning of gross photosynthesis and respiration by isotopic methods usually assumes no recycling. Recycling, however, will have an effect on the isotopic composition of respired CO2. After correcting for the recycling effects on the carbon isotope ratios of respired CO2 leaving the canopy, we calculated that the average gross photosynthesis for this crop was 40.4μ moles/m2s and gross respiration was in the order of 17.8 μ moles/m2s. These values are similar to those

  1. Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis (United States)

    Guttman, Miklos; Wales, Thomas E.; Whittington, Dale; Engen, John R.; Brown, Jeffery M.; Lee, Kelly K.


    Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra.

  2. Transportation of medical isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Nielsen, D.L.


    A Draft Technical Information Document (HNF-1855) is being prepared to evaluate proposed interim tritium and medical isotope production at the Fast Flux Test Facility (FFTF). This assessment examines the potential health and safety impacts of transportation operations associated with the production of medical isotopes. Incident-free and accidental impacts are assessed using bounding source terms for the shipment of nonradiological target materials to the Hanford Site, the shipment of irradiated targets from the FFTF to the 325 Building, and the shipment of medical isotope products from the 325 Building to medical distributors. The health and safety consequences to workers and the public from the incident-free transportation of targets and isotope products would be within acceptable levels. For transportation accidents, risks to works and the public also would be within acceptable levels. This assessment is based on best information available at this time. As the medical isotope program matures, this analysis will be revised, if necessary, to support development of a final revision to the Technical Information Document.

  3. Through a temporal window, we see isotopic signatures

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, Hiroshi [Senshu Univ. of Ishinomaki, Miyagi (Japan)


    Stable isotope composition of bioelements is different between diet and assimilated tissues. Furthermore, the apparent fractionation factors from diet to tissues seem to differ among different tissues: each tissue of an organism reflects the isotope abundances of diet in a different manner. The turnover rate of a tissue, its biochemical composition, its immediate source, and distribution of available resources within an individuals body are among the possible factors that would affect the fractionation factor. Stable isotope composition of an animal tissue or particular biochemical molecules would give a glimpse of the animal itself and its environments only through a particular window, whose width and height are dependent on many factors including animal age. Some tissues that form in a relatively short period during which material exchanges in an animal body can be considered nearly in a steady state would give a clearly defined window frame. One example is feathers of adult birds: the change in the isotope composition from diet to the tissue has been shown stable with time. Tissues formed during a rapid growth of animal body or during a metamorphosis would be an example of another extreme, the window frame being subject to a rapid change with time in its shape. Isotopic knowledge on characteristics of the window is needed to extend the applicability of stable isotope study into researches in ecogeochemistry and environmental chemistry.

  4. VT Telephone Exchange Boundaries (United States)

    Vermont Center for Geographic Information — (Link to Metadata) The UtilityTelecom_EXCHANGE represents Vermont Telephone Exchange boundaries as defined by the VT Public Service Board. The original data was...

  5. Carbon isotope fractionation for cotton genotype selection

    Directory of Open Access Journals (Sweden)

    Giovani Greigh de Brito


    Full Text Available The objective of this work was to evaluate the carbon isotope fractionation as a phenomic facility for cotton selection in contrasting environments and to assess its relationship with yield components. The experiments were carried out in a randomized block design, with four replicates, in the municipalities of Santa Helena de Goiás (SHGO and Montividiu (MONT, in the state of Goiás, Brazil. The analysis of carbon isotope discrimination (Δ was performed in 15 breeding lines and three cultivars. Subsequently, the root growth kinetic and root system architecture from the selected genotypes were determined. In both locations, Δ analyses were suitable to discriminate cotton genotypes. There was a positive correlation between Δ and seed-cotton yield in SHGO, where water deficit was more severe. In this site, the negative correlations found between Δ and fiber percentage indicate an integrative effect of gas exchange on Δ and its association with yield components. As for root robustness and growth kinetic, the GO 05 809 genotype performance contributes to sustain the highest values of Δ found in MONT, where edaphoclimatic conditions were more suitable for cotton. The use of Δ analysis as a phenomic facility can help to select cotton genotypes, in order to obtain plants with higher efficiency for gas exchange and water use.

  6. Isotopes in Condensed Matter

    CERN Document Server

    G Plekhanov, Vladimir


    This book provides a concise introduction to the newly created sub-discipline of solid state physics isotopetronics. The role of isotopes in materials and their properties are describe  in this book. The problem of the enigma of the atomic mass in microphysics is briefly discussed.  The range of the applications of isotopes is wide: from biochemical process in living organisms to modern technical applications in quantum information. Isotopetronics promises to improve nanoelectronic and optoelectronic devices. With numerous illustrations this book is useful to researchers, engineers and graduate students.

  7. Investigating the behaviour of Mg isotopes during the formation of clay minerals (United States)

    Wimpenny, Joshua; Colla, Christopher A.; Yin, Qing-Zhu; Rustad, James R.; Casey, William H.


    We present elemental and isotopic data detailing how the Mg isotope system behaves in natural and experimentally synthesized clay minerals. We show that the bulk Mg isotopic composition (δ26Mg) of a set of natural illite, montmorillonite and kaolinite spans a 2‰ range, and that their isotopic composition depends strongly on a balance between the relative proportions of structural and exchangeable Mg. After acid leaching, these natural clays become relatively enriched in isotopically heavy Mg by between 0.2‰ and 1.6‰. Results of exchange experiments indicate that the Mg that has adsorbed to interlayer spaces and surface charged sites is relatively enriched in isotopically light Mg compared to the residual clay. The isotopic composition of this exchangeable Mg (-1.49‰ to -2.03‰) is characteristic of the isotopic composition of Mg found in many natural waters. Further experiments with an isotopically characterized MgCl2 solution shows that the clay minerals adsorb this exchangeable Mg with little or no isotopic fractionation, although we cannot discount the possibility that the uptake of exchangeable Mg does so with a slight preference for 24Mg. To characterize the behaviour of Mg isotopes during clay mineral formation we synthesized brucite (Mg(OH)2), which we consider to be a good analogue for the incorporation of Mg into the octahedral sheet of Mg-rich clay minerals or into the brucitic layer of clays such as chlorite. In our experiment the brucite mineral becomes enriched in the heavy isotopes of Mg while the corresponding solution is always relatively enriched in isotopically light Mg. The system reaches a steady state after 10 days with a final fractionation factor (αsolid-solution) of 1.0005 at near-neutral pH. This result is consistent with the general consensus that secondary clay minerals preferentially take up isotopically heavy Mg during their formation. However our results also show that exchangeable Mg is an important component within bulk

  8. Oxygen Isotope Measurements of a Rare Murchison Type A CAI and Its Rim (United States)

    Matzel, J. E. P.; Simon, J. I.; Hutcheon, I. D.; Jacobsen, B.; Simon, S. B.; Grossman, L.


    Ca-, Al-rich inclusions (CAIs) from CV chondrites commonly show oxygen isotope heterogeneity among different mineral phases within individual inclusions reflecting the complex history of CAIs in both the solar nebula and/or parent bodies. The degree of isotopic exchange is typically mineral-specific, yielding O-16-rich spinel, hibonite and pyroxene and O-16-depleted melilite and anorthite. Recent work demonstrated large and systematic variations in oxygen isotope composition within the margin and Wark-Lovering rim of an Allende Type A CAI. These variations suggest that some CV CAIs formed from several oxygen reservoirs and may reflect transport between distinct regions of the solar nebula or varying gas composition near the proto-Sun. Oxygen isotope compositions of CAIs from other, less-altered chondrites show less intra-CAI variability and 16O-rich compositions. The record of intra-CAI oxygen isotope variability in CM chondrites, which commonly show evidence for low-temperature aqueous alteration, is less clear, in part because the most common CAIs found in CM chondrites are mineralogically simple (hibonite +/- spinel or spinel +/- pyroxene) and are composed of minerals less susceptible to O-isotopic exchange. No measurements of the oxygen isotope compositions of rims on CAIs in CM chondrites have been reported. Here, we present oxygen isotope data from a rare, Type A CAI from the Murchison meteorite, MUM-1. The data were collected from melilite, hibonite, perovskite and spinel in a traverse into the interior of the CAI and from pyroxene, melilite, anorthite, and spinel in the Wark-Lovering rim. Our objectives were to (1) document any evidence for intra-CAI oxygen isotope variability; (2) determine the isotopic composition of the rim minerals and compare their composition(s) to the CAI interior; and (3) compare the MUM-1 data to oxygen isotope zoning profiles measured from CAIs in other chondrites.

  9. Hydrogen and oxygen in brine shrimp chitin reflect environmental water and dietary isotopic composition (United States)

    Nielson, Kristine E.; Bowen, Gabriel J.


    Hydrogen and oxygen isotope ratios of the common structural biopolymer chitin are a potential recorder of ecological and environmental information, but our understanding of the mechanisms of incorporation of H and O from environmental substrates into chitin is limited. We report the results of a set of experiments in which the isotopic compositions of environmental water and diet were varied independently in order to assess the contribution of these variables to the H and O isotopic composition of Artemia franciscana chitin. Hydrogen isotope ratios of chitin were strongly linearly correlated with both food and water, with approximately 26% of the hydrogen signal reflecting food and approximately 38% reflecting water. Oxygen isotopes were also strongly correlated with the isotopic composition of water and food, but whereas 69% of oxygen in chitin exchanged with environmental water, only 10% was derived from food. We propose that these observations reflect the position-specific, partial exchange of H and O atoms with brine shrimp body water during the processes of digestion and chitin biosynthesis. Comparison of culture experiments with a set of natural samples collected from the Great Salt Lake, UT in 2006 shows that, with some exceptions, oxygen isotope compositions of chitin track those of water, whereas hydrogen isotopes vary inversely with those of lake water. The different behavior of the two isotopic systems can be explained in terms of a dietary shift from allochthonous particulate matter with relatively higher δ 2H values in the early spring to autochthonous particulate matter with significantly lower δ 2H values in the late summer to autumn. These results suggest oxygen in chitin may be a valuable proxy for the oxygen isotopic composition of environmental water, whereas hydrogen isotope values from the same molecule may reveal ecological and biogeochemical changes within lakes.

  10. Ideal Heat Exchange System (United States)

    Tsirlin, A. M.


    The requirements with which a heat exchange system should comply in order that at certain values of the total contact surface and heat load the entropy production in it should be minimal have been determined. It has been shown that this system can serve as a standard for real systems of irreversible heat exchange. We have found the conditions for physical realizability of a heat exchange system in which heat exchange occurs by a law linear with respect to the temperature difference between contacting flows. Analogous conditions are given without deriving for the case of heat exchange by the Fourier law.

  11. Resolution exchange simulation. (United States)

    Lyman, Edward; Ytreberg, F Marty; Zuckerman, Daniel M


    We extend replica-exchange simulation in two ways and apply our approaches to biomolecules. The first generalization permits exchange simulation between models of differing resolution--i.e., between detailed and coarse-grained models. Such "resolution exchange" can be applied to molecular systems or spin systems. The second extension is to "pseudoexchange" simulations, which require little CPU usage for most levels of the exchange ladder and also substantially reduce the need for overlap between levels. Pseudoexchanges can be used in either replica or resolution exchange simulations. We perform efficient, converged simulations of a 50-atom peptide to illustrate the new approaches.

  12. Discoveries of isotopes by fission

    Indian Academy of Sciences (India)

    About 3000 different isotopes have been discovered until now. A recent compilation sum- marized details of the discovery of all isotopes [1–4] including the year, laboratory and country of discovery as well as the production mechanism used to produce the isotopes. Fission, one of the largest contributing production ...

  13. Natural radium and radon tracers to quantify water exchange and movement in reservoirs (United States)

    Smith, Christopher G.; Baskaran, Mark


    Radon and radium isotopes are routinely used to quantify exchange rates between different hydrologic reservoirs. Since their recognition as oceanic tracers in the 1960s, both radon and radium have been used to examine processes such as air-sea exchange, deep oceanic mixing, benthic inputs, and many others. Recently, the application of radon-222 and the radium-quartet (223,224,226,228Ra) as coastal tracers has seen a revelation with the growing interest in coastal groundwater dynamics. The enrichment of these isotopes in benthic fluids including groundwater makes both radium and radon ideal tracers of coastal benthic processes (e.g. submarine groundwater discharge). In this chapter we review traditional and recent advances in the application of radon and radium isotopes to understand mixing and exchange between various hydrologic reservoirs, specifically: (1) atmosphere and ocean, (2) deep and shallow oceanic water masses, (3) coastal groundwater/benthic pore waters and surface ocean, and (4) aquifer-lakes. While the isotopes themselves and their distribution in the environment provide qualitative information about the exchange processes, it is mixing/exchange and transport models for these isotopes that provide specific quantitative information about these processes. Brief introductions of these models and mixing parameters are provided for both historical and more recent studies.

  14. Global Cr-isotope distributions in surface seawater and incorporation of Cr isotopes into carbonate shells


    Paulukat, Cora Stefanie; Frei, Robert; Vögelin, Andrea Regula; Samankassou, Elias


    In this study we present the Cr-isotope composition of surface seawater from several locations worldwide. In addition to the samples from the oceans (Atlantic Ocean, Pacific Ocean, Southern Ocean and Artic Ocean) we analysed water samples from areas with a more limited water exchange (Mediterranean Sea, Baltic Sea, Øresund and Kattegat). The long residence time of Cr (7,000 to 40,000 years) [1,2,3] relative to the ocean mixing time (1,000 to 2,000 years) [4] could lead to the expectation that...

  15. Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane

    Energy Technology Data Exchange (ETDEWEB)

    Jewett, J.R., Fluor Daniel Hanford


    Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing all hydrogen isotopes mixed with the stable helium isotopes. The application of this mass spectrometer were demonstrated by analyzing mixtures of deuterated methanes. In addition, it was employed to study the radiochemical Witzbach exchange reaction between tritium and methanes. A laser-Raman spectrometer was designed for analysis of tritium-containing gases and was built from individual components. A tritium-compatible, metal-sealed Raman cuvette having windows with good optical properties and additional means for measuring the stray light was first used successfully in this work. The Raman spectra of the hydrogen isotopes were acquired in the pure rotation mode and in the rotation-vibration mode and were used for on. The deuterated methanes were measured by Raman spectroscopy, the wavenumbers determined were assigned to the corresponding vibrations, and the wavenumbers for the rotational fine-structure were summarized in tables. The fundamental Vibrations of the deuterated methanes produced Witzbach reactions were detected and assigned. The fundamental vibrations of the molecules were obtained with Raman spectroscopy for the first time in this work. The @-Raman spectrometer assembled is well suited for the analysis of tritium- containing gases and is practical in combination with mass spectrometry using an Omegatron, for studying gases used in fusion.

  16. Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence (United States)

    Bullen, Thomas D.; Chadwick, Oliver A.


    Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils

  17. Hydrogen Isotopes in Amino Acids and Soils Offer New Potential to Study Complex Processes (United States)

    Fogel, M. L.; Newsome, S. D.; Williams, E. K.; Bradley, C. J.; Griffin, P.; Nakamoto, B. J.


    Hydrogen isotopes have been analyzed extensively in the earth and biogeosciences to trace water through various environmental systems. The majority of the measurements have been made on water in rocks and minerals (inorganic) or non-exchangeable H in lipids (organic), important biomarkers that represent a small fraction of the organic molecules synthesized by living organisms. Our lab has been investigating hydrogen isotopes in amino acids and complex soil organic matter, which have traditionally been thought to be too complex to interpret owing to complications from potentially exchangeable hydrogen. For the amino acids, we show how hydrogen in amino acids originates from two sources, food and water, and demonstrate that hydrogen isotopes can be routed directly between organisms. Amino acid hydrogen isotopes may unravel cycling in extremophiles in order to discover novel biochemical pathways central to the organism. For soil organic matter, recent approaches to understanding the origin of soil organic matter are pointing towards root exudates along with microbial biomass as the source, rather than aboveground leaf litter. Having an isotope tracer in very complex, potentially exchangeable organic matter can be handled with careful experimentation. Although no new instrumentation is being used per se, extension of classes of organic matter to isotope measurements has potential to open up new doors for understanding organic matter cycling on earth and in planetary materials.

  18. Zinc isotope fractionation during adsorption on calcite (United States)

    Dong, S.; Wasylenki, L. E.


    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (δ66/64Zn from -0.1 to 0.5‰), but modern ferromanganese crusts (δ66/64Zn from 0.5 to 1.2‰), as well as carbonates (δ66/64Zn from 0.3 to 1.4‰), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with Δ68/66Zncalcite-solution of approximately 0.3‰. The variation of Δ68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a

  19. Uranium Isotope Systematic in Saanich Inlet (United States)

    Amini, M.; Holmden, C.; Francois, R.


    As a redox-sensitive element Uranium has become the focus of stable isotope studies. Based on the nuclear field shift effect [1], U isotope fractionation was predicted as a function of U(IV)-U(VI) exchange reactions with the insoluble reduced U(IV) species being heavier than the soluble oxidized U(VI) species. Recently, variations in 238U/235U were reported in low temperature aqueous and sedimentary environments [2,3] indicating that U deposited in well-oxygenated environments is characterized by light isotopic composition, whereas suboxic and anoxic deposits tend towards a heavy isotopic signature. U isotope fractionation has been hence proposed as a promising new paleo-redox proxy. In order to test the efficacy of U isotope fractionation to record oxidation states in marine systems, we are investigating sediment samples deposited over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. We have also made δ238U measurements for water samples from above and below the redoxcline. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10 permil (2sd). Eleven analyses of seawater performed over the course of this work yielded δ238U of -0.41±0.07 permil (2sd). No clear difference in δ238U values has been found, thus far, in water samples collected at 10m (O2~380μM) and 200m (O2~1μM) depths from a single location in the middle of the inlet. The mean of two measurements of the deepwater sample yielded -0.43±0.01 permil (2sd). Two measurements of the shallow water sample yielded a mean value of -0.38±0.03 permil (2sd). The δ238U values for HF-HNO3 digestions of the organic rich sediments, one taken in the middle of the basin (3.11% organic carbon) below seasonally anoxic bottom waters (-0.22±0.01 permil, n=2), and the other taken from the sill (1

  20. A general procedure for isotopic (deuterium) labelling of non-steroidal antiinflammatory 2-arylpropionic acids

    Energy Technology Data Exchange (ETDEWEB)

    Castell, J.V. (Valencia Univ. Hospital (Spain). Centro de Investigacion); Martinez, L.A. (Valencia Univ. Hospital (Spain). Centro de Investigacion Universidad Politecnica de Valencia (Spain). Dept. de Quimica); Miranda, M.A.; Tarrega, Pilar (Universidad Politecnica de Valencia (Spain). Dept. de Quimica)


    Alkaline treatment of nonsteroidal antiinflammatory 2-arylpropionic acids in deuterium oxide led in all cases to isotopic exchange of the proton located at the [alpha]-position of the side chain. Monodeuteration was observed in the case of carprofen, ibuprofen, ketoprofen, fenoprofen, flurbiprofen and naproxen. Additional exchange of one or two protons of the heterocyclic ring occurred in indoprofen, suprofen and tiaprofenic acid. The isotopic labelling survived under the conditions required to perform in vitro photoallergic studies (photolysis in non-deuterated aqueous media). (Author).

  1. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions (United States)

    Nomura, Masao; Kudo, Takashi; Adachi, Atsuhiko; Aida, Masao; Fujii, Yasuhiko


    Mass independent fractionation (MIF) has been a very interesting topic in the field of inorganic isotope chemistry, in particular, geo- and cosmo- chemistry. In the present work, we studied the isotope fractionation of Ni(II) and Pb(II) ions in complex formation with chelating reagent EDTA. To obtain clear results on the mass dependence of the isotope fractionation, we have conducted long-distance ion exchange chromatography of Ni(II) and Pb(II), using chelate complex reagent EDTA. The results apparently show that the isotope fractionation in Ni complex formation system is governed by the mass dependent rule. On the other hand the isotope fractionation in the Pb complex system is governed by the mass independent rule or the nuclear volume effect.

  2. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)


    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  3. Stable isotopes in tree rings: towards a mechanistic understanding of isotope fractionation and mixing processes from the leaves to the wood. (United States)

    Gessler, Arthur; Ferrio, Juan Pedro; Hommel, Robert; Treydte, Kerstin; Werner, Roland A; Monson, Russell K


    The mechanistic understanding of isotope fractionation processes is increasing but we still lack detailed knowledge of the processes that determine the isotopic composition of the tree-ring archive over the long term. Especially with regard to the path from leaf photosynthate production to wood formation, post-assimilation fractionations/processes might cause at least a partial decoupling between the leaf isotope signals that record processes such as stomatal conductance, transpiration and photosynthesis, and the wood or cellulose signals that are stored in the paleophysiological record. In this review, we start from the rather well understood processes at the leaf level such as photosynthetic carbon isotope fractionation, leaf water evaporative isotope enrichment and the issue of the isotopic composition of inorganic sources (CO2 and H2O), though we focus on the less explored 'downstream' processes related to metabolism and transport. We further summarize the roles of cellulose and lignin as important chemical constituents of wood, and the processes that determine the transfer of photosynthate (sucrose) and associated isotopic signals to wood production. We cover the broad topics of post-carboxylation carbon isotope fractionation and of the exchange of organic oxygen with water within the tree. In two case studies, we assess the transfer of carbon and oxygen isotopic signals from leaves to tree rings. Finally we address the issue of different temporal scales and link isotope fractionation at the shorter time scale for processes in the leaf to the isotopic ratio as recorded across longer time scales of the tree-ring archive. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email:

  4. Stable isotope and fluid inclusion studies of metamorphic fluid flow in an evolving tectonic system

    Energy Technology Data Exchange (ETDEWEB)

    Wesolowski, D.; Cole, D.R.; Drummond, M.S.; Stakes, D.R.


    The Southern Appalachian borehole represents a unique opportunity to couple O-H-C-S isotope and fluid inclusion studies with textures, mineralogies, and chemical compositions in order to assess the role of fluids in metamorphism, deformation, element migration, and heat transfer throughout the evolution of a complex orogen. Studies which focus on hydrothermal veins, felsic/mafic intrusives and juxtaposed but chemically and isotopically distinct lithologies such as volcanics/-clastics and silicates/carbonates will be particularly informative. That large-scale metamorphic fluid flow has occurred in the Southern Appalachians is evidenced by devolatilization of enormous masses of rock during prograde metamorphism and extensive revolatilization, along major shear zones exhibiting retrograde assemblages. The authors own textural, chemical and oxygen isotope studies of granitoids and their host rocks in Northern Alabama document substantial isotopic, major and trace element (e.g. U, Th, Pb, Rb, and Sr) redistribution over thousands of cubic kilometers via exchange with infiltrating metamorphic fluids. Even chemically and mineralogically unaltered granites in the area have been isotopically enriched, perhaps reflecting differing chemical and isotopic exchange capacities of the fluid/rock system. These observations suggest that the chemical and isotopic effects of metamorphic fluid flow must be quantified in order to determine the origins of sedimentary and igneous rocks based on their geochemical signatures and age dates and to evaluate the role of fluids in the tectonic evolution of the proposed study area.

  5. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1) (United States)

    Jahn, A.; Lindsay, K.; Giraud, X.; Gruber, N.; Otto-Bliesner, B. L.; Liu, Z.; Brady, E. C.


    Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air-sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  6. Carbon isotopes in the ocean model of the Community Earth System Model (CESM1

    Directory of Open Access Journals (Sweden)

    A. Jahn


    Full Text Available Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM, containing the cycling of the stable isotope 13C and the radioactive isotope 14C. We implemented the 14C tracer in two ways: in the "abiotic" case, the 14C tracer is only subject to air–sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14C additionally follows the 13C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14C bomb uptake and the 13C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

  7. Adaptively Compressed Exchange Operator

    CERN Document Server

    Lin, Lin


    The Fock exchange operator plays a central role in modern quantum chemistry. The large computational cost associated with the Fock exchange operator hinders Hartree-Fock calculations and Kohn-Sham density functional theory calculations with hybrid exchange-correlation functionals, even for systems consisting of hundreds of atoms. We develop the adaptively compressed exchange operator (ACE) formulation, which greatly reduces the computational cost associated with the Fock exchange operator without loss of accuracy. The ACE formulation does not depend on the size of the band gap, and thus can be applied to insulating, semiconducting as well as metallic systems. In an iterative framework for solving Hartree-Fock-like systems, the ACE formulation only requires moderate modification of the code, and can be potentially beneficial for all electronic structure software packages involving exchange calculations. Numerical results indicate that the ACE formulation can become advantageous even for small systems with tens...

  8. Laser Processed Heat Exchangers (United States)

    Hansen, Scott


    The Laser Processed Heat Exchanger project will investigate the use of laser processed surfaces to reduce mass and volume in liquid/liquid heat exchangers as well as the replacement of the harmful and problematic coatings of the Condensing Heat Exchangers (CHX). For this project, two scale unit test articles will be designed, manufactured, and tested. These two units are a high efficiency liquid/liquid HX and a high reliability CHX.

  9. Microsoft Exchange 2013 cookbook

    CERN Document Server

    Van Horenbeeck, Michael


    This book is a practical, hands-on guide that provides the reader with a number of clear, step-by-step exercises.""Microsoft Exchange 2013 Cookbook"" is targeted at network administrators who deal with the Exchange server in their day-to-day jobs. It assumes you have some practical experience with previous versions of Exchange (although this is not a requirement), without being a subject matter expert.

  10. Hafnium at subduction zones: isotopic budget of input and output fluxes; L'hafnium dans les zones de subduction: bilan isotopique des flux entrant et sortant

    Energy Technology Data Exchange (ETDEWEB)

    Marini, J.Ch


    Subduction zones are the primary regions of mass exchanges between continental crust and mantle of Earth through sediment subduction toward the earth's mantle and by supply of mantellic magmas to volcanic arcs. We analyze these mass exchanges using Hafnium and Neodymium isotopes. At the Izu-Mariana subduction zone, subducting sediments have Hf and Nd isotopes equivalent to Pacific seawater. Altered oceanic crust has Hf and Nd isotopic compositions equivalent to the isotopic budget of unaltered Pacific oceanic crust. At Luzon and Java subduction zones, arc lavas present Hf isotopic ratios highly radiogenic in comparison to their Nd isotopic ratios. Such compositions of the Luzon and Java arc lavas are controlled by a contamination of their sources by the subducted oceanic sediments. (author)


    Directory of Open Access Journals (Sweden)

    Riccardo Petrini


    Full Text Available O, H, B and Sr isotopes were identified from surface-waters, ground-waters and waters percolating in soils at the Pialassa Baiona lagoon and nearby inland areas. The preliminary data demonstrate the occurrence of both conservative mixtures between seawater and freshwaters and cation exchange at the salt/fresh water interface during the intrusion. The O and H isotopes indicate that the freshwater component in the binary mixing had the isotopic features of the rainwater from Apennine catchments. Coupled O-H-B isotopes also show that the major contribution of the moving seawater was confined to the deeper aquifers and some of the soil waters. The Sr isotopes highlight the role of cation exchanges when seawater flushes freshwater aquifers, and allow the recognition of the different components of the solute. Deviations from these processes as revealed by B isotopes are interpreted as the evidence of possible anthropogenic inputs.

  12. Lattice Boltzmann simulation of water isotope fractionation during ice crystal growth in clouds (United States)

    Lu, Guoping; DePaolo, Donald J.


    We describe a lattice Boltzmann (LB) method for simulating water isotope fractionation during diffusion-limited ice crystal growth by vapor deposition from water-oversaturated air. These conditions apply to the growth of snow crystals in clouds where the vapor composition is controlled by the presence of both ice crystals and water droplets. Modeling of water condensation with the LB method has the advantage of allowing concentration fields to evolve based on local conditions so that the controls on grain shapes of the condensed phase can be studied simultaneously with the controls on isotopic composition and growth rate. Water isotope fractionation during snow crystal growth involves kinetic effects due to diffusion of water vapor in air, which requires careful consideration of the boundary conditions at the ice-vapor interface. The boundary condition is relatively simple for water isotopes because the molecular exchange rate for water at the interface is large compared to the crystal growth rate. Our results for the bulk crystal isotopic composition are consistent with simpler models using analytical solutions for radial geometry. However, the model results are sufficiently different for oxygen isotopes that they could affect the interpretation of D-excess values of snow and ice. The extent of vapor oversaturation plays a major role in determining the water isotope fractionation as well as the degree of dendritic growth. Departures from isotopic equilibrium increase at colder temperatures as diffusivity decreases. Dendritic crystals are isotopically heterogeneous. Isotopic variations within individual snow crystals could yield information on the microphysics of ice condensation as well as on the accommodation or sticking coefficient of water associated with vapor deposition. Our results are ultimately a first step in implementing LB models for kinetically controlled condensation or precipitation reactions, but needs to be extended also to cases where the

  13. Microtube strip heat exchanger (United States)

    Doty, F. D.


    During the last quarter, Doty Scientific, Inc. (DSI) continued to make progress on the microtube strip (MTS) heat exchanger. The DSI completed a heat exchanger stress analysis of the ten-module heat exchanger bank; and performed a shell-side flow inhomogeneity analysis of the three-module heat exchanger bank. The company produced 50 tubestrips using an in-house CNC milling machine and began pressing them onto tube arrays. The DSI revised some of the tooling required to encapsulate a tube array and press tubestrips into the array to improve some of the prototype tooling.

  14. Isotope dilution gamma spectrometry for Pu using low energy photons

    Energy Technology Data Exchange (ETDEWEB)

    Paul, S.; Sarkar, A.; Alamelu, D.; Shah, R.V.; Aggarwal, S.K. [Bhabha Atomic Reseach Centre, Mumbai (India). Fuel Chemistry Div.


    Isotope dilution gamma spectrometry (IDGS) for determination of the Pu concentration, using high resolution gamma-ray spectrometry (HRGS) in the 40-150 keV energy range, is developed and described. The methodology involves purification of Pu by an anion exchange procedure, followed by the determination of Pu isotopic composition using HRGS. For isotope dilution, a pre-calibrated power reactor grade Pu ({proportional_to} 70 at. % {sup 239}Pu) solution from an Indian PHWR was used as a spike for research reactor grade Pu ({proportional_to} 95 at. % {sup 239}Pu) samples and vice versa. Changes in {sup 240}Pu/{sup 239}Pu (45.24 keV/51.62 keV) and {sup 241}Pu/{sup 239}Pu (148.57 keV/129.29 keV) activity ratios in the spiked samples were determined by gamma spectrometry. Using the atom ratios calculated from the measured activity ratios, the concentration of Pu in the sample was calculated using two different efficiency calibration methods. The isotopic composition and concentration of Pu samples both from power reactor and research reactor grade agreed well with the values obtained by isotope dilution-thermal ionization mass spectrometry. The present method also shows the superiority of using the {sup 240}Pu/{sup 239}Pu atom ratio against the {sup 241}Pu/{sup 239}Pu atom ratio in IDGS with respect to the accuracy and precision. (orig.)

  15. Quantum instanton evaluation of the kinetic isotope effects

    Energy Technology Data Exchange (ETDEWEB)

    Vanicek, Jiri; Miller, William H.; Castillo, Jesus F.; Aoiz, F.Javier


    A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum instanton approximation for the rate constant and on the path integral Metropolis Monte-Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method is more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single reaction path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte-Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H+H{sub 2} {yields} H{sub 2}+H. In all seven test cases, for temperatures between 250 K and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than {approx}10%.

  16. New Isotope 263Hs

    Energy Technology Data Exchange (ETDEWEB)

    Dragojevic, I.; Gregorich, K.E.; Dullmann, Ch.E.; Dvorak, J.; Ellison, P.A.; Gates, J.M.; Nelson, S.L.; Stavsetra, L.; Nitsche, H.


    A new isotope of Hs was produced in the reaction 208Pb(56Fe, n)263Hs at the 88-Inch Cyclotron of the Lawrence Berkeley National Laboratory. Six genetically correlated nuclear decay chains have been observed and assigned to the new isotope 263Hs. The measured cross section was 21+13-8.4 pb at 276.4 MeV lab-frame center-of-target beam energy. 263Hs decays with a half-life of 0.74 ms by alpha-decay and the measured alpha-particle energies are 10.57 +- 0.06, 10.72 +- 0.06, and 10.89 +- 0.06 MeV. The experimental cross section is compared to a theoretical prediction based on the Fusion by Diffusion model [W. J. Swiatecki et al., Phys. Rev. C 71, 014602 (2005)].


    Energy Technology Data Exchange (ETDEWEB)



    The use of isotope labels has had a fundamentally important role in the determination of mechanisms of homogeneously catalyzed reactions. Mechanistic data is valuable since it can assist in the design and rational improvement of homogeneous catalysts. There are several ways to use isotopes in mechanistic chemistry. Isotopes can be introduced into controlled experiments and followed where they go or don't go; in this way, Libby, Calvin, Taube and others used isotopes to elucidate mechanistic pathways for very different, yet important chemistries. Another important isotope method is the study of kinetic isotope effects (KIEs) and equilibrium isotope effect (EIEs). Here the mere observation of where a label winds up is no longer enough - what matters is how much slower (or faster) a labeled molecule reacts than the unlabeled material. The most careti studies essentially involve the measurement of isotope fractionation between a reference ground state and the transition state. Thus kinetic isotope effects provide unique data unavailable from other methods, since information about the transition state of a reaction is obtained. Because getting an experimental glimpse of transition states is really tantamount to understanding catalysis, kinetic isotope effects are very powerful.

  18. Gallium isotope fractionation during Ga adsorption on calcite and goethite (United States)

    Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques


    Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its

  19. GRUNDTVIG in transnational exchange

    DEFF Research Database (Denmark)

    Grundtvig in transnational exchange is the report from the seminar in december 2015 in cooperation with University of Cape Town and University of Hamburg.......Grundtvig in transnational exchange is the report from the seminar in december 2015 in cooperation with University of Cape Town and University of Hamburg....

  20. Optimization of Heat Exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Ivan Catton


    The objective of this research is to develop tools to design and optimize heat exchangers (HE) and compact heat exchangers (CHE) for intermediate loop heat transport systems found in the very high temperature reator (VHTR) and other Generation IV designs by addressing heat transfer surface augmentation and conjugate modeling. To optimize heat exchanger, a fast running model must be created that will allow for multiple designs to be compared quickly. To model a heat exchanger, volume averaging theory, VAT, is used. VAT allows for the conservation of mass, momentum and energy to be solved for point by point in a 3 dimensional computer model of a heat exchanger. The end product of this project is a computer code that can predict an optimal configuration for a heat exchanger given only a few constraints (input fluids, size, cost, etc.). As VAT computer code can be used to model characteristics )pumping power, temperatures, and cost) of heat exchangers more quickly than traditional CFD or experiment, optimization of every geometric parameter simultaneously can be made. Using design of experiment, DOE and genetric algorithms, GE, to optimize the results of the computer code will improve heat exchanger disign.

  1. Education and Industry Exchange (United States)

    Webb, Gerald A.


    Through an exchange plan a school representative worked at the personnel counter of a local company, and a supervisor from that company worked with counselors, faculty, administrators, and students from the local school. The exchange of ideas and insights were of benefit to the school and the company. (KP)

  2. Therapeutic use of radioactive isotopes

    CERN Multimedia

    Caroline Duc


    In December, researchers from ISOLDE-CERN, the Paul Scherrer Institute (PSI) and the Institut Laue-Langevin (ILL) published the results of an in vivo study which successfully proved the effectiveness of four terbium isotopes for diagnosing and treating cancerous tumours.   Four terbium isotopes suitable for clinical purposes. “ISOLDE is the only installation capable of supplying terbium isotopes of such purity and intensity in the case of three out of the four types used in this study,” explains Karl Johnson, a physicist at ISOLDE.  “Producing over a thousand different isotopes, our equipment offers the widest choice of isotopes in the world!” Initially intended for fundamental physics research, ISOLDE has diversified its activities over time to invest in various projects in the materials science, biochemistry and nuclear medicine fields. The proof-of-concept study has confirmed that the four terbium isotopes 149Tb, 152Tb, 155Tb produ...

  3. Do foraminifera accurately record seawater neodymium isotope composition? (United States)

    Scrivner, Adam; Skinner, Luke; Vance, Derek


    , Earth Planet. Sci. Lett. 265, 571-587. Lacan, F., and Jeandel, C., 2005a. Neodymium isotopes as a new tool for quantifying exchange fluxes at the continent-ocean interface, Earth Planet. Sci. Lett. 232, 245-257. Piepgras, D.J., and Wasserburg, G.J., 1987. Rare earth element transport in the western North Atlantic inferred from Nd isotopic observations. Geochim. Cosmochim. Acta 51, 1257-1271. Rutberg, R.L., Hemming, S.R., and Goldstein, S.L., 2000. Reduced North Atlantic deep water flux to the glacial southern ocean inferred from neodymium isotope ratios. Nature 405, 935-938. Tachikawa, K., Roy-Barman, M., Michard, A., Thouron, D., Yeghicheyan, D., and Jeandel, C., 2004. Neodymium isotopes in the Mediterranean Sea: comparison between seawater and sediment signals. Geochim. Cosmochim. Acta 68, 3095-3106.

  4. Non-destructive measurement of carbonic anhydrase activity and the oxygen isotope composition of soil water (United States)

    Jones, Sam; Sauze, Joana; Ogée, Jérôme; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa


    Carbonic anhydrases are a group of metalloenzymes that catalyse the hydration of aqueous carbon dioxide (CO2). The expression of carbonic anhydrase by bacteria, archaea and eukarya has been linked to a variety of important biological processes including pH regulation, substrate supply and biomineralisation. As oxygen isotopes are exchanged between CO2 and water during hydration, the presence of carbonic anhydrase in plants and soil organisms also influences the oxygen isotope budget of atmospheric CO2. Leaf and soil water pools have distinct oxygen isotope compositions, owing to differences in pool sizes and evaporation rates, which are imparted on CO2during hydration. These differences in the isotopic signature of CO2 interacting with leaves and soil can be used to partition the contribution of photosynthesis and soil respiration to net terrestrial CO2 exchange. However, this relies on our knowledge of soil carbonic anhydrase activity and currently, the prevalence and function of these enzymes in soils is poorly understood. Isotopic approaches used to estimate soil carbonic anhydrase activity typically involve the inversion of models describing the oxygen isotope composition of CO2 fluxes to solve for the apparent, potentially catalysed, rate of oxygen exchange during hydration. This requires information about the composition of CO2 in isotopic equilibrium with soil water obtained from destructive, depth-resolved soil water sampling. This can represent a significant challenge in data collection given the considerable potential for spatial and temporal variability in the isotopic composition of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by constraining carbonic anhydrase activity and the composition of soil water in isotopic equilibrium with CO2 by solving simultaneously the mass balance for two soil CO2 steady states differing only in the

  5. Combined simulation of carbon and water isotopes in a global ocean model (United States)

    Paul, André; Krandick, Annegret; Gebbie, Jake; Marchal, Olivier; Dutkiewicz, Stephanie; Losch, Martin; Kurahashi-Nakamura, Takasumi; Tharammal, Thejna


    Carbon and water isotopes are included as passive tracers in the MIT general circulation model (MITgcm). The implementation of the carbon isotopes is based on the existing MITgcm carbon cycle component and involves the fractionation processes during photosynthesis and air-sea gas exchange. Special care is given to the use of a real freshwater flux boundary condition in conjunction with the nonlinear free surface of the ocean model. The isotopic content of precipitation and water vapor is obtained from an atmospheric GCM (the NCAR CAM3) and mapped onto the MITgcm grid system, but the kinetic fractionation during evaporation is treated explicitly in the ocean model. In a number of simulations, we test the sensitivity of the carbon isotope distributions to the formulation of fractionation during photosynthesis and compare the results to modern observations of δ13C and Δ14C from GEOSECS, WOCE and CLIVAR. Similarly, we compare the resulting distribution of oxygen isotopes to modern δ18O data from the NASA GISS Global Seawater Oxygen-18 Database. The overall agreement is good, but there are discrepancies in the carbon isotope composition of the surface water and the oxygen isotope composition of the intermediate and deep waters. The combined simulation of carbon and water isotopes in a global ocean model will provide a framework for studying present and past states of ocean circulation such as postulated from deep-sea sediment records.

  6. Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations (United States)

    Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.


    Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic (δ13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

  7. Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides (United States)

    Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio


    The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope

  8. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.


    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

  9. Divergent biochemical fractionation, not convergent temperature, explains cellulose oxygen isotope enrichment across latitudes. (United States)

    Sternberg, Leonel; Ellsworth, Patricia Fernandes Vendramini


    Recent findings based on the oxygen isotope ratios of tree trunk cellulose indicate that the temperature of biomass production in biomes ranging from boreal to subtropical forests converge to an average leaf temperature of 21.4°C. The above conclusion has been drawn under the assumption that biochemically related isotopic fractionations during cellulose synthesis are not affected by temperature. Here we test the above assumption by heterotrophically generating cellulose at different temperatures and measuring the proportion of carbohydrate oxygen that exchange with water during cellulose synthesis and the average biochemical fractionation associated with this exchange. We observed no variation in the proportion of oxygen that exchange with different temperatures, which averaged 0.42 as it has been observed in other studies. On the other hand, the biochemical oxygen isotope fractionation during cellulose synthesis is affected by temperature and can be described by a 2(nd) order polynomial equation. The biochemical fractionation changes little between temperatures of 20 and 30°C averaging 26‰ but increases at lower temperatures to values of 31‰. This temperature sensitive biochemical fractionation explains the pattern of cellulose oxygen isotope ratios of aquatic plants encompassing several latitudes. The observed temperature sensitive biochemical fractionation also indicates that divergent biochemical fractionation and not convergent leaf temperature explains the increase in oxygen isotope enrichment of cellulose across several biomes.

  10. Chromatographic hydrogen isotope separation (United States)

    Aldridge, Frederick T.


    Intermetallic compounds with the CaCu.sub.5 type of crystal structure, particularly LaNiCo.sub.4 and CaNi.sub.5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors.

  11. Cold regions isotope applications

    Energy Technology Data Exchange (ETDEWEB)

    Perrigo, L.D.; Divine, T.E.


    Pacific Northwest Laboratories (PNL) started the Cold Regions Isotope Applications Program in FY-1975 to identify special conditions in the Arctic and similar geographic areas (Cold Regions) where radioisotope power, heater, or sterilization systems would be desirable and economically viable. Significant progress was made in the first year of this program and all objectives for this initial 12-month period were achieved. The major conclusions and recommendations resulting for this effort are described below. The areas of interest covered include: radiosterilization of sewage; heating of septic tanks; and radioisotope thermoelectric generators as power sources for meteorological instruments and navigational aids. (TFD)


    Clewett, G.H.; Lee, DeW.A.


    A new method is described for isotopic enrichment of uranium. It has been found that when an aqueous acidic solution of ionic tetravalent uraniunn is contacted with chelate complexed tetravalent uranium, the U/sup 238/ preferentially concentrates in the complexed phase while U/sup 235/ concentrates in the ionic phase. The effect is enhanced when the chelate compound is water insoluble and is dissolved in a water-immiscible organic solvent. Cupferron is one of a number of sultable complexing agents, and chloroform is a suitable organic solvent.

  13. Heat exchanger design handbook

    CERN Document Server

    Thulukkanam, Kuppan


    Completely revised and updated to reflect current advances in heat exchanger technology, Heat Exchanger Design Handbook, Second Edition includes enhanced figures and thermal effectiveness charts, tables, new chapter, and additional topics--all while keeping the qualities that made the first edition a centerpiece of information for practicing engineers, research, engineers, academicians, designers, and manufacturers involved in heat exchange between two or more fluids.See What's New in the Second Edition: Updated information on pressure vessel codes, manufacturer's association standards A new c

  14. Anion exchange membrane (United States)

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


    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.

  15. Molecular Exchange Dynamics in Block Copolymer Micelles (United States)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy


    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  16. Tracing carbonate-silicate interaction during subduction using magnesium and oxygen isotopes. (United States)

    Wang, Shui-Jiong; Teng, Fang-Zhen; Li, Shu-Guang


    Subduction of carbonates and carbonated eclogites into the mantle plays an important role in transporting carbon into deep Earth. However, to what degree isotopic exchanges occur between carbonate and silicate during subduction remains unclear. Here we report Mg and O isotopic compositions for ultrahigh pressure metamorphic marbles and enclosed carbonated eclogites from China. These marbles include both calcite- and dolomite-rich examples and display similar O but distinct Mg isotopic signatures to their protoliths. Their δ(26)Mg values vary from -2.508 to -0.531‰, and negatively correlate with MgO/CaO ratios, unforeseen in sedimentary carbonates. Carbonated eclogites have extremely heavy δ(18)O (up to +21.1‰) and light δ(26)Mg values (down to -1.928‰ in garnet and -0.980‰ in pyroxene) compared with their protoliths. These unique Mg-O isotopic characteristics reflect differential isotopic exchange between eclogites and carbonates during subduction, making coupled Mg and O isotopic studies potential tools for tracing deep carbon recycling.

  17. The use of exchangeable nuclei to observe enantiomers through deuterium NMR in chiral liquid crystalline solvents. (United States)

    Palomino, Martina; Khudr, Hussein; Courtieu, Jacques; Merlet, Denis; Meddour, Abdelkrim


    It is demonstrated that (2)H NMR in chiral liquid crystalline solvents can be used to measure enantiomeric excesses using exchangeable deuterons in alcohols. This is performed in a trivial way at low temperature (260-270 K) where a slow exchange regime was reached. Among the various alcohols used to explore the possibilities of this technique, an unusually large isotopic effect on molecular orientation between two isotopomers has been observed. Copyright © 2012 John Wiley & Sons, Ltd.

  18. What controls the isotopic composition of Greenland surface snow?

    Directory of Open Access Journals (Sweden)

    H. C. Steen-Larsen


    Full Text Available Water stable isotopes in Greenland ice core data provide key paleoclimatic information, and have been compared with precipitation isotopic composition simulated by isotopically enabled atmospheric models. However, post-depositional processes linked with snow metamorphism remain poorly documented. For this purpose, monitoring of the isotopic composition (δ18O, δD of near-surface water vapor, precipitation and samples of the top (0.5 cm snow surface has been conducted during two summers (2011–2012 at NEEM, NW Greenland. The samples also include a subset of 17O-excess measurements over 4 days, and the measurements span the 2012 Greenland heat wave. Our observations are consistent with calculations assuming isotopic equilibrium between surface snow and water vapor. We observe a strong correlation between near-surface vapor δ18O and air temperature (0.85 ± 0.11‰ °C−1 (R = 0.76 for 2012. The correlation with air temperature is not observed in precipitation data or surface snow data. Deuterium excess (d-excess is strongly anti-correlated with δ18O with a stronger slope for vapor than for precipitation and snow surface data. During nine 1–5-day periods between precipitation events, our data demonstrate parallel changes of δ18O and d-excess in surface snow and near-surface vapor. The changes in δ18O of the vapor are similar or larger than those of the snow δ18O. It is estimated using the CROCUS snow model that 6 to 20% of the surface snow mass is exchanged with the atmosphere. In our data, the sign of surface snow isotopic changes is not related to the sign or magnitude of sublimation or deposition. Comparisons with atmospheric models show that day-to-day variations in near-surface vapor isotopic composition are driven by synoptic variations and changes in air mass trajectories and distillation histories. We suggest that, in between precipitation events, changes in the surface snow isotopic composition are driven by these changes in near

  19. Data Exchange Inventory System (DEXI) (United States)

    Social Security Administration — Enterprise tool used to identify data exchanges occurring between SSA and our trading partners. DEXI contains information on both incoming and outgoing exchanges and...

  20. Method of separating boron isotopes (United States)

    Jensen, Reed J.; Thorne, James M.; Cluff, Coran L.; Hayes, John K.


    A method of boron isotope enrichment involving the isotope preferential photolysis of (2-chloroethenyl)dichloroborane as the feed material. The photolysis can readily be achieved with CO.sub.2 laser radiation and using fluences significantly below those required to dissociate BCl.sub.3.

  1. Microplate Heat Exchanger Project (United States)

    National Aeronautics and Space Administration — We propose a microplate heat exchanger for cryogenic cooling systems used for continuous flow distributed cooling systems, large focal plane arrays, multiple cooling...

  2. Exchange Risk Management Policy

    CERN Document Server


    At the Finance Committee of March 2005, following a comment by the CERN Audit Committee, the Chairman invited the Management to prepare a document on exchange risk management policy. The Finance Committee is invited to take note of this document.

  3. HUD Exchange Grantee Database (United States)

    Department of Housing and Urban Development — The About Grantees section of the HUD Exchange brings up contact information, reports, award, jurisdiction, and location data for organizations that receive HUD...

  4. NASA Earth Exchange (NEX) (United States)

    National Aeronautics and Space Administration — The NASA Earth Exchange (NEX) represents a new platform for the Earth science community that provides a mechanism for scientific collaboration and knowledge sharing....

  5. Anion exchange polymer electrolytes (United States)

    Kim, Yu Seung; Kim, Dae Sik


    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.

  6. Concurrent reduction and distillation: an improved technique for the recovery and chemical refinement of the isotopes of cadmium and zinc

    Energy Technology Data Exchange (ETDEWEB)

    Caudill, H.H.; McBride, L.E.; McDaniel, E.W.


    The Electromagnetic Isotope Separations Program of the Oak Ridge National Laboratory has been involved in the separation, chemical recovery, and refinement of the stable isotopes of cadmium and zinc since 1946. Traditionally, the chemical refinement procedures for these elements consisted of ion exchange separations using anion exchange resins followed by pH-controlled hydrogen sulfide precipitations. The procedures were quite time-consuming and made it difficult to remove trace quantities of sulfur which interferes in subsequent attempts to prepare rolled metal foils. As demands for /sup 113/Cd and /sup 68/Zn (a precursor for the production of the radiopharmaceutical /sup 67/Ga) increased, it became evident that a quicker, more efficient refinement procedure was needed. Details of an improved method, which employs concurrent hydrogen reduction and distillation in the recovery and refinement of isotopically enriched zinc, are described. Modifications of the procedure suitable for the refinement of cadmium isotopes are also described. 3 figures, 1 table.

  7. Chromium isotope uptake in carbonates

    DEFF Research Database (Denmark)

    Rodler, Alexandra

    retain an isotopically light Cr signature. Cr(VI) enriched in heavy Cr isotopes is then transported via river waters to the oceans and sequestered into marine sediments. Marine chemical sediments such asbanded iron formations and modern marine carbonates have proven useful in recording the Cr isotope...... with calcium carbonate in order to test the reliability of the Cr carbonate compositions. Several experimental approaches have been employed to elucidate the fractionation behavior of Cr isotopes when Cr(VI) is incorporated into calcium carbonate phases. These results indicate that at lower Cr concentrations......Chromium (Cr) is a redox sensitive element potentially capable of tracing fine-scale fluctuations of the oxygenation of Earth’s early surface environments and seawater. The Cr isotope composition of carbonates could perhaps be used as paleo-redox proxy to elucidate changes in the geological past...

  8. Cryptographic Combinatorial Securities Exchanges (United States)

    Thorpe, Christopher; Parkes, David C.

    We present a useful new mechanism that facilitates the atomic exchange of many large baskets of securities in a combinatorial exchange. Cryptography prevents information about the securities in the baskets from being exploited, enhancing trust. Our exchange offers institutions who wish to trade large positions a new alternative to existing methods of block trading: they can reduce transaction costs by taking advantage of other institutions’ available liquidity, while third party liquidity providers guarantee execution—preserving their desired portfolio composition at all times. In our exchange, institutions submit encrypted orders which are crossed, leaving a “remainder”. The exchange proves facts about the portfolio risk of this remainder to third party liquidity providers without revealing the securities in the remainder, the knowledge of which could also be exploited. The third parties learn either (depending on the setting) the portfolio risk parameters of the remainder itself, or how their own portfolio risk would change if they were to incorporate the remainder into a portfolio they submit. In one setting, these third parties submit bids on the commission, and the winner supplies necessary liquidity for the entire exchange to clear. This guaranteed clearing, coupled with external price discovery from the primary markets for the securities, sidesteps difficult combinatorial optimization problems. This latter method of proving how taking on the remainder would change risk parameters of one’s own portfolio, without revealing the remainder’s contents or its own risk parameters, is a useful protocol of independent interest.

  9. Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices (United States)

    Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.; Gillette, J. S.; Zare, R. N.


    The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

  10. Distribution of uranium, thorium, and isotopic composition of uranium in soil samples of south Serbia: Evidence of depleted uranium


    Sahoo Sarata Kumar; Fujimoto Kenzo; Čeliković Igor; Ujić Predrag; Žunić Zora S.


    Inductively coupled plasma mass spectrometry and thermal ionization mass spectrom - etry were used to measure concentration of uranium and thorium as well as isotopic composition of uranium respectively in soil samples collected around south Serbia. An analytical method was established for a routine sample preparation procedure for uranium and thorium. Uranium was chemically separated and purified from soil samples by anion exchange resin and UTEVA extraction chromatography and its isotopic c...

  11. BOREAS TE-5 CO2 Concentration and Stable Isotope Composition (United States)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry


    The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Activity Archive Center (DAAC).

  12. Fe atom exchange between aqueous Fe2+ and magnetite. (United States)

    Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M


    The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

  13. Integration of ecohydrological processes in space and time: insights from stable isotope measurements in the soil-plant-atmosphere continuum (United States)

    Williams, D. G.


    Isotope hydrology has helped to crystallize our understanding of the origin, flow, age and fate of water in terrestrial landscapes. Within an ecohydrological context, stable isotope measurements are providing new insight into interactions and feedbacks between vegetation and the water cycle. Subtle variations in isotopic signatures within the soil-plant-atmosphere continuum provide unique information about how plant ecophysiology controls the hydrologic cycle and on the spatial and temporal integration of these processes. Beyond the fairly routine application of isotopes to identify source water used by plants, the approach is rapidly expanding in ecohydrological studies for investigations of carbon-water cycle interactions and biosphere-atmosphere gas exchange processes. The isotopic signature of water vapor released by transpiration often is very distinct from that derived from soil and open water evaporation allowing the partitioning of evapotranspiration fluxes at ecosystem and larger scales. Partitioning of these fluxes provides key insight into biosphere-atmosphere interactions and a clearer understanding of the drivers of ecosystem change. The oxygen isotope ratio of leaf and soil water are becoming increasingly important for understanding patterns and dynamics of photosynthesis and respiration at ecosystem to global levels. Carbon dioxide that exchanges with leaves and soil carries an oxygen isotope signature of the water present in those ecosystem components, and thus provides a powerful tool for resolving sources and sinks of CO2 exchange. However, there are still many uncertainties in the application of isotopes in these types of studies. In parallel with recent advances in modeling, several international monitoring efforts are underway to characterize variation in these isotopic signals, eventually leading to a better understanding of vegetation-hydrology interactions at ecosystem to global scales.

  14. Stable isotope anatomy of tropical cyclone Ita, North-Eastern Australia, April 2014. (United States)

    Munksgaard, Niels C; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I


    The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall.

  15. Stable isotope anatomy of tropical cyclone Ita, North-Eastern Australia, April 2014.

    Directory of Open Access Journals (Sweden)

    Niels C Munksgaard

    Full Text Available The isotope signatures registered in speleothems during tropical cyclones (TC provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall.

  16. Mercury isotope fractionation during precipitation of metacinnabar (β-HgS) and montroydite (HgO). (United States)

    Smith, Robin S; Wiederhold, Jan G; Kretzschmar, Ruben


    To utilize stable Hg isotopes as a tracer for Hg cycling and pollution sources in the environment, it is imperative that fractionation factors for important biogeochemical processes involving Hg are determined. Here, we report experimental results on Hg isotope fractionation during precipitation of metacinnabar (β-HgS) and montroydite (HgO). In both systems, we observed mass-dependent enrichments of light Hg isotopes in the precipitates relative to the dissolved Hg. Precipitation of β-HgS appeared to follow equilibrium isotope fractionation with an enrichment factor ε(202)Hg(precipitate-supernatant) of -0.63‰. Precipitation of HgO resulted in kinetic isotope fractionation, which was described by a Rayleigh model with an enrichment factor of -0.32‰. Small mass-independent fractionation was observed in the HgS system, presumably related to nuclear volume fractionation. We propose that Hg isotope fractionation in the HgS system occurred in solution during the transition of O- to S-coordination of Hg(II), consistent with theoretical predictions. In the HgO system, fractionation was presumably caused by the faster precipitation of light Hg isotopes, and no isotopic exchange between solid and solution was observed on the timescale investigated. The results of this work emphasize the importance of Hg solution speciation and suggest that bonding partners of Hg in solution complexes may control the overall isotope fractionation. The determined fractionation factor and mechanistic insights will have implications for the interpretation of Hg isotope signatures and their use as an environmental tracer.

  17. Competition from Isotopic Modelling

    Directory of Open Access Journals (Sweden)

    Virginie Fabre


    Full Text Available During later MOIS3, in Europe two populations were present, autochthonous Neanderthals and modern humans. Ecological competition between these two populations has often been evoked but never demonstrated. Our aim is to establish whether resource competition occurred. In this paper, in order to examine the possibility of ecological competition between these two populations, 599 isotopic data were subjected to rigorous statistical treatment and analysis through mixing models. The aim of this paper was to compare dietary strategies of Neanderthals and modern humans over time. Our conclusions suggest that Neanderthals and modern humans shared dietary habits in the particular environmental context of MOIS3 characterised in Europe by climatic deterioration. In this environmental context, the resource competition between Neanderthals and modern humans may have accelerated the disappearance of the Neanderthal population.

  18. Molecular exchange in block copolymer micelles: when corona chains overlap (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung


    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  19. Microbes: Agents of Isotopic Change (United States)

    Fogel, M. L.


    Microbes drive many of the important oxidation and reduction reactions on Earth; digest almost all forms of organic matter; and can serve as both primary and secondary producers. Because of their versatile biochemistry and physiology, they impart unique isotopic signatures to organic and inorganic materials, which have proven to be key measurements for understanding elemental cycling now and throughout Earth's history. Understanding microbial isotope fractionations in laboratory experiments has been important for interpreting isotopic patterns measured in natural settings. In fact, the pairing of simple experiment with natural observation has been the pathway for interpreting the fingerprint of microbial processes in ancient sediments and rocks. Examples of how key experiments have explained stable isotope fractionations by microbes and advanced the field of microbial ecology will be presented. Learning the isotopic signatures of Earth's microbes is a valuable exercise for predicting what isotopic signatures could be displayed by possible extant or extinct extraterrestrial life. Given the potential for discovery on Mars, Enceladus, and other solar system bodies, new methods and techniques for pinpointing what is unique about microbial isotope signatures is particularly relevant.

  20. Isotopic criteria in the characterization of aromatic molecules. 2. Influence of the chemical elaboration process. (United States)

    Martin, Gerard J; Heck, Georg; Djamaris-Zainal, Risnayeti; Martin, Maryvonne L


    Most valued natural aromatic molecules can be substituted by their low-cost chemical counterparts. Isotopic methods, which offer the most powerful tool to infer the origin of a molecule, are applied to the characterization of a large number of chemical aromatic species. Isotopic affiliation between precursors and products is investigated in several types of reactions: oxidation of benzyl chloride and benzyl alcohol and hydrolysis of benzylidene chloride and cinnamaldehyde. The isotopic parameters strongly depend not only on the type of process but, for a given process, on the experimental conditions of the reaction. Kinetic isotope effects occurring in several formylation reactions are estimated. It is shown that, in the drastic experimental conditions of many industrial processes, the benzenic hydrogen atoms may be affected by exchange phenomena. Consequently, the site-specific isotopic parameters of the ring fragment of chemical species are usually much less stable than those of the corresponding natural molecules biosynthesized in mild environments. The isotope ratios of substituents such as CH3, CH2Cl, and CHO are more resistant to exchange and provide useful criteria for characterizing both the raw materials and the process. It is shown in particular that radical hydrogen abstraction in toluene to produce benzyl chloride induces relatively moderate fractionation effects. In contrast, oxidation reactions frequently produce strong fractionation effects. In particular, industrial direct oxidation of toluene into benzaldehyde is characterized by deuterium enrichments at the formyl site, which may exceed 900 ppm. Taking into account the large magnitude and high variability of many fractionation effects occurring in chemical reactions, the isotopic fingerprint may provide unambiguous criteria, not only for excluding a natural origin and characterizing the type of process, but also for differentiating molecules synthesized by a given process in different industrial

  1. Exchanging Description Logic Knowledge Bases

    NARCIS (Netherlands)

    Arenas, M.; Botoeva, E.; Calvanese, D.; Ryzhikov, V.; Sherkhonov, E.


    In this paper, we study the problem of exchanging knowledge between a source and a target knowledge base (KB), connected through mappings. Differently from the traditional database exchange setting, which considers only the exchange of data, we are interested in exchanging implicit knowledge. As

  2. Separation and Analysis of Boron Isotope in High Plant by Thermal Ionization Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Qingcai Xu


    Full Text Available Knowledge of boron and its isotope in plants is useful to better understand the transposition and translocation of boron within plant, the geochemical behavior in the interface between soil and plant, and the biogeochemical cycle of boron. It is critical to develop a useful method to separate boron from the plant for the geochemical application of boron and its isotope. A method was developed for the extraction of boron in plant sample, whose isotope was determined by thermal ionization mass spectrometry. The results indicated that this method of dry ashing coupled with two-step ion-exchange chromatography is powerful for the separation of boron in plant sample with large amounts of organic matters completely. The ratios of boron isotope composition in those plant tissue samples ranged from -19.45‰ to +28.13‰ (total range: 47.58‰ with a mean value of 2.61±11.76‰ SD. The stem and root isotopic compositions were lower than those in flower and leaf. The molecular mechanism of boron isotope may be responsible for the observed variation of boron isotopic composition and are considered as a useful tool for the better understanding of boron cycling process in the environment and for the signature of living systems.

  3. Iron stable isotopes track pelagic iron cycling during a subtropical phytoplankton bloom. (United States)

    Ellwood, Michael J; Hutchins, David A; Lohan, Maeve C; Milne, Angela; Nasemann, Philipp; Nodder, Scott D; Sander, Sylvia G; Strzepek, Robert; Wilhelm, Steven W; Boyd, Philip W


    The supply and bioavailability of dissolved iron sets the magnitude of surface productivity for ∼ 40% of the global ocean. The redox state, organic complexation, and phase (dissolved versus particulate) of iron are key determinants of iron bioavailability in the marine realm, although the mechanisms facilitating exchange between iron species (inorganic and organic) and phases are poorly constrained. Here we use the isotope fingerprint of dissolved and particulate iron to reveal distinct isotopic signatures for biological uptake of iron during a GEOTRACES process study focused on a temperate spring phytoplankton bloom in subtropical waters. At the onset of the bloom, dissolved iron within the mixed layer was isotopically light relative to particulate iron. The isotopically light dissolved iron pool likely results from the reduction of particulate iron via photochemical and (to a lesser extent) biologically mediated reduction processes. As the bloom develops, dissolved iron within the surface mixed layer becomes isotopically heavy, reflecting the dominance of biological processing of iron as it is removed from solution, while scavenging appears to play a minor role. As stable isotopes have shown for major elements like nitrogen, iron isotopes offer a new window into our understanding of the biogeochemical cycling of iron, thereby allowing us to disentangle a suite of concurrent biotic and abiotic transformations of this key biolimiting element.

  4. Enzymatic synthesis and RNA interference of nucleosides incorporating stable isotopes into a base moiety. (United States)

    Hatano, Akihiko; Shiraishi, Mitsuya; Terado, Nanae; Tanabe, Atsuhiro; Fukuda, Kenji


    Thymidine phosphorylase was used to catalyze the conversion of thymidine (or methyluridine) and uracil incorporating stable isotopes to deoxyuridine (or uridine) with the uracil base incorporating the stable isotope. These base-exchange reactions proceeded with high conversion rates (75-96%), and the isolated yields were also good (64-87%). The masses of all synthetic compounds incorporating stable isotopes were identical to the theoretical molecular weights via EIMS. (13)C NMR spectra showed spin-spin coupling between (13)C and (15)N in the synthetic compounds, and the signals were split, further proving incorporation of the isotopes into the compounds. The RNA interference effects of this siRNA with uridine incorporating stable isotopes were also investigated. A 25mer siRNA had a strong knockdown effect on the MARCKS protein. The insertion position and number of uridine moieties incorporating stable isotopes introduced into the siRNA had no influence on the silencing of the target protein. This incorporation of stable isotopes into RNA and DNA has the potential to function as a chemically benign tracer in cells. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Hydrogen and oxygen isotope ratios in human hair are related to geography. (United States)

    Ehleringer, James R; Bowen, Gabriel J; Chesson, Lesley A; West, Adam G; Podlesak, David W; Cerling, Thure E


    We develop and test a model to predict the geographic region-of-origin of humans based on the stable isotope composition of their scalp hair. This model incorporates exchangeable and nonexchangeable hydrogen and oxygen atoms in amino acids to predict the delta(2)H and delta(18)O values of scalp hair (primarily keratin). We evaluated model predictions with stable isotope analyses of human hair from 65 cities across the United States. The model, which predicts hair isotopic composition as a function of drinking water, bulk diet, and dietary protein isotope ratios, explains >85% of the observed variation and reproduces the observed slopes relating the isotopic composition of hair samples to that of local drinking water. Based on the geographical distributions of the isotope ratios of tap waters and the assumption of a "continental supermarket" dietary input, we constructed maps of the expected average H and O isotope ratios in human hair across the contiguous 48 states. Applications of this model and these observations are extensive and include detection of dietary information, reconstruction of historic movements of individuals, and provision of region-of-origin information for unidentified human remains.

  6. Theoretical and experimental investigation of nickel isotopic fractionation in species relevant to modern and ancient oceans (United States)

    Fujii, Toshiyuki; Moynier, Frédéric; Dauphas, Nicolas; Abe, Minori


    Nickel plays a central role as an enzyme co-factor in the metabolism of methanogenic Archaea. Methanogens can fractionate Ni isotopes during assimilation, opening the possibility of using the stable isotopic composition of Ni as a biomarker. However, other sources of Ni isotopic variations need to be evaluated before one can establish Ni isotopes as an unambiguous tracer of methanogenesis in the rock record. Equilibrium exchange of Ni between the different species present in the ocean is a potential source of isotopic fractionation. Through controlled laboratory experiments and theoretical calculations, we quantify equilibrium Ni isotope fractionation between different species relevant to the modern and ancient ocean: Ni(H 2O) 62+, Ni(H 2O) 182+, NiOH(H 2O) 5+, Ni(OH) 2(H 2O) 4, NiCl(H 2O) 5+, cis-NiCl 2(H 2O) 4, trans-NiCl 2(H 2O) 4, NiHS(H 2O) 5+, Ni(HS) 2(H 2O) 4, NiSO 4(H 2O) 4, NiHCO 3(H 2O) 4+, NiCO 3(H 2O) 4, and organic ligands (crown ether and oxalic acid). The magnitude of ligand-controlled Ni isotopic fractionation, approximately 1.25‰/amu (2.5‰ for the 60Ni/ 58Ni ratio), is similar to that previously measured in cultures of methanogenic Archaea.

  7. Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates (United States)

    Blättler, Clara L.; Higgins, John A.


    Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

  8. Effects of moisture and nitrogen stress on gas exchange and nutrient resorption in Quercus rubra seedlings (United States)

    K. Francis Salifu; Douglass F. Jacobs


    The effects of simulated soil fertility at three levels (poor, medium, and rich soils) and moisture stress at two levels (well watered versus moisture stressed) on gas exchange and foliar nutrient resorption in 1+0 bareroot northern red oak (Quercus rubra) seedlings were evaluated. Current nitrogen (N) uptake was labeled with the stable isotope

  9. Compelling Research Opportunities using Isotopes

    Energy Technology Data Exchange (ETDEWEB)



    Isotopes are vital to the science and technology base of the US economy. Isotopes, both stable and radioactive, are essential tools in the growing science, technology, engineering, and health enterprises of the 21st century. The scientific discoveries and associated advances made as a result of the availability of isotopes today span widely from medicine to biology, physics, chemistry, and a broad range of applications in environmental and material sciences. Isotope issues have become crucial aspects of homeland security. Isotopes are utilized in new resource development, in energy from bio-fuels, petrochemical and nuclear fuels, in drug discovery, health care therapies and diagnostics, in nutrition, in agriculture, and in many other areas. The development and production of isotope products unavailable or difficult to get commercially have been most recently the responsibility of the Department of Energy's Nuclear Energy program. The President's FY09 Budget request proposed the transfer of the Isotope Production program to the Department of Energy's Office of Science in Nuclear Physics and to rename it the National Isotope Production and Application program (NIPA). The transfer has now taken place with the signing of the 2009 appropriations bill. In preparation for this, the Nuclear Science Advisory Committee (NSAC) was requested to establish a standing subcommittee, the NSAC Isotope Subcommittee (NSACI), to advise the DOE Office of Nuclear Physics. The request came in the form of two charges: one, on setting research priorities in the short term for the most compelling opportunities from the vast array of disciplines that develop and use isotopes and two, on making a long term strategic plan for the NIPA program. This is the final report to address charge 1. NSACI membership is comprised of experts from the diverse research communities, industry, production, and homeland security. NSACI discussed research opportunities divided into three areas: (1

  10. Nitrogen isotopic studies in the suboxic Arabian Sea (United States)

    Naqvi, S. W. A.; Yoshinari, T.; Brandes, J. A.; Devol, A. H.; Jayakumar, D. A.; Narvekar, P. V.; Altabet, M. A.; Codispoti, L. A.


    Measurements of15N/14N in dissolved molecular nitrogen (N2), nitrate (NO{3/-}) and nitrous oxide (N2O) and18O/16O in N2O [expressed as δ15N and δ18O, relative to atmospheric N2 and oxygen (O2), respectively] have been made in water column at several locations in the Arabian Sea, a region with one of the thickest and most intense O2 minima observed in the open ocean. Microbially-mediated reduction of NO{3/-} to N2 (denitrification) in the oxygen minimum zone (OMZ) appears to greatly affect the natural isotopic abundances. The δ15N of NO{3/-} increases from 6‰ in deep waters (2500 m) to 15‰ within the core of the denitrifying layer (250-350 m); the δ15N of N2 concurrently decreases from 0.6‰ to 0.20‰ Values of the isotopic fractionation factor (ɛ) during denitrification estimated using simple advection-reaction and diffusion-reaction models are 22‰ and 25‰, respectively. A strong decrease in δ15N of NO{3/-} is observed from ˜ 200m (> 11‰) to 80m (˜ 6‰); this is attributed to the input of isotopically light nitrogen through nitrogen fixation. Isotopic analysis of N2O reveals extremely large enrichments of both15N and18O within the OMZ, presumably due to the preferential reduction of lighter N2O to N2. However, isotopically light N2O is observed to accumulate in high concentrations above the OMZ indicating that the N2O emitted to the atmosphere from this region cannot be very heavy. The isotope data from the intense upwelling zone off the southwest coast of India, where some of the highest concentrations of N2O ever found at the sea surface are observed, show moderate depletion of15N, but slight enrichment of18O relative to air. These results suggest that the ocean-atmosphere exchange cannot counter inputs of heavier isotopes (particularly18O) associated with the stratospheric back flux, as proposed by previous workers. This calls for additional sources and/or sinks of N2O in the atmosphere. Also, the N2O isotope data cannot be explained by

  11. Development of analytical techniques of vanadium isotope in seawater (United States)

    Huang, T.; Owens, J. D.; Sarafian, A.; Sen, I. S.; Huang, K. F.; Blusztajn, J.; Nielsen, S.


    Vanadium (V) is a transition metal with isotopes of 50V and 51V, and oxidation states of +2, +3, +4 and +5. The average concentration in seawater is 1.9 ppb, which results in a marine residence time of ~50 kyrs. Its various oxidation states make it a potential tool for investigating redox conditions in the ocean and sediments due to redox related changes in the valance state of vanadium. In turn, chemical equilibrium between different oxidation states of V will likely cause isotopic fractionation that can potentially be utilized to quantify past ocean redox states. In order to apply V isotopes as a paleo-redox tracer, it is required that we know the isotopic composition of seawater and the relation to marine sources and sinks of V. We developed a novel method for pre-concentrating V and measuring the isotope ratio in seawater samples. In our method, we used four ion exchange chromatography columns to separate vanadium from seawater matrix elements, in particular titanium and chromium, which both have an isobaric interference on 50V. The first column uses the NOBIAS resin, which effectively separates V and other transition metals from the majority of seawater matrix. Subsequent columns are identical to those utilized when separating V from silicate samples (Nielsen et al, Geostand. Geoanal. Res., 2011). The isotopic composition of the purified V is measured using a Thermo Scientific Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS) in medium resolution mode. This setup resolves all molecular interferences from masses 49, 50, 51, 52 and 53 including S-O species on mass 50. To test the new method, we spiked an open ocean seawater sample from the Bermuda Atlantic Time Series (BATS) station with 10-25 μg of Alfa Aesar vanadium solution, which has an isotopic composition of δ51V = 0 [where δ51V = 1000 × [(51V/50Vsample - 51V/50VAA)/51V/50VAA]. The average of six spiked samples is -0.03±0.19‰, which is within error of the true

  12. Microgravity condensing heat exchanger (United States)

    Thomas, Christopher M. (Inventor); Ma, Yonghui (Inventor); North, Andrew (Inventor); Weislogel, Mark M. (Inventor)


    A heat exchanger having a plurality of heat exchanging aluminum fins with hydrophilic condensing surfaces which are stacked and clamped between two cold plates. The cold plates are aligned radially along a plane extending through the axis of a cylindrical duct and hold the stacked and clamped portions of the heat exchanging fins along the axis of the cylindrical duct. The fins extend outwardly from the clamped portions along approximately radial planes. The spacing between fins is symmetric about the cold plates, and are somewhat more closely spaced as the angle they make with the cold plates approaches Passageways extend through the fins between vertex spaces which provide capillary storage and communicate with passageways formed in the stacked and clamped portions of the fins, which communicate with water drains connected to a pump externally to the duct. Water with no entrained air is drawn from the capillary spaces.

  13. Ion exchange phenomena

    Energy Technology Data Exchange (ETDEWEB)

    Bourg, I.C.; Sposito, G.


    Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).

  14. Heat exchanger panel (United States)

    Warburton, Robert E. (Inventor); Cuva, William J. (Inventor)


    The present invention relates to a heat exchanger panel which has broad utility in high temperature environments. The heat exchanger panel has a first panel, a second panel, and at least one fluid containment device positioned intermediate the first and second panels. At least one of the first panel and the second panel have at least one feature on an interior surface to accommodate the at least one fluid containment device. In a preferred embodiment, each of the first and second panels is formed from a high conductivity, high temperature composite material. Also, in a preferred embodiment, the first and second panels are joined together by one or more composite fasteners.

  15. Microscale Regenerative Heat Exchanger (United States)

    Moran, Matthew E.; Stelter, Stephan; Stelter, Manfred


    The device described herein is designed primarily for use as a regenerative heat exchanger in a miniature Stirling engine or Stirling-cycle heat pump. A regenerative heat exchanger (sometimes called, simply, a "regenerator" in the Stirling-engine art) is basically a thermal capacitor: Its role in the Stirling cycle is to alternately accept heat from, then deliver heat to, an oscillating flow of a working fluid between compression and expansion volumes, without introducing an excessive pressure drop. These volumes are at different temperatures, and conduction of heat between these volumes is undesirable because it reduces the energy-conversion efficiency of the Stirling cycle.

  16. Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone (United States)

    Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.


    The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to

  17. Isotope-based quantum information

    CERN Document Server

    G Plekhanov, Vladimir


    The present book provides to the main ideas and techniques of the rapid progressing field of quantum information and quantum computation using isotope - mixed materials. It starts with an introduction to the isotope physics and then describes of the isotope - based quantum information and quantum computation. The ability to manipulate and control electron and/or nucleus spin in semiconductor devices provides a new route to expand the capabilities of inorganic semiconductor-based electronics and to design innovative devices with potential application in quantum computing. One of the major challenges towards these objectives is to develop semiconductor-based systems and architectures in which the spatial distribution of spins and their properties can be controlled. For instance, to eliminate electron spin decoherence resulting from hyperfine interaction due to nuclear spin background, isotopically controlled devices are needed (i.e., nuclear spin-depleted). In other emerging concepts, the control of the spatial...

  18. Isotope Geochronology: Models Versus Reality

    National Research Council Canada - National Science Library

    Jan Burchart


    Majority of the papers on isotopic dating of minerals and rocks have been devoted to some new geochronological data important for geology or to developments of apparatus and improvements of laboratory...

  19. Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (United States)

    Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.


    Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein–protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent. PMID:22298288

  20. Cadmium isotope fractionation during adsorption to Mn-oxyhydroxide (United States)

    Wasylenki, L. E.; Swihart, J. W.


    The heavy metal cadmium is of interest both as a toxic contaminant in groundwater and as a critical nutrient for some marine diatoms [1], yet little is known about the biogeochemistry of this element. Horner et al. [2] suggested that Cd stable isotopes could potentially enable reconstruction of biological use of Cd in the marine realm: since cultured diatoms fractionate Cd isotopes [3], and ferromanganese crusts appear to incorporate a faithful record of deepwater Cd isotopes [2], depth profiles in such crusts may yield information about the extent of Cd assimilation of isotopically light Cd by diatoms over time. Although no work has yet been published regarding the use of stable isotopes to track reactive transport of Cd in contaminated aquifers, others have recently demonstrated the potential of isotopes to track reactions affecting the mobility of other toxic metals (e.g., [4]). With both of these potential applications in mind, we conducted two sets of experiments, at low and high ionic strength, in which Cd partially adsorbed to potassium birnessite. Our goals are to quantify the fractionations and to constrain the mechanisms governing Cd isotope behavior during adsorption to an environmentally abundant scavenger of Cd. Suspensions of synthetic birnessite were doped with various amounts of dissolved Cd2+ at pH ~8.3. Following reaction, the dissolved and adsorbed pools of Cd were separated by filtration, purified by anion exchange chromatography, and analyzed by multicollector ICP-MS using a double-spike routine. In all cases, lighter isotopes preferentially adsorbed to the birnessite particles. At low ionic strength (I<0.01m), we observed a small fractionation of 0.15‰×0.05 (Δ114/112) that was constant as a function of the fraction of Cd adsorbed. This indicates a small equilibrium isotope effect, likely driven by a subtle shift in coordination geometry for Cd during adsorption. In a groundwater system with continuous flow of dissolved Cd, this

  1. Triple oxygen isotope composition of the Campi Flegrei magma systems (United States)

    Iovine, Raffaella Silvia; Wörner, Gerhard; Pack, Andreas; Sengupta, Sukanya; Carmine Mazzeo, Fabio; Arienzo, Ilenia; D'Antonio, Massimo


    Sr-O isotope relationships in igneous rocks are a powerful tool to distinguish magma sources and quantify assimilation processes in magmatic rocks. Isotopic (87Sr/86Sr and 18O/16O-17O/16O) data have been acquired on whole rocks and separated minerals (feldspar, Fe-cpx, Mg-cpx, olivine phenocrysts) from pyroclastic products of the Campi Flegrei volcanic complex (Gulf of Naples, Southern Italy). Oxygen isotope ratios were measured by infrared laser fluorination using a Thermo MAT253 gas source isotope ratio mass spectrometer in dual inlet mode, on ˜2 mg of hand-picked phenocrysts. Variations in triple oxygen isotope ratios (17O/16O, 18O/16O) are expressed as the δ notation relative to VSMOW. Sr isotopic compositions were determined by thermal ionization mass spectrometry after standard cation-exchange methods on separated hand-picked phenocrysts (˜300 mg), and on whole rocks, in case of insufficient sample size to separate crystals. Sr-isotopes in Campi Flegrei minerals range from 0.707305 to 0.707605 and δ18O varies from 6.5 to 8.3‰ . Recalculated δ18Omelt values accordingly show a large range between 7.2 and 8.6‰ . Our data, compared with published δ18O-isotope data from other Italian volcanic centers (Alban Hills, Mts. Ernici, Ischia, Mt. Vesuvius, Aeolian Islands, Tuscany and Sardinia) and from subduction zones worldwide (Kamchatka, Lesser Antilles, Indonesia and Central Andean ignimbrites), show compositions that are very different from typical mantle values. Distinct trends and sources are recognized in our compilation from global data: (1) serpentinized mantle (Kamchatka), (2) sediment-enrichment in the mantle source (Indonesia, Lesser Antilles, Eolian arc), (3) assimilation of old radiogenic continental crust affecting magmas derived from sediment-modified mantle sources (Tuscany, Sardinia), (4) assimilation of lower crustal lithologies (Central Andes, Alban Hills, Mts. Ernici, Ischia). Sr-O-isotope values of Campi Flegrei and Vesuvius magmas

  2. Dissolved strontium in the subterranean estuary - Implications for the marine strontium isotope budget (United States)

    Beck, Aaron J.; Charette, Matthew A.; Cochran, J. Kirk; Gonneea, Meagan E.; Peucker-Ehrenbrink, Bernhard


    Submarine groundwater discharge (SGD) to the ocean supplies Sr with less radiogenic 87Sr/86Sr than seawater, and thus constitutes an important term in the Sr isotope budget of the modern ocean. However, few data exist for Sr in coastal groundwater or in the geochemically dynamic subterranean estuary (STE). We examined Sr concentrations and isotope ratios from nine globally-distributed coastal sites and characterized the behavior of Sr in the STE. Dissolved Sr generally mixed conservatively in the STE, although large differences were observed in the meteoric groundwater end-member Sr concentrations among sites (0.1-24 μM Sr). Strontium isotope exchange was observed in the STE at five of the sites studied, and invariably favored the meteoric groundwater end-member signature. Most of the observed isotope exchange occurred in the salinity range 5-15, and reached up to 40% exchange at salinity 10. Differences in fresh groundwater Sr concentrations and isotope ratios (87Sr/86Sr = 0.707-0.710) reflected aquifer lithology. The SGD end-member 87Sr/86Sr must be lower than modern seawater (i.e., less than 0.70916) in part because groundwater Sr concentrations are orders of magnitude higher in less-radiogenic carbonate and volcanic island aquifers. A simple lithological model and groundwater Sr data compiled from the literature were used to estimate a global average groundwater end-member of 2.9 μM Sr with 87Sr/86Sr = 0.7089. This represents a meteoric-SGD-driven Sr input to the ocean of 0.7-2.8 × 1010 mol Sr y-1. Meteoric SGD therefore accounts for 2-8% of the oceanic Sr isotope budget, comparable to other known source terms, but is insufficient to balance the remainder of the budget. Using reported estimates for brackish SGD, the estimated volume discharge at salinity 10 (7-11 × 1015 L y-1) was used to evaluate the impact of isotope exchange in the STE on the brackish SGD Sr flux. A moderate estimate of 25% isotope exchange in the STE gives an SGD Sr end-member 87Sr/86Sr

  3. Stable Chlorine Isotope Fractionation (United States)

    Sharp, Z.


    Chlorine isotope partitioning between different phases is not well understood. Pore fluids can have δ37Cl values as low as -8‰, with neoform sediments having strongly positive values. Most strikingly, volcanic gases have δ37Cl values that cover a range in excess of 14‰ (Barnes et al., this meeting). The large range is difficult to explain in terms of equilibrium fractionation, which, although calculated to be very large for Cl in different oxidation states, should be less than 2‰ between chloride species (Schauble et al., 2003, GCA). To address the discrepancy between Nature and theory, we have measured Cl isotope fractionation for selected equilibrium and disequilibrium experiments in order to identify mechanisms that might lead to large fractionations. 1) NaCl (s,l) NaCl (v): NaCl was sealed in an evacuated silica tube and heated at one end, causing vaporization and reprecipitation of NaCl (v) at the cool end of the tube. The fractionation is 0.2‰ at 700°C (halite-vapor) and 0.7‰ at 800°C (liquid-vapor), respectively. The larger fractionation at higher temperature may be related to equilibrium fractionation between liquid and gas vs. `stripping' of the solid in the lower T experiments. 2) Sodalite NaCl(l): Nepheline and excess NaCl were sealed in a Pt crucible at 825°C for 48 hrs producing sodalite. The measured newly-formed sodalite-NaCl fractionation is -0.2‰. 3) Volatilization of HCl: Dry inert gas was bubbled through HCl solutions and the vapor was collected in a downstream water trap. There was no fractionation for 12.4M HCl (HCl fuming) vapor at 25°C. For a 1 M boiling HCl solution, the HCl-vapor fractionation was ~9‰. The difference is probably related to the degree of dissociation in the acid, with HCl dissolved in water for the highly acidic solutions, and dissociated H3O+ and Cl- for lower concentrations. The HCl volatilization experiments are in contrast to earlier vapor-liquid experiments in NaCl-H2O system, where fractionation was

  4. Solvent exchange of buried water and hydrogen exchange of peptide NH groups hydrogen bonded to buried waters in bovine pancreatic trypsin inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Tuechsen, E.; Hayes, J.M.; Ramaprasad, S.; Copie, V.; Woodward, C.


    Solvent exchange of /sup 18/O-labeled buried water in bovine pancreatic trypsin inhibitor (BPTI), trypsin, and trypsin-BPTI complex is measured by high-precision isotope ratio mass spectroscopy. Buried water is labeled by equilibrium of the protein in /sup 18/O-enriched water. Protein samples are then rapidly dialyzed against water of normal isotope composition by gel filtration and stored. The exchangeable /sup 18/O label eluting with the protein in 10-300 s is determined by an H/sub 2/O-CO/sub 2/ equilibration technique. Exchange of buried waters with solvent water is complete before 10-15 s in BPTI, trypsin, and BPTI-trypsin, as well as in lysozyme and carboxypeptidase measured as controls. When in-exchange dialysis and storage are carried out at pH greater than or equal to 2.5, trypsin-BPTI and trypsin, but not free BPTI, have the equivalent of one /sup 18/O atom that exchanges slowly (after 300 s and before several days). This oxygen is probably covalently bound to a specific site in trypsin. When in-exchange dialysis and storage are carried out at pH 1.1, the equivalent of three to seven /sup 18/O atoms per molecule is associated with the trypsin-BPTI complex, apparently due to nonspecific covalent /sup 18/O labeling of carboxyl groups at low pH. In addition to /sup 18/O exchange of buried waters, the hydrogen isotope exchange of buried NH groups H bonded to buried waters was also measured. Their base-catalyzed exchange rate constants are on the order of NH groups that in the crystal are exposed to solvent and hydrogen-bonded main chain O, and their pH/sub min/ is similar to that for model compounds. The pH dependence of their exchange rate constants suggests that direct exchange with water may significantly contribute to their observed exchange rate.

  5. Light stable isotope study of the Roosevelt Hot Springs thermal area, Southwestern Utah

    Energy Technology Data Exchange (ETDEWEB)

    Rohrs D.T.; Bowman, J.R.


    The isotopic composition of hydrogen, oxygen, and carbon has been determined for regional cold springs, thermal fluids, and rocks and minerals from the Roosevelt Hot Springs thermal area. The geothermal system has developed within plutonic granitic rocks and amphibolite facies gneiss, relying upon fracture-controlled permeability for the migration of the thermal fluids. Probably originating as meteoric waters in the upper elevations of the Mineral Mountains, the thermal waters sampled in the production wells display an oxygen isotopic shift of at least +1.2. Depletions of delta /sup 18/O in wole rock, K-feldspar, and biotite have a positive correlation with alteration intensity. W/R mass ratios, calculated from the isotopic shifts of rock and water, range up to 3.0 in a producing horizon of one well, although the K-feldspar has experienced only 30% exchange with the thermal waters. While veinlet quartz has equilibrated with the thermal waters, the /sup 18/O values of K-mica clay, an alteration product of plagioclase, mimic the isotopic composition of K-feldspar and whole rock. This suggests that locally small W/R ratios enable plagioclase to influence its alteration products by isotopic exchange.

  6. Nature's Heat Exchangers. (United States)

    Barnes, George


    Discusses the heat-transfer systems of different animals. Systems include heat conduction into the ground, heat transferred by convection, heat exchange in lizards, fish and polar animals, the carotid rete system, electromagnetic radiation from animals and people, and plant and animal fiber optics. (MDH)

  7. Basic Exchange Rate Theories

    NARCIS (Netherlands)

    J.G.M. van Marrewijk (Charles)


    textabstractThis four-chapter overview of basic exchange rate theories discusses (i) the elasticity and absorption approach, (ii) the (long-run) implications of the monetary approach, (iii) the short-run effects of monetary and fiscal policy under various economic conditions, and (iv) the transition

  8. Technology Performance Exchange

    Energy Technology Data Exchange (ETDEWEB)


    To address the need for accessible, high-quality data, the Department of Energy has developed the Technology Performance Exchange (TPEx). TPEx enables technology suppliers, third-party testing laboratories, and other entities to share product performance data. These data are automatically transformed into a format that technology evaluators can easily use in their energy modeling assessments to inform procurement decisions.

  9. Telephone Exchange Maintenance

    CERN Document Server


    Urgent maintenance work on CERN telephone exchanges will be performed on 24 March from 6 a.m. to 8 a.m. Telephone services may be disrupted or even interrupted during this time. For more details, please contact us by email at

  10. Baltic Exchange toodi Tallinna

    Index Scriptorium Estoniae


    Viimane osa merekonteineritesse kokkupakitud Londoni laevandus- ja merebörsi Baltic Exchange'i endise peakorteri detailidest jõudis 2007. a. juunis Tallinna. Hoone detailid ostnud ärimehed Heiti Hääl ja Eerik-Niiles Kross plaanivad leida hoonele koha Tallinna kesklinnas. E.-N. Krossi kommentaar

  11. Heat exchanger. Varmeveksler

    Energy Technology Data Exchange (ETDEWEB)

    Rosman, I.E.; Wagner, W.R.


    The invention concerns a manifold for a plate-type heat exchanger, and includes a side channel connected the inlet of the manifold. The plates can be designed as an integral assembly together with the integrated side- and external end-manifolds as well. 16 drawings.

  12. Chemical exchange program analysis.

    Energy Technology Data Exchange (ETDEWEB)

    Waffelaert, Pascale


    As part of its EMS, Sandia performs an annual environmental aspects/impacts analysis. The purpose of this analysis is to identify the environmental aspects associated with Sandia's activities, products, and services and the potential environmental impacts associated with those aspects. Division and environmental programs established objectives and targets based on the environmental aspects associated with their operations. In 2007 the most significant aspect identified was Hazardous Materials (Use and Storage). The objective for Hazardous Materials (Use and Storage) was to improve chemical handling, storage, and on-site movement of hazardous materials. One of the targets supporting this objective was to develop an effective chemical exchange program, making a business case for it in FY07, and fully implementing a comprehensive chemical exchange program in FY08. A Chemical Exchange Program (CEP) team was formed to implement this target. The team consists of representatives from the Chemical Information System (CIS), Pollution Prevention (P2), the HWMF, Procurement and the Environmental Management System (EMS). The CEP Team performed benchmarking and conducted a life-cycle analysis of the current management of chemicals at SNL/NM and compared it to Chemical Exchange alternatives. Those alternatives are as follows: (1) Revive the 'Virtual' Chemical Exchange Program; (2) Re-implement a 'Physical' Chemical Exchange Program using a Chemical Information System; and (3) Transition to a Chemical Management Services System. The analysis and benchmarking study shows that the present management of chemicals at SNL/NM is significantly disjointed and a life-cycle or 'Cradle-to-Grave' approach to chemical management is needed. This approach must consider the purchasing and maintenance costs as well as the cost of ultimate disposal of the chemicals and materials. A chemical exchange is needed as a mechanism to re-apply chemicals on site. This

  13. Dynamics of urokinase receptor interaction with Peptide antagonists studied by amide hydrogen exchange and mass spectrometry

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J D; Gårdsvoll, Henrik; Danø, Keld


    on the peptide ligand. This yields bimodal isotope patterns from which dissociation rate constants can be determined. In addition, the distinct bimodal isotope distributions also allow investigation of the exchange kinetics of receptor-bound peptides providing information about the local structural motions......Using amide hydrogen exchange combined with electrospray ionization mass spectrometry, we have in this study determined the number of amide hydrogens on several peptides that become solvent-inaccessible as a result of their high-affinity interaction with the urokinase-type plasminogen activator...... hydrogens in the receptor complex. Interestingly, a naturally occurring O-linked fucose on Thr(18) confers protection of two additional amide hydrogens in GFD when it forms a complex with uPAR. Dissociation of the uPAR-peptide complexes is accompanied by a correlated exchange of nearly all amide hydrogens...

  14. Counterflow Regolith Heat Exchanger (United States)

    Zubrin, Robert; Jonscher, Peter


    A problem exists in reducing the total heating power required to extract oxygen from lunar regolith. All such processes require heating a great deal of soil, and the heat energy is wasted if it cannot be recycled from processed material back into new material. The counterflow regolith heat exchanger (CoRHE) is a device that transfers heat from hot regolith to cold regolith. The CoRHE is essentially a tube-in-tube heat exchanger with internal and external augers attached to the inner rotating tube to move the regolith. Hot regolith in the outer tube is moved in one direction by a right-hand - ed auger, and the cool regolith in the inner tube is moved in the opposite direction by a left-handed auger attached to the inside of the rotating tube. In this counterflow arrangement, a large fraction of the heat from the expended regolith is transferred to the new regolith. The spent regolith leaves the heat exchanger close to the temperature of the cold new regolith, and the new regolith is pre-heated close to the initial temperature of the spent regolith. Using the CoRHE can reduce the heating requirement of a lunar ISRU system by 80%, reducing the total power consumption by a factor of two. The unique feature of this system is that it allows for counterflow heat exchange to occur between solids, instead of liquids or gases, as is commonly done. In addition, in variants of this concept, the hydrogen reduction can be made to occur within the counterflow heat exchanger itself, enabling a simplified lunar ISRU (in situ resource utilization) system with excellent energy economy and continuous nonbatch mode operation.

  15. NOx cycle and the tropospheric ozone isotope anomaly: an experimental investigation (United States)

    Michalski, G.; Bhattacharya, S. K.; Girsch, G.


    The oxygen isotope composition of nitrogen oxides (NOx) in the atmosphere is a useful tool for understanding the oxidation of NOx into nitric acid / nitrate in the atmosphere. A set of experiments was conducted to examine change in isotopic composition of NOx due to NOx-O2-O3 photochemical cycling. At low NOx / O2 mixing ratios, NOx became progressively and nearly equally enriched in 17O and 18O over time until it reached a steady state with Δ17O values of 39.3 ± 1.9‰ and δ18O values of 84.2 ± 4‰, relative to the isotopic composition of the initial O2 gas. As the mixing ratios were increased, the isotopic enrichments were suppressed by isotopic exchange between O atoms, O2, and NOx. A kinetic model was developed to simulate the observed data and it showed that the isotope effects occurring during O3 formation play a dominant role in controlling NOx isotopes and, in addition, secondary kinetic isotope effects or isotope exchange reactions are also important during NOx cycling. The data and model were consistent with previous studies which showed that the NO + O3 reactions occur mainly via the transfer of the terminal atoms of O3. The model predicts that under tropospheric concentrations of NOx and O3, the timescale of NOx-O3 isotopic equilibrium ranges from hours (for ppbv NOx / O2 mixing ratios) to days (for pptv mixing ratios) and yields steady state Δ17O and δ18O values of 45‰ and 117‰ respectively (relative to Vienna Standard Mean Ocean Water (VSMOW)) in both cases. Under atmospheric conditions when O3 has high concentrations, the equilibrium between NOx and O3 should occur rapidly (h) but this equilibrium cannot be reached during polar winters and/or nights if the NOx conversion to HNO3 is faster. The experimentally derived rate coefficients can be used to model the major NOx-O3 isotopologue reactions at various pressures and in isotope modeling of tropospheric nitrate.

  16. Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium (United States)

    Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin


    In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

  17. Electron linac for medical isotope production with improved energy efficiency and isotope recovery (United States)

    Noonan, John; Walters, Dean; Virgo, Matt; Lewellen, John


    A method and isotope linac system are provided for producing radio-isotopes and for recovering isotopes. The isotope linac is an energy recovery linac (ERL) with an electron beam being transmitted through an isotope-producing target. The electron beam energy is recollected and re-injected into an accelerating structure. The ERL provides improved efficiency with reduced power requirements and provides improved thermal management of an isotope target and an electron-to-x-ray converter.

  18. Chain exchange in block copolymer micelles (United States)

    Lu, Jie; Bates, Frank; Lodge, Timothy


    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  19. Analytical applications of ion exchangers

    CERN Document Server

    Inczédy, J


    Analytical Applications of Ion Exchangers presents the laboratory use of ion-exchange resins. This book discusses the development in the analytical application of ion exchangers. Organized into 10 chapters, this book begins with an overview of the history and significance of ion exchangers for technical purposes. This text then describes the properties of ion exchangers, which are large molecular water-insoluble polyelectrolytes having a cross-linked structure that contains ionic groups. Other chapters consider the theories concerning the operation of ion-exchange resins and investigate th

  20. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits (United States)

    Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.


    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  1. Nitrogen and Oxygen Isotopes of Low-Level Nitrate in Groundwater For Environmental Forensics (United States)

    Wang, Y.


    Sources of nitrate in water from human activities include fertilizers, animal feedlots, septic systems, wastewater treatment lagoons, animal wastes, industrial wastes and food processing wastes. Nitrogen and Oxygen isotopic analysis of nitrate in groundwater is essential to source identification and environmental forensics as nitrate from different sources carry distinctly different N and O isotopic compositions. Nitrate is extracted from groundwater samples and converted into AgNO3 using ion exchange techniques. The purified AgNO3 is then broken down into N2 and CO for N and O isotopic measurement. Since nitrate concentrations in natural ground waters are usually less than 2 mg/L, however, such method has been limited by minimum sample size it requires, in liters, which is highly nitrate concentration dependent. Here we report a TurboVap- Denitrifier method for N and O isotopic measurement of low-level dissolved nitrate, based on sample evaporation and isotopic analysis of nitrous oxide generated from nitrate by denitrifying bacteria that lack N2O- reductase activity. For most groundwater samples with mg/L-level of nitrate direct injection of water samples in mLs is applied. The volume of sample is adjusted according to its nitrate concentration to achieve a final sample size optimal for the system. For water samples with ug/L-level of nitrate, nitrate is highly concentrated using a TurboVap evaporator, followed by isotopic measurement with Denitrifier method. Benefits of TurboVap- Denitrifier method include high sensitivity and better precision in both isotopic data. This method applies to both freshwater and seawater. The analyses of isotopic reference materials in nitrate-free de-ionized water and seawater are included as method controls to correct for any blank effects. The isotopic data from groundwater and ocean profiles demonstrate the consistency of the data produced by the TurboVap-Denitrifier method.

  2. The nature of oxygen exchange in ZrW2O8 revealed by two-dimensional solid-state 17O NMR. (United States)

    Hampson, Matthew R; Hodgkinson, Paul; Evans, John S O; Harris, Robin K; King, Ian J; Allen, Simon; Fayon, Franck


    17O magic angle spinning (MAS) NMR has been used to determine the nature of oxygen exchange in ZrW(2)O(8). A highly effective isotopic labelling technique has been developed and 1D NMR and 2D exchange spectroscopy (EXSY) experiments have revealed that mutual exchange occurs between all oxygen sites, even at temperatures considerably below the alpha to beta order-disorder phase transition.

  3. Iodine isotopes species fingerprinting environmental conditions in surface water along the northeastern Atlantic Ocean

    DEFF Research Database (Denmark)

    He, Peng; Hou, Xiaolin; Aldahan, Ala


    Concentrations and species of iodine isotopes (127I and 129I) provide vital information about iodine geochemistry, environmental conditions and water masses exchange in oceans. Despite extensive investigations of anthropogenic 129I in the Arctic Ocean and the Nordic Seas, concentrations...... of the isotope in the Atlantic Ocean are, however, still unknown. We here present first data on 129I and 127I, and their species (iodide and iodate) in surface water transect along the northeastern Atlantic between 30° and 50°N. The results show iodate as the predominant species in the analyzed marine waters...... 129I in ocean environments and impact on climate at the ocean boundary layer....

  4. Oxygen exchange between nitrate molecules during nitrite oxidation by Nitrobacter. (United States)

    DiSpirito, A A; Hooper, A B


    During oxidation of nitrite, cells of Nitrobacter winogradskyi are shown to catalyze the active exchange of oxygen atoms between exogenous nitrate molecules (production of 15N16/18O3- during incubation of 14N16/18O3-, 15N16O3-, and 15N16O2- in H216O). Little, if any, exchange of oxygens between nitrate and water also occurs (production of 15N16/18O3- during incubation of 15N16O3- and 14N16O2- in H218O). 15N species of nitrate were assayed by 18O-isotope shift in 15N NMR. Taking into account the O-exchange reactions which occur during nitrite oxidation, H2O is seen to be the source of O in nitrate produced by oxidation of nitrite by N. winogradskyi. The data do not establish whether the nitrate-nitrate O exchange is catalyzed by nitrite oxidase (H2O + HNO2----HNO3 + 2H+ + 2e-) or nitrate reductase (HNO3 + 2H+ + 2e-----HNO2 + H2O) or both enzymes in consort. The nitrate-nitrate exchange reaction suggests the existence of an oxygen derivative of a H2O-utilizing oxidoreductase.

  5. Data Exchange Inventory (DEXI) System (United States)

    Social Security Administration — DEXI is an intranet application used by SSA users to track all incoming and outgoing data exchanges between SSA and our data exchange partners. Information such as...

  6. Solution-phase deuterium/hydrogen exchange at a specific residue using nozzle-skimmer and electron capture dissociation mass spectrometry. (United States)

    Hagman, Charlotte; Tsybin, Yury O; Håkansson, Per


    Information about protein conformation can be obtained with hydrogen/deuterium exchange (HDX) mass spectrometry. The isotopic solution-phase exchange of specific amide hydrogen atoms can be followed using low-vacuum nozzle-skimmer collision-induced dissociation (CID). In this study, the nozzle-skimmer technique was complemented by electron capture dissociation (ECD) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). The solution-phase exchange at a specific residue is monitored by comparing isotopic distributions of two consecutive b- or c-type ions. While nozzle-skimmer fragmentation takes place in the low-vacuum region of the mass spectrometer, ECD occurs at ultra-high vacuum within the mass analyzer cell of the FTICR mass spectrometer. The dissociations take place at 10(-4) and 10(-9) mbar, respectively. Low-vacuum nozzle-skimmer fragmentation can result in intramolecular exchange between product ions and solvent molecules in the gas phase. Consequently, the solution-phase information about protein or peptide conformation is lost. It was not possible to monitor isotopic solution-phase exchange at the eighth residue in substance P, (Phe)8, with nozzle-skimmer CID. By using the in-cell ECD fragmentation method, the solution-phase exchange at the (Phe)8 residue was preserved during mass spectrometric analysis. This result shows the complementary aspects of applying fragmentation at low and at high vacuum, when studying isotopic exchange in solution at specific residues using FTICRMS. Copyright 2006 John Wiley & Sons, Ltd.

  7. Isotope shifts in francium isotopes Fr-213206 and 221Fr (United States)

    Collister, R.; Gwinner, G.; Tandecki, M.; Behr, J. A.; Pearson, M. R.; Zhang, J.; Orozco, L. A.; Aubin, S.; Gomez, E.; FrPNC Collaboration


    We present the isotope shifts of the 7 s1 /2 to 7 p1 /2 transition for francium isotopes 206 -213Fr with reference to 221Fr collected from two experimental periods. The shifts are measured on a sample of atoms prepared within a magneto-optical trap by a fast sweep of radio-frequency sidebands applied to a carrier laser. King plot analysis, which includes literature values for 7 s1 /2 to 7 p3 /2 isotope shifts, provides a field shift constant ratio of 1.0520(10) and a difference between the specific mass shift constants of 170(100) GHz amu between the D1 and D2 transitions, of sufficient precision to differentiate between ab initio calculations.

  8. Dynamical Clustering of Exchange Rates


    Fenn, Daniel J.; Porter, Mason A.; Mucha, Peter J; Mark McDonald; Stacy Williams; Johnson, Neil F.; Jones, Nick S


    We use techniques from network science to study correlations in the foreign exchange (FX) market over the period 1991--2008. We consider an FX market network in which each node represents an exchange rate and each weighted edge represents a time-dependent correlation between the rates. To provide insights into the clustering of the exchange rate time series, we investigate dynamic communities in the network. We show that there is a relationship between an exchange rate's functional role withi...

  9. Serial tempering without exchange. (United States)

    Nymeyer, Hugh


    Serial tempering is a computational method that turns the temperature T (or more generally any independent λ parameter) into a dynamical variable. It is shown that, under conditions for which this variable is fast, serial tempering is equivalent to the umbrella sampling method with a single effective potential. This equivalence is demonstrated using both a small one-dimensional system and a small solvated peptide. The suggestion is then made to replace the serial tempering protocol with the equivalent umbrella sampling calculation. This approach, serial tempering without exchange (STeWiE), has the same performance as serial tempering in the limit that exchanges are frequent, is simpler to implement, and has fewer adjustable parameters than conventional serial tempering. The equivalence of serial tempering and STeWiE also provides a convenient route for estimating and optimizing the performance of serial tempering simulations and other generalized-ensemble methods.

  10. Lipid exchange by ultracentrifugation

    DEFF Research Database (Denmark)

    Drachmann, Nikolaj Düring; Olesen, Claus


    Lipids play an important role in maintaining P-type ATPase structure and function, and often they are crucial for ATPase activity. When the P-type ATPases are in the membrane, they are surrounded by a mix of different lipids species with varying aliphatic chain lengths and saturation......, and the complex interplay between the lipids and the P-type ATPases are still not well understood. We here describe a robust method to exchange the majority of the lipids surrounding the ATPase after solubilisation and/or purification with a target lipid of interest. The method is based on an ultracentrifugation...... step, where the protein sample is spun through a dense buffer containing large excess of the target lipid, which results in an approximately 80-85 % lipid exchange. The method is a very gently technique that maintains protein folding during the process, hence allowing further characterization...

  11. Exchange rate rebounds after foreign exchange market interventions (United States)

    Hoshikawa, Takeshi


    This study examined the rebounds in the exchange rate after foreign exchange intervention. When intervention is strongly effective, the exchange rate rebounds at next day. The effect of intervention is reduced slightly by the rebound after the intervention. The exchange rate might have been 67.12-77.47 yen to a US dollar without yen-selling/dollar-purchasing intervention of 74,691,100 million yen implemented by the Japanese government since 1991, in comparison to the actual exchange rate was 103.19 yen to the US dollar at the end of March 2014.

  12. Isotopes a very short introduction

    CERN Document Server

    Ellam, Rob


    An isotope is a variant form of a chemical element, containing a different number of neutrons in its nucleus. Most elements exist as several isotopes. Many are stable while others are radioactive, and some may only exist fleetingly before decaying into other elements. In this Very Short Introduction, Rob Ellam explains how isotopes have proved enormously important across all the sciences and in archaeology. Radioactive isotopes may be familiar from their use in nuclear weapons, nuclear power, and in medicine, as well as in carbon dating. They have been central to establishing the age of the Earth and the origins of the solar system. Combining previous and new research, Ellam provides an overview of the nature of stable and radioactive isotopes, and considers their wide range of modern applications. ABOUT THE SERIES: The Very Short Introductions series from Oxford University Press contains hundreds of titles in almost every subject area. These pocket-sized books are the perfect way to get ahead in a new subjec...

  13. Toward Closing the Water Cycle over the ARM/CART Region: Implementation of Stable Water Isotope Physics in MM5 (United States)

    Kemball-Cook, S. R.; Miller, N. L.; DePaolo, D. J.


    To date, atmospheric water isotope modeling has been performed on a global scale. The development of a stable water isotope scheme in a mesoscale model will lead to a simulated spatial distribution that will improve our understanding of present day climate variability, as well as historical climate patterns. The purpose of this study was to add water isotope tracers to the regional atmospheric model MM5 (NCAR's Mesoscale Model 5) in order to link existing global and basin-scale isotope models, and to work toward an improved knowledge of the water budget over the ARM site. In order to include isotopic processes in MM5, eight new prognostic variables were added to the model's dynamical core. These are the isotopic mixing ratios for water vapor, cloud liquid water, cloud ice, and rain for the stable isotopes O18 and deuterium. The isotopes are treated in a manner similar to the natural water vapor, cloud liquid water, etc. in terms of diffusion, advection, nudging, and filtering. Isotope fractionation and diffusion are handled using the approach of Gedzelman and Arnold (1994). Processes treated in this model are fractionation during deposition of water vapor onto cloud ice and condensation of water vapor onto cloud water, and also diffusive exchange of isotopes between vapor and falling rain drops. The bulk flux model of Hoffman et al. (1998) is used here as a first order approximation for isotopic evaporative processes. For the runs to be discussed here, lateral boundary conditions were generated by the Melbourne University General Circulation Model. This GCM runs at a resolution of R21, and predicts values of the O18 and deuterium mixing ratios at each grid point. Results of preliminary model runs will be discussed.

  14. O3 and NOx Exchange

    NARCIS (Netherlands)

    Loubet, B.; Castell, J.F.; Laville, P.; Personne, E.; Tuzet, A.; Ammann, C.; Emberson, L.; Ganzeveld, L.; Kowalski, A.S.; Merbold, L.; Stella, P.; Tuovinen, J.P.


    This discussion was based on the background document “Review on modelling atmosphere-biosphere exchange of Ozone and Nitrogen oxides”, which reviews the processes contributing to biosphere-atmosphere exchange of O3 and NOx, including stomatal and non-stomatal exchange of O3 and NO, NO2.

  15. The stability of exchange networks

    NARCIS (Netherlands)

    Doğan, G.; Assen, M. van; Rijt, A. van de; Buskens, V.W.


    Economic and sociological exchange theories predict divisions of exchange benefits given an assumed fixed network of exchange relations. Since network structure has been found to have a large impact on actors’ payoffs, actors have strong incentives for network change.Weanswer the question what

  16. Integrated foreign exchange risk management

    DEFF Research Database (Denmark)

    Aabo, Tom; Høg, Esben; Kuhn, Jochen


    Empirical research has focused on export as a proxy for exchange rate exposure and the use of foreign exchange derivatives as an instrument to deal with this exposure. This empirical study applies an integrated foreign exchange risk management approach with a particular focus on the role of impor...

  17. Integrated Foreign Exchange Risk Management

    DEFF Research Database (Denmark)

    Aabo, Tom; Høg, Esben; Kuhn, Jochen

    Empirical research has focused on export as a proxy for the exchange rate exposure and the use of foreign exchange derivatives as the instrument to deal with this exposure. This empirical study applies an integrated foreign exchange risk management approach with a particular focus on the role...

  18. Scraped surface heat exchangers. (United States)

    Rao, Chetan S; Hartel, Richard W


    Scraped surface heat exchangers (SSHEs) are commonly used in the food, chemical, and pharmaceutical industries for heat transfer, crystallization, and other continuous processes. They are ideally suited for products that are viscous, sticky, that contain particulate matter, or that need some degree of crystallization. Since these characteristics describe a vast majority of processed foods, SSHEs are especially suited for pumpable food products. During operation, the product is brought in contact with a heat transfer surface that is rapidly and continuously scraped, thereby exposing the surface to the passage of untreated product. In addition to maintaining high and uniform heat exchange, the scraper blades also provide simultaneous mixing and agitation. Heat exchange for sticky and viscous foods such as heavy salad dressings, margarine, chocolate, peanut butter, fondant, ice cream, and shortenings is possible only by using SSHEs. High heat transfer coefficients are achieved because the boundary layer is continuously replaced by fresh material. Moreover, the product is in contact with the heating surface for only a few seconds and high temperature gradients can be used without the danger of causing undesirable reactions. SSHEs are versatile in the use of heat transfer medium and the various unit operations that can be carried out simultaneously. This article critically reviews the current understanding of the operations and applications of SSHEs.

  19. Timing Foreign Exchange Markets

    Directory of Open Access Journals (Sweden)

    Samuel W. Malone


    Full Text Available To improve short-horizon exchange rate forecasts, we employ foreign exchange market risk factors as fundamentals, and Bayesian treed Gaussian process (BTGP models to handle non-linear, time-varying relationships between these fundamentals and exchange rates. Forecasts from the BTGP model conditional on the carry and dollar factors dominate random walk forecasts on accuracy and economic criteria in the Meese-Rogoff setting. Superior market timing ability for large moves, more than directional accuracy, drives the BTGP’s success. We explain how, through a model averaging Monte Carlo scheme, the BTGP is able to simultaneously exploit smoothness and rough breaks in between-variable dynamics. Either feature in isolation is unable to consistently outperform benchmarks throughout the full span of time in our forecasting exercises. Trading strategies based on ex ante BTGP forecasts deliver the highest out-of-sample risk-adjusted returns for the median currency, as well as for both predictable, traded risk factors.

  20. Paste heat exchange

    Energy Technology Data Exchange (ETDEWEB)


    The subject of coal paste heat exchangers is discussed in this letter report from Gelsenberg A.G. to I.G. Farbenindustrie A.G. Gelsenberg had given little consideration to the heating of coal paste by means of regeneration (heat exchange) because of the lack of experience in paste regeneration with bituminous coal, especially at 700 atmospheres. At the I.G. Farben plant at Poelitz, paste regeneration was carried out so that low concentration coal paste was heated in the regenerator together with the process gas, and the remaining coal was fed into the cold pass of the preheater in a thicker paste. Later tests proved this process viable. Gelsenberg heated normal coal paste and the gas in heat exchangers with the goal of relieving the preheater. Good results were achieved without change in design. The coal paste was heated with process gas in the regenerator at up to 315 degrees with constant pressure difference, so that after three months no decrease in K-values and no deposition or thickening was observed. Through the omission of paste gas, the pressure difference of the system became more constant and did not rise above the former level. The temperature also was more controllable, the chamber smoother running. Principal thermal data are given in a table. 1 table, 1 graph.

  1. The exchangeability of shape

    Directory of Open Access Journals (Sweden)

    Kaba Dramane


    Full Text Available Abstract Background Landmark based geometric morphometrics (GM allows the quantitative comparison of organismal shapes. When applied to systematics, it is able to score shape changes which often are undetectable by traditional morphological studies and even by classical morphometric approaches. It has thus become a fast and low cost candidate to identify cryptic species. Due to inherent mathematical properties, shape variables derived from one set of coordinates cannot be compared with shape variables derived from another set. Raw coordinates which produce these shape variables could be used for data exchange, however they contain measurement error. The latter may represent a significant obstacle when the objective is to distinguish very similar species. Results We show here that a single user derived dataset produces much less classification error than a multiple one. The question then becomes how to circumvent the lack of exchangeability of shape variables while preserving a single user dataset. A solution to this question could lead to the creation of a relatively fast and inexpensive systematic tool adapted for the recognition of cryptic species. Conclusions To preserve both exchangeability of shape and a single user derived dataset, our suggestion is to create a free access bank of reference images from which one can produce raw coordinates and use them for comparison with external specimens. Thus, we propose an alternative geometric descriptive system that separates 2-D data gathering and analyzes.

  2. Deuterium isotope effects on 13C chemical shifts of 10-Hydroxybenzo[h]quinolines

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Kamounah, Fadhil S.; Gryko, Daniel T.


    Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...... with calculated OH stretching frequencies. Isotope effects on chemical shifts are calculated for systems with OH exchanged by OD. Hydrogen bond potentials are discussed. New and more soluble nitro derivatives are synthesized.......Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found...... to be negative, indicating transmission via the hydrogen bond. In addition unusual long-range effects are seen. Structures, NMR chemical shifts and changes in nuclear shieldings upon deuteriation are calculated using DFT methods. Two-bond deuterium isotope effects on 13C chemical shifts are correlated...

  3. A solvent extraction technique for the isotopic measurement of dissolved copper in seawater. (United States)

    Thompson, Claire M; Ellwood, Michael J; Wille, Martin


    Stable copper (Cu) isotope geochemistry provides a new perspective for investigating and understanding Cu speciation and biogeochemical Cu cycling in seawater. In this work, sample preparation for isotopic analysis employed solvent-extraction with amino pyrollidine dithiocarbamate/diethyl dithiocarbamate (APDC/DDC), coupled with a nitric acid back-extraction, to concentrate Cu from seawater. This was followed by Cu-purification using anion-exchange. This straightforward technique is high yielding and fractionation free for Cu and allows precise measurement of the seawater Cu isotopic composition using multi-collector inductively coupled plasma mass-spectrometry. A deep-sea profile measured in the oligotrophic north Tasman Sea shows fractionation in the Cu isotopic signature in the photic zone but is relatively homogenised at depth. A minima in the Cu isotopic profile correlates with the chlorophyll a maximum at the site. These results indicate that a range of processes are likely to fractionate stable Cu isotopes in seawater. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

  4. Isotope Fractionation Associated with the Indirect Photolysis of Substituted Anilines in Aqueous Solution. (United States)

    Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Bolotin, Jakov; Hofstetter, Thomas B


    Organic micropollutants containing aniline substructures are susceptible to different light-induced transformation processes in aquatic environments and water treatment operations. Here, we investigated the magnitude and variability of C and N isotope fractionation during the indirect phototransformation of four para-substituted anilines in aerated aqueous solutions. The model photosensitizers, namely 9,10-anthraquinone-1,5-disulfonate and methylene blue, were used as surrogates for dissolved organic matter chromophores generating excited triplet states in sunlit surface waters. The transformation of aniline, 4-CH3-, 4-OCH3-, and 4-Cl-aniline by excited triplet states of the photosensitizers was associated with inverse and normal N isotope fractionation, whereas C isotope fractionation was negligible. The apparent 15N kinetic isotope effects (AKIE) were almost identical for both photosensitizers, increased from 0.9958±0.0013 for 4-OCH3-aniline to 1.0035±0.0006 for 4-Cl-aniline, and correlated well with the electron donating properties of the substituent. N isotope fractionation is pH-dependent in that H+ exchange reactions dominate below and N atom oxidation processes above the pKa value of the substituted aniline's conjugate acid. Correlations of C and N isotope fractionation for indirect phototransformation were different from those determined previously for the direct photolysis of chloroanilines and offer new opportunities to distinguish between abiotic degradation pathways.

  5. Stable iron isotope fractionation between aqueous Fe(II) and hydrous ferric oxide. (United States)

    Wu, Lingling; Beard, Brian L; Roden, Eric E; Johnson, Clark M


    Despite the ubiquity of poorly crystalline ferric hydrous oxides (HFO, or ferrihydrite) in natural environments, stable Fe isotopic fractionation between HFO and other Fe phases remains unclear. In particular, it has been difficult to determine equilibrium Fe isotope fractionation between aqueous Fe(II) and HFO due to fast transformation of the latter to more stable minerals. Here we used HFO stabilized by the presence of dissolved silica (2.14 mM), or a Si-HFO coprecipitate, to determine an equilibrium Fe(II)-HFO fractionation factor using a three-isotope method. Iron isotope exchange between Fe(II) and HFO was rapid and near complete with the Si-HFO coprecipitate, and rapid but incomplete for HFO in the presence of dissolved silica, the latter case likely reflecting blockage of oxide surface sites by sorbed silica. Equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factors of -3.17 ± 0.08 (2σ)‰ and -2.58 ± 0.14 (2σ)‰ were obtained for HFO plus silica and the Si-HFO coprecipitate, respectively. Structural similarity between ferrihydrite and hematite, as suggested by spectroscopic studies, combined with the minor isotopic effect of dissolved silica, imply that the true equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factor in the absence of silica may be ∼-3.2‰. These results provide a critical interpretive context for inferring the stable isotope effects of Fe redox cycling in nature.

  6. Hydrogen isotope alteration of normal alkanes during artificial maturation experiments (United States)

    Wang, C.; Eley, Y.; Oakes, A.; Hren, M. T.


    Hydrogen isotopes of normal alkanes provide a record of past climate, hydrocarbon source and migration, and thermal history. Numerous authors have investigated the preservation potential of organic compounds during burial diagenesis and developed a range of molecular indicators of thermal maturity. A key uncertainty in application of organic biomarkers for paleoenvironmental work is how the δD values of individual molecular compounds changes during burial heating and thermal cracking. Studies suggest that n-alkanes are unlikely to exchange hydrogen at modest temperatures (below 150°C) over geologic time, however there is still debate over the potential for alteration of primary isotopic signatures due to the combined effect of exchange and cracking of more complex molecules. We conducted a suite of heating experiments in ambient air and oxygen-free systems using pure alkane mixtures and natural soil extracts to evaluate the preservation potential of the hydrogen isotopic composition of both short (nC20) carbon chain n-alkanes. Our data show that for pure mixtures, there is a positive shift in the δD of long carbon chains during heating of up to 12‰ and a negative shift in short chains of up to 28‰. Experiments with natural sediment extracts show 2H enrichment of long carbon chains during heating in both ambient air and oxygen free systems, and at temperatures below 150°C. These changes are accompanied by shifts in the carbon preference and average chain length. Experimental data show that there is potential for 2H/1H alteration of long-carbon chain normal alkanes during shallow burial, however these changes rarely exceed 10-15‰ before compounds are degraded to quantities below useful abundances for isotope measurements. A potentially significant result is that low temperature alteration of organics within sediments can shift the average chain length, particularly in the presence of oxygen. Thus, lithology and gas permeability may play an important role in

  7. Exciting baryon resonances in isobar charge-exchange reactions (United States)

    Benlliure, J.; Rodriguez-Sanchez, J. L.; Vargas, J.; Alavarez-Pol, H.; Aumann, T.; Atkinson, J.; Ayyad, Y.; Beceiro, S.; Boretzky, K.; Chatillon, A.; Cortina, D.; Diaz, P.; Estrade, A.; Geissel, H.; Lenske, H.; Litvinov, Y.; Mostazo, M.; Paradela, C.; Pietri, S.; Prochazka, A.; Takechi, M.; Vidaña, I.; Weick, H.; Winfield, J.


    Isobaric charge-exchange reactions induced by different tin isotopes have been investigated at GSI. The high-resolving power of the FRS spectrometer made it possible to separate elastic and inelastic components in the missing-energy spectra of the ejectiles. The inelastic component was associated to the in-medium excitation of nucleon resonances such as the Delta and Roper resonances. These data are expected to contribute to better understand the in-medium properties of baryon resonances but also to investigate the abundance of protons and neutrons at the nuclear periphery.

  8. Oxygen surface exchange kinetics of SrTi1-xFexO3-d mixed conducting oxides

    NARCIS (Netherlands)

    Yoo, C.-Y.; Bouwmeester, Henricus J.M.


    The oxygen surface exchange kinetics of mixed conducting perovskite oxides SrTi1−xFexO3−δ (x = 0, 0.01, 0.05, 0.35, 0.5) has been investigated as a function of temperature and oxygen partial pressure using the pulse-response 18O–16O isotope exchange (PIE) technique. Arrhenius activation energies

  9. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    The isotopic fractionation associated with photodissociation of N2O, OCS and CO2, at different altitudes in Earth’s atmosphere, is investigated theoretically using constructed quantum mechanical models of the dissociation processes (i.e. potential energy surfaces and relevant coupling elements......’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...... in heavy carbon. The sulfur fractionation is weak and photolysis of OCS in the stratosphere produces only a small and mass dependent enrichment of heavy sulfur isotopes in the remaining OCS. Sulfur fractionation from the two remaining chemical sinks (oxidation by O(3P) and OH, respectively) is weak...

  10. Isotope specific arbitrary material sorter (United States)

    Barty, Christopher P.J.


    A laser-based mono-energetic gamma-ray source is used to provide a rapid and unique, isotope specific method for sorting materials. The objects to be sorted are passed on a conveyor in front of a MEGa-ray beam which has been tuned to the nuclear resonance fluorescence transition of the desired material. As the material containing the desired isotope traverses the beam, a reduction in the transmitted MEGa-ray beam occurs. Alternately, the laser-based mono-energetic gamma-ray source is used to provide non-destructive and non-intrusive, quantitative determination of the absolute amount of a specific isotope contained within pipe as part of a moving fluid or quasi-fluid material stream.

  11. Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria (United States)

    Kappler, A.; Johnson, C.M.; Crosby, H.A.; Beard, B.L.; Newman, D.K.


    Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3 – Fe(II)aq fractionation factor of +3.0 ‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and

  12. Automated Sample Preparation for Radiogenic and Non-Traditional Metal Isotopes: Removing an Analytical Barrier for High Sample Throughput (United States)

    Field, M. Paul; Romaniello, Stephen; Gordon, Gwyneth W.; Anbar, Ariel D.; Herrmann, Achim; Martinez-Boti, Miguel A.; Anagnostou, Eleni; Foster, Gavin L.


    MC-ICP-MS has dramatically improved the analytical throughput for high-precision radiogenic and non-traditional isotope ratio measurements, compared to TIMS. The generation of large data sets, however, remains hampered by tedious manual drip chromatography required for sample purification. A new, automated chromatography system reduces the laboratory bottle neck and expands the utility of high-precision isotope analyses in applications where large data sets are required: geochemistry, forensic anthropology, nuclear forensics, medical research and food authentication. We have developed protocols to automate ion exchange purification for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U) using the new prepFAST-MC™ (ESI, Nebraska, Omaha). The system is not only inert (all-flouropolymer flow paths), but is also very flexible and can easily facilitate different resins, samples, and reagent types. When programmed, precise and accurate user defined volumes and flow rates are implemented to automatically load samples, wash the column, condition the column and elute fractions. Unattended, the automated, low-pressure ion exchange chromatography system can process up to 60 samples overnight. Excellent reproducibility, reliability, recovery, with low blank and carry over for samples in a variety of different matrices, have been demonstrated to give accurate and precise isotopic ratios within analytical error for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U). This illustrates the potential of the new prepFAST-MC™ (ESI, Nebraska, Omaha) as a powerful tool in radiogenic and non-traditional isotope research.

  13. Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Shikha; Sack, Andrea; Adams, James P.; Vesper, Dorothy; J Capo, Rosemary C.; Hartsock, Angela; Edenborn, Harry M.


    Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing.

  14. Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry (United States)

    Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F.


    Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

  15. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.


    indicates that at high OH radical concentrations, photochemical formation or removal of nitrophenols can be faster than exchange between the two phases. The dependence between the concentrations and isotope ratios of the nitrophenols and meteorological conditions as well as pollution levels (NO2, O3, SO2 and CO) demonstrate that the influence of precursor concentrations on nitrophenol concentrations is far more important than the extent of photochemical processing. While it cannot be excluded that primary emissions contribute to the observed levels of nitrophenols, overall the available evidence demonstrates that secondary formation is the dominant source for atmospheric nitrophenols in Toronto.

  16. Cosmology: Rare isotopic insight into the Universe (United States)

    Prantzos, Nikos


    Light isotopes of hydrogen and helium formed minutes after the Big Bang. The study of one of these primordial isotopes, helium-3, has now been proposed as a useful strategy for constraining the physics of the standard cosmological model.

  17. A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science (United States)

    Coplen, Tyler B.; Qi, Haiping


    The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

  18. Developmentand Application of Accelerator Isotopes in China


    YANG Yuan-you; LI Fei-ze; LIAO Jia-li; Liu, Ning


    Compared with the isotopes generated by nuclear reactor, the isotopes prepared by accelerator always show high specific activity and short half-life period. And most of such isotopes always were neutron-deficient nuclides, giving β+ or single energy γ ray. As one of the most important methods preparing radionuclides, the preparation of isotopes by accelerator has attracted more and more attention from the beginning of 21th century. The development of the preparation and application of the acc...

  19. Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques (United States)

    Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine


    Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet

  20. The Dynamics of Multilateral Exchange (United States)

    Hausken, Kjell; Moxnes, John F.

    The article formulates a dynamic mathematical model where arbitrarily many players produce, consume, exchange, loan, and deposit arbitrarily many goods over time to maximize utility. Consuming goods constitutes a benefit, and producing, exporting, and loaning away goods constitute a cost. Utilities are benefits minus costs, which depend on the exchange ratios and bargaining functions. Three-way exchange occurs when one player acquires, through exchange, one good from another player with the sole purpose of using this good to exchange against the desired good from a third player. Such a triple handshake is not merely a set of double handshakes since the player assigns no interest to the first good in his benefit function. Cognitive and organization costs increase dramatically for higher order exchanges. An exchange theory accounting for media of exchange follows from simple generalization of two-way exchange. The examples of r-way exchange are the triangle trade between Africa, the USA, and England in the 17th and 18th centuries, the hypothetical hypercycle involving RNAs as players and enzymes as goods, and reaction-diffusion processes. The emergence of exchange, and the role of trading agents are discussed. We simulate an example where two-way exchange gives zero production and zero utility, while three-way exchange causes considerable production and positive utility. Maximum utility for each player is reached when exchanges of the same order as the number of players in society are allowed. The article merges micro theory and macro theory within the social, natural, and physical sciences.

  1. Stable isotopes and biomarkers in microbial ecology

    NARCIS (Netherlands)

    Boschker, H.T.S.; Middelburg, J.J.


    The use of biomarkers in combination with stable isotope analysis is a new approach in microbial ecology and a number of papers on a variety of subjects have appeared. We will first discuss the techniques for analysing stable isotopes in biomarkers, primarily gas chromatography-combustion-isotope

  2. Use of Isotopes for Studying Reaction Mechanisms

    Indian Academy of Sciences (India)

    In the first part of this series, we discussed how isotopes can be used as markers to determine the nature of intermediates in chemical reactions. The second part covered the effect of isotopes on equilibria and reactions, in processes where the bond to the isotopic a tom is broken. We showed with specific examples how.

  3. Cryogenic regenerative heat exchangers

    CERN Document Server

    Ackermann, Robert A


    An in-depth survey of regenerative heat exchangers, this book chronicles the development and recent commercialization of regenerative devices for cryogenic applications. Chapters cover historical background, concepts, practical applications, design data, and numerical solutions, providing the latest information for engineers to develop advanced cryogenic machines. The discussions include insights into the operation of a regenerator; descriptions of the cyclic and fluid temperature distributions in a regenerator; data for various matrix geometries and materials, including coarse and fine bronze, stainless steel-woven wire mesh screens, and lead spheres; and unique operating features of cryocoolers that produce deviations from ideal regenerator theory.

  4. Chromatographic measurement of hydrogen isotopic and permanent gas impurities in tritium

    Energy Technology Data Exchange (ETDEWEB)

    Warner, D.K.; Kinard, C.; Bohl, D.C.


    This paper describes a gas chromatograph that was designed for dedicated analysis of hydrogen isotopic and permanent gas impurities in tritium and tritium-deuterium mixtures. The instrument that was developed substantially improved the accuracy and precision of hydrogen isotopic analysis in the 20 ppM to one mole percent range as compared with other analytical methods. Several unique design features of the instrument were required due to the radiation and isotopic exchange properties of the tritium in the samples; descriptions of these features are presented along with details of the complete chromatographic system. The experimental procedures used to calibrate the detector and statistically evaluate its performance are given, and the sources of analytical error are cited. The limitations of the present system are also discussed.

  5. Planetary fertility during the past 400 ka based on the triple isotope composition of O2 in trapped gases from the Vostok ice core


    Blunier, T.; M. L. Bender; Barnett, B.; Fischer, J C


    The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately, atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration affect δ17O approximately half as much as δ18O. An "anomalous" (also termed mass independent) fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 an...

  6. Fragmentation of exotic oxygen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Leistenschneider, A.; Elze, Th.W.; Gruenschloss, A.; Palit, R. [Johann Wolfgang Goethe-Univ., Frankfurt (Germany). Inst. fuer Kernphysik; Aumann, T.; Cortina, D.; Datta Pramanik, U.; Emling, H.; Geissel, H.; Helariutta, K.; Hellstroem, M.; Ilievski, S.; Jones, K.; Muenzenberg, G.; Scheidenberger, C.; Schmidt, K.-H.; Suemmerer, K. [Gesellschaft fuer Schwerionenforschung (GSI), Darmstadt (Germany); Boretzky, K.; Kratz, J.V.; Le Hong, Khiem [Johannes Gutenberg-Univ., Mainz (Germany). Inst. fue Kernchemie; Canto, L.F. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Fisica; Carlson, B.V. [Centro Tecnico Aeroespacial (CTA), Sao Jose dos Campos, SP (Brazil). Inst. Tecnologico de Aeronautica (ITA). Dept. de Fisica; Hussein, M.S. [Sao Paulo Univ. (USP), SP (Brazil). Inst. de Fisica; Kulessa, R.; Lubkiewicz, E.; Wajda, E.; Walus, W. [Uniwersytet Jagellonski, Krakow (Poland). Instytut Fizyki; Reiter, P. [Ludwig-Maximilians-Univ., Garching (Germany). Sektion Physik; Simon, H. [Technische Univ., Darmstadt (Germany). Inst. fuer Kernphysik


    Abrasion-ablation models and the empirical EPAX parametrization of projectile fragmentation are described. Their cross section predictions are compared to recent data of the fragmentation of secondary beams of neutron-rich, unstable {sup 19,20,21} O isotopes at beam energies near 600 MeV/nucleon as well as data for stable {sup 17,18} O beams. (author)

  7. Isotope Harvesting Opportunities at FRIB (United States)

    Morrissey, David


    The fragmentation of fast heavy ion beams now at the National Superconducting Cyclotron Laboratory (NSCL) and in the future at the Facility for Rare Isotope Beams (FRIB) under construction produce an unprecedentedly broad spectrum of radionuclides but only a small fraction are used in the on-line rare-isotope program. Projectile fragmentation facilities provide an electromagnetically purified beam of a single projectile fragment for nuclear physics experiments ranging from low energy astrophysics, through nuclear structure studies, to probing fundamental symmetries. By augmenting the NSCL and FRIB production facilities with complimentary collection and purification of discarded ions, called isotope harvesting with chemical purification, many other nuclides will become available for off-line experiments in parallel with the primary experiment. A growing user community has established a list of key target isotopes and is working with the FRIB design team to allow inclusion of necessary equipment in the future. An overview of the possibilities and the techniques will be presented in this talk. Supported by Office of Science, US DOE and Michigan State University.

  8. Charge radii of radium isotopes

    NARCIS (Netherlands)

    Wansbeek, L. W.; Schlesser, S.; Sahoo, B. K.; Dieperink, A. E. L.; Onderwater, C. J. G.; Timmermans, R. G. E.


    We present a combined analysis of the available isotope-shift data from the optical spectra of Ra atoms and Ra+ ions. Atomic structure calculations of the field-shift and specific mass-shift constants of the low-lying levels in Ra+ are used. The nuclear radial differences delta for the radium

  9. Modeling equilibrium Fe isotope fractionation (United States)

    Anbar, A.; Jarzecki, A.; Spiro, T.


    Research into the stable isotope biogeochemistry of Fe and other transition metals has been driven primarily by analytical innovations which have revealed significant isotope effects in nature and the laboratory. Further development of these new isotope systems requires complementary theoretical research to guide analytical efforts. The results of the first such studies show some discrepancies with experiments. For example, Johnson et al. (2002) report an experimentally-determined 56Fe/54Fe equilibrium fractionation factor between Fe(II) and Fe(III) aquo complexes of ˜1.0025. This effect is ˜50% smaller than predicted theoretically by Schauble et al. (2001). It is important to resolve such discrepancies. Equilibrium isotope fractionation factors can be predicted from vibrational spectroscopic data of isotopically-substituted complexes, or from theoretical predictions of some or all of these frequencies obtained using force field models. The pioneering work of Schauble et al. (2001) utilized a modified Urey-Bradley force field (MUBFF) model. This approach is limiting in at least three ways: First, it is not ab initio, requiring as input some measured vibrational frequencies. Such data are not always available, or may have significant uncertainties. Second, the MUBFF does not include potentially important effects of solvent interaction. Third, because it makes certain assumptions about molecular symmetry, the MUBFF-based approach is not able to model the spectra of mixed-ligand complexes. To address these limitations, we are evaluating the use of density functional theory (DFT) as an ab initio method to predict vibrational frequencies of isotopically-substituted complexes and, hence, equilibrium fractionation factors. In a preliminary examination of the frequency shift upon isotope substitution of the bending and asymmetric stretching modes of the tetrahedral FeCl_42- complex, we find substantial differences between MUBFF and DFT predictions. Results for other Fe

  10. Dynamics of Chain Exchange in Block Copolymer Micelles (United States)

    Lodge, Timothy

    Block copolymer micelles are rarely at equilibrium. The primary reason is the large number of repeat units in the insoluble block, Ncore, which makes the thermodynamic penalty for extracting a single chain (``unimer exchange'') substantial. As a consequence, the critical micelle concentration (CMC) is rarely accessed experimentally; however, in the proximity of a critical micelle temperature (CMT), equilibration is possible. We have been using time-resolved small angle neutron scattering (TR-SANS) to obtain a detailed picture of the mechanisms and time scales for chain exchange, at or near equilibrium. Our model system is poly(styrene)-block-poly(ethylene-alt-propylene)) (PS-PEP), in the PEP-selective solvent squalane (C30H62) . Equivalent micelles with either normal (hPS) or perdeuterated (dPS) cores are initially mixed in a blend of isotopically substituted squalane, designed to contrast-match a 50:50 hPS:dPS core. Samples are then annealed at a target temperature, and chain exchange is revealed quantitatively by the temporal decay in scattered intensity. The rate of exchange as function of concentration, temperature, Ncore, Ncorona, and chain architecture (diblock versus triblock) will be discussed.

  11. The isotopic contamination in electromagnetic isotope separators; La contagion isotopique dans les separateurs electromagnetiques d'isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Cassignol, Ch. [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires


    In the early years of isotope separation, and in particular electromagnetic isotope separation, needs for rapid results have conducted to empiric research. This paper describes fundamental research on the electromagnetic isotope separation to a better understanding of isotope separators as well as improving the performances. Focus has been made on the study of the principle of isotope contamination and the remedial action on the separator to improve the isotope separation ratio. In a first part, the author come back to the functioning of an electromagnetic separator and generalities on isotope contamination. Secondly, it describes the two stages separation method with two dispersive apparatus, an electromagnetic separation stage followed by an electrostatic separation stage, both separated by a diaphragm. The specifications of the electrostatic stage are given and its different settings and their consequences on isotope separation are investigated. In a third part, mechanisms and contamination factors in the isotope separation are discussed: natural isotope contamination, contamination by rebounding on the collector, contamination because of a low resolution, contamination by chromatism and diffusion effect, breakdown of condenser voltage. Analysis of experimental results shows the diffusion as the most important contamination factor in electromagnetic isotope separation. As contamination factors are dependent on geometric parameters, sector angle, radius of curvature in the magnetic field and clearance height are discussed in a fourth part. The better understanding of the mechanism of the different contamination factors and the study of influential parameters as pressure and geometric parameters lead to define a global scheme of isotope contamination and determinate optima separator design and experimental parameters. Finally, the global scheme of isotope contamination and hypothesis on optima specifications and experimental parameters has been checked during a

  12. Isotopic Compositions of the Elements 1989 (United States)

    De Laeter, J. R.; Heumann, K. G.; Rosman, K. J. R.


    The Subcommittee for Isotopic Abundance Measurements (SIAM) of the IUPAC Commission on Atomic Weights and Isotopic Abundances has carried out its biennial review of isotopic compositions, as determined by mass spectrometry and other relevant methods. The Subcommittee's critical evaluation of the published literature element by element forms the basis of the Table of Isotopic Compositions of the Elements as Determined by Mass Spectrometry 1989, which is presented in this Report. Atomic Weights calculated from the tabulated isotopic abundances are consistent with Ar(E) values listed in the Table of Standard Atomic Weights 1989.

  13. Stable isotope compounds - production, detection, and application. (United States)

    Zachleder, Vilém; Vítová, Milada; Hlavová, Monika; Moudříková, Šárka; Mojzeš, Peter; Heumann, Hermann; Becher, Johannes R; Bišová, Kateřina


    Stable isotopes are used in wide fields of application from natural tracers in biology, geology and archeology through studies of metabolic fluxes to their application as tracers in quantitative proteomics and structural biology. We review the use of stable isotopes of biogenic elements (H, C, N, O, S, Mg, Se) with the emphasis on hydrogen and its heavy isotope deuterium. We will discuss the limitations of enriching various compounds in stable isotopes when produced in living organisms. Finally, we overview methods for measuring stable isotopes, focusing on methods for detection in single cells in situ and their exploitation in modern biotechnologies. Copyright © 2018. Published by Elsevier Inc.

  14. Modelling stable water isotopes: Status and perspectives

    Directory of Open Access Journals (Sweden)

    Werner M.


    Full Text Available Modelling of stable water isotopes H2 18O and HDO within various parts of the Earth’s hydrological cycle has clearly improved our understanding of the interplay between climatic variations and related isotope fractionation processes. In this article key principles and major research results of stable water isotope modelling studies are described. Emphasis is put on research work using explicit isotope diagnostics within general circulation models as this highly complex model setup bears many resemblances with studies using simpler isotope modelling approaches.

  15. Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

    Energy Technology Data Exchange (ETDEWEB)

    Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.; Varga, Tamas; Blake, Ruth E.


    A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction of phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic

  16. Reaction Kinetics of HBr with HO2: A New Channel for Isotope Scrambling Reactions. (United States)

    Church, Jonathan R; Skodje, Rex T


    The gas phase reaction kinetics of HBr with the HO2 radical are investigated over the temperature range of T = 200-1500 K using a theoretical approach based on transition state theory. The parameters for the potential energy surface are computed using density functional theory with the M11 exchange functional. The rate coefficient for the HBr + HO2 → Br + H2O2 abstraction channel is found to be somewhat larger than previous estimates at low temperatures due to quantum tunneling. The present study reveals the existence of a novel exchange pathway, HBr + H'O2 → H'Br + HO2, which exhibits a much lower reaction barrier than does the abstraction route. The transition state for this process is a symmetrical planar five-membered-ring-shaped structure. At low temperatures, this concerted double hydrogen transfer reaction is several orders of magnitude faster than the abstraction channel. The exchange process may be observed using isotope scrambling reactions; such reactions may contribute to observed isotope abundances in the atmosphere. The rate coefficients for the isotopically labeled reactions are computed.

  17. High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry. (United States)

    Paul, Maxence; Bridgestock, Luke; Rehkämper, Mark; van DeFlierdt, Tina; Weiss, Dominik


    A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a (207)Pb-(204)Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28±21 pg (1sd) and typical Pb recoveries of 40-60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12±4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700-1500 ppm and 1000-2000 ppm were achieved for (207)Pb/(206)Pb, (208)Pb/(206)Pb and (206)Pb/(204)Pb, (207)Pb/(204)Pb, (208)Pb/(204)Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor (204)Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the (206)Pb/(204)Pb ratios are well correlated

  18. Combined S-33 and O-18 Isotope Tracing of Intracellular Sulfur Metabolism during Microbial Sulfate Reduction (United States)

    Antler, Gilad; Bosak, Tanja; Ono, Shuhei; Sivan, Orit; Turchyn, Alexandra V.


    composition of oxygen showed that the kinetic isotopic fractionation was negligible and that δ18O in sulfate should be 22.5o higher than δ18O in water (at 22° C). This relationship indicates that more intracellular sulfite may be oxidized back to sulfate when the flux of electrons from the electron donor to sulfite is low, allowing isotopic exchange of oxygen between sulfite and water. The use of our experimental results as constraints in a reactive transport model implies that the magnitudes of the oxygen isotope fractionation and sulfur isotope fractionation are correlated under a broad range of sulfate reduction rates in marine and marginal marine environments. This correlation suggests a strong role for the electron donor in controlling the intracellular redox fluxes of sulfur and the fractionation of oxygen isotopes in the natural environment.

  19. Zinc isotopic compositions of breast cancer tissue. (United States)

    Larner, Fiona; Woodley, Laura N; Shousha, Sami; Moyes, Ashley; Humphreys-Williams, Emma; Strekopytov, Stanislav; Halliday, Alex N; Rehkämper, Mark; Coombes, R Charles


    An early diagnostic biomarker for breast cancer is essential to improve outcome. High precision isotopic analysis, originating in Earth sciences, can detect very small shifts in metal pathways. For the first time, the natural intrinsic Zn isotopic compositions of various tissues in breast cancer patients and controls were determined. Breast cancer tumours were found to have a significantly lighter Zn isotopic composition than the blood, serum and healthy breast tissue in both groups. The Zn isotopic lightness in tumours suggests that sulphur rich metallothionein dominates the isotopic selectivity of a breast tissue cell, rather than Zn-specific proteins. This reveals a possible mechanism of Zn delivery to Zn-sequestering vesicles by metallothionein, and is supported by a similar signature observed in the copper isotopic compositions of one breast cancer patient. This change in intrinsic isotopic compositions due to cancer has the potential to provide a novel early biomarker for breast cancer.

  20. Measuring SNM Isotopic Distributions using FRAM

    Energy Technology Data Exchange (ETDEWEB)

    Geist, William H. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    The first group of slides provides background information on the isotopic composition of plutonium. It is shown that 240Pu is the critical isotope in neutron coincidence/multiplicity counting. Next, response function analysis to determine isotopic composition is discussed. The isotopic composition can be determined by measuring the net peak counts from each isotope and then taking the ratio of the counts for each isotope relative to the total counts for the element. Then FRAM (Fixed energy Response function Analysis with Multiple efficiencies) is explained. FRAM can control data acquisition, automatically analyze newly acquired data, analyze previously acquired data, provide information on the quality of the analysis, and facilitate analysis in unusual situations (non-standard energy calibrations, gamma rays from non-SNM isotopes, poor spectra (within limits)).

  1. Developing bulk exchange spring magnets

    Energy Technology Data Exchange (ETDEWEB)

    Mccall, Scott K.; Kuntz, Joshua D.


    A method of making a bulk exchange spring magnet by providing a magnetically soft material, providing a hard magnetic material, and producing a composite of said magnetically soft material and said hard magnetic material to make the bulk exchange spring magnet. The step of producing a composite of magnetically soft material and hard magnetic material is accomplished by electrophoretic deposition of the magnetically soft material and the hard magnetic material to make the bulk exchange spring magnet.

  2. Characteristics of model heat exchanger (United States)

    Kolínský, Jan


    The aim of this paper is thermal analysis of model water to water heat exchanger at different mass flow rates. Experimental study deals with determination of total heat transfer - power of the heat exchanger. Furthermore the paper deals with analysis of heat exchanger charakcteristic using a definition of thermal efficiency. It is demonstrated that it is advisable to monitor the dependence of thermal efficiency and flow ratio.

  3. Transendothelial exchange of low-density lipoprotein is unaffected by the presence of severe atherosclerosis

    DEFF Research Database (Denmark)

    Kornerup, Karen; Nordestgaard, Børge Grønne; Jensen, Trine Krogsgaard


    OBJECTIVE: We tested the hypothesis that transendothelial exchange of low-density lipoprotein (LDL) is influenced by the presence of severe atherosclerosis; we previously found this exchange elevated in diabetes patients. METHODS: By an in vivo isotope method, we compared transendothelial LDL...... exchange in 24 patients with angiographically verified coronary atherosclerosis, 11 patients with angiographically verified peripheral atherosclerosis, 60 patients with diabetes, and in 42 controls. Autologous 131-iodinated LDL ((131)I-LDL) and 125-iodinated albumin ((125)I-albumin) were injected...... intravenously (i.v.), and the 1-h fractional escape rates (FER(LDL) and FER(alb)) were taken as indices of transendothelial exchange. RESULTS: Patients with coronary or peripheral atherosclerosis had FER(LDL) similar to that of controls [4.3 (3.5-5.1) and 3.2 (2.3-4.1) versus 4.2 (3.7-4.7)%/h; P>0.05], even...

  4. Plausibility of potassium ion-exchanged ZSM-5 as soot combustion catalysts. (United States)

    Lu, Chenxi; Liu, Taizheng; Shi, Qiaolan; Li, Qian; Xin, Ying; Zheng, Lei; Zhang, Zhaoliang


    Potassium (K) ion-exchanged ZSM-5 zeolites were investigated for catalytic soot combustion. X-ray absorption fine-structure (XAFS), Raman, in situ IR and NH3-temperature programmed desorption (NH3-TPD) confirmed the location of K+ at the ion-exchanged sites. Temperature-programmed oxidation (TPO) reactions showed that K-ZSM-5 decreased ignition tempeatures of soot combustion and increased selectivity to CO2. The improved activity for soot combustion by increasing K+-exchanged amounts via decreasing the Si/Al ratio reinforced the K+ ions participating in soot combustion. 18O2 isotopic isothermal reactions suggested the activation of gaseous oxygen by the K+ ions. This demonstrated a new appliction of alkali metal exchanged zeolites and the strategy for enhancement of catalytic soot combustion activity.

  5. Isotope hydrology of catchment basins: lithogenic and cosmogenic isotopic systems

    Energy Technology Data Exchange (ETDEWEB)

    Nimz, G. J., LLNL


    A variety of physical processes affect solute concentrations within catchment waters. The isotopic compositions of the solutes can indicate which processes have determined the observed concentrations. These processes together constitute the physical history of the water. Many solutes in natural waters are derived from the interaction between the water and the rock and/or soil within the system - these are termed `lithogenic` solutes. The isotopic compositions of these solutes provide information regarding rock-water interactions. Many other solutes have their isotopic compositions determined both within and outside of the catchment - i.e., in addition to being derived from catchment rock and soil, they are solutes that are also transported into the catchment. Important members of this group include solutes that have isotopic compositions produced by atomic particle interactions with other nuclides. The source of the atomic particles can be cosmic radiation (producing `cosmogenic` nuclides in the atmosphere and land surface), anthropogenic nuclear reactions (producing `thermonuclear` nuclides), or radioactive and fission decay of naturally-occurring elements, principally {sup 238}U (producing `in-situ` lithogenic nuclides in the deep subsurface). Current language usage often combines all of the atomic particle-produced nuclides under the heading `cosmogenic nuclides`, and for simplicity we will often follow that usage here, although always indicating which variety is being discussed. This paper addresses the processes that affect the lithogenic and cosmogenic solute concentrations in catchment waters, and how the isotopic compositions of the solutes can be used in integrative ways to identify these processes, thereby revealing the physical history of the water within a catchment system. The concept of a `system` is important in catchment hydrology. A catchment is the smallest landscape unit that can both participate in all of the aspects of the hydrologic cycle and

  6. What Drives Stock Exchange Integration?

    National Research Council Canada - National Science Library

    Ekaterina Dorodnykh


    .... After a broad discussion of the existent literature, the investigation combines a large number of potentially relevant determinants for the explanation of whether stock exchanges are participating...

  7. Mastering Microsoft Exchange Server 2013

    CERN Document Server

    Elfassy, David


    The bestselling guide to Exchange Server, fully updated for the newest version Microsoft Exchange Server 2013 is touted as a solution for lowering the total cost of ownership, whether deployed on-premises or in the cloud. Like the earlier editions, this comprehensive guide covers every aspect of installing, configuring, and managing this multifaceted collaboration system. It offers Windows systems administrators and consultants a complete tutorial and reference, ideal for anyone installing Exchange Server for the first time or those migrating from an earlier Exchange Server version.Microsoft

  8. Methane clumped isotopes: Progress and potential for a new isotopic tracer

    Energy Technology Data Exchange (ETDEWEB)

    Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.; Sessions, Alex L.; Lawson, Michael; Shuai, Yanhua; Bishop, Andrew; Podlaha, Olaf G.; Ferreira, Alexandre A.; Santos Neto, Eugenio V.; Niemann, Martin; Steen, Arne S.; Huang, Ling; Chimiak, Laura; Valentine, David L.; Fiebig, Jens; Luhmann, Andrew J.; Seyfried, William E.; Etiope, Giuseppe; Schoell, Martin; Inskeep, William P.; Moran, James J.; Kitchen, Nami


    The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.

  9. Hybrid Heat Exchangers (United States)

    Tu, Jianping Gene; Shih, Wei


    A hybrid light-weight heat exchanger concept has been developed that uses high-conductivity carbon-carbon (C-C) composites as the heat-transfer fins and uses conventional high-temperature metals, such as Inconel, nickel, and titanium as the parting sheets to meet leakage and structural requirements. In order to maximize thermal conductivity, the majority of carbon fiber is aligned in the fin direction resulting in 300 W/m.K or higher conductivity in the fin directions. As a result of this fiber orientation, the coefficient of thermal expansion (CTE) of the C-C composite in both non-fiber directions matches well with the CTE of various high-temperature metal alloys. This allows the joining of fins and parting sheets by using high-temperature braze alloys.

  10. The Radioecology Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, Catherine L.; Beresford, Nicholas A.; Patel, Sabera; Wells, Claire; Howard, Brenda J. [NERC Centre for Ecology and Hydrology, CEH Lancaster, Lancaster Environment Centre, Library Av., Bailrigg, Lancaster, LA1 4AP (United Kingdom); Mora, Juan Carlos; Real, Almudena [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avenida complutense 22, Madrid, 28040 (Spain); Beaugelin-Seiller, Karine; Gilbin, Rodolphe; Hinton, Thomas [IRSN-Institut de Radioprotection et de Surete Nucleaire, 31, Avenue de la Division Leclerc, 92260 Fontenay-Aux-Roses (France); Vesterbacka, Pia; Muikku, Maarit; Outola, Iisa [Radiation and Nuclear Safety Authority, P.O. Box 14, FI-00881 Helsinki (Finland); Skuterud, Lavrans; AlbumYtre-Eide, Martin [Norwegian Radiation Protection Authority, Grini Naeringspark 13, Oesteraas, 1332 (Norway); Bradshaw, Clare; Stark, Karolina; Jaeschke, Ben [Stockholms Universitet, Universitetsvaegen 10, Stockholm, 10691 (Sweden); Oughton, Deborah; Skipperud, Lindis [NMBU Norwegian University of Life Science P.O. Box 5003N-1432 Aas, Oslo (Norway); Vandenhove, Hildegarde; Vanhoudt, Nathalie [SCK.CEN, Studiecentrum voor Kernenergie/Centre d' Etude de l' Energie Nucleaire, Avenue Herrmann-Debroux 40, BE-1160 Brussels (Belgium); Willrodt, Christine; Steiner, Martin [Bundesamt fuer Strahlenschutz, Willy-Brandt-Strasse 5, 38226 Salzgitter (Germany)


    The Radioecology Exchange ( was created in 2011 under the EU FP7 STAR (Strategy for Allied Radioecology) network of excellence. The project aims to integrate the research efforts on radioecology of nine European organisations into a sustainable network. The web site (together with associated Twitter feeds and Facebook page) currently provides the gateway to project outputs and other on-line radiation protection and radioecological resources. In 2013, the EU FP7 COMET (Coordination and implementation of a pan-European instrument for radioecology) project commenced; it aims to strengthen research on the impact of radiation on man and the environment. COMET includes the STAR partners with the addition of one Japanese and two Ukrainian research institutes. As STAR and COMET interact closely together and with the European Radioecology Alliance (, the Radioecology Exchange will be modified to become an international 'hub' for information related to radioecology. Project specific information will be hosted on separate web sites and This paper will present an overview of the resources hosted on the Radioecology Exchange inviting other scientists to contribute. Highlighted aspects of the site include: Social media (News blog, Twitter, Facebook) - Items announcing project outputs, training courses, jobs, studentships etc. Virtual laboratory - Information which encourages integration through joint research and integrated use of data and sample materials. These pages will focus on three categories: (1) Methodological: descriptions and video clips of commonly used analytical methods and protocols and the procedures used in STAR and COMET; (2) Informative: databases made available by STAR/COMET partners together with details of sample archives held. Fact-sheets on radio-ecologically important radionuclides and 'topical descriptions' which show absorbed

  11. Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS (United States)

    Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.


    The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes

  12. Preparation of radioactive acetyl-l-carnitine by an enzymatic exchange reaction

    Energy Technology Data Exchange (ETDEWEB)

    Emaus, R.; Bieber, L.L.


    A rapid method for the preparation of (1-/sup 14/C)acetyl-L-carnitine is described. The method involves exchange of (1-/sup 14/C)acetic acid into a pool of unlabeled acetyl-L-carnitine using the enzymes acetyl-CoA synthetase and carnitine acetyltransferase. After isotopic equilibrium is attained, radioactive acetylcarnitine is separated from the other reaction components by chromatography on Dowex 1 (C1/sup -/) anion exchange resin. One of the procedures used to verify the product (1-/sup 14/C)acetyl-L-carnitine can be used to synthesize (3S)-(5-/sup 14/C)citric acid.

  13. Dual temperature dual pressure water-hydrogen chemical exchange for water detritiation

    Energy Technology Data Exchange (ETDEWEB)

    Sugiyama, Takahiko, E-mail: [Faculty of Engineering, Nagoya University, Fro-cho 1, Chikusa-ku, Nagoya 464-8603 (Japan); Takada, Akito; Morita, Youhei [Faculty of Engineering, Nagoya University, Fro-cho 1, Chikusa-ku, Nagoya 464-8603 (Japan); Kotoh, Kenji [Graduate School of Engineering, Kyushu University, Moto-oka 744, Nishi-ku, Fukuoka 819-0395 (Japan); Munakata, Kenzo [Faculty of Engineering and Resource Science, Akita University, Tegata-gakuen-machi 1-1, Akita 010-8502 (Japan); Taguchi, Akira [Hydrogen Isotope Research Center, University of Toyama, Gofuku 3190, Toyama 930-8555 (Japan); Kawano, Takao; Tanaka, Masahiro; Akata, Naofumi [National Institute for Fusion Science, Oroshi-cho 322-6, Toki, Gifu 509-5292 (Japan)


    Experimental and analytical studies on hydrogen-tritium isotope separation by a dual temperature dual pressure catalytic exchange (DTDP-CE) with liquid phase chemical exchange columns were carried out in order to apply it to a part of the water detritiation system for DEMO fuel cycle. A prototype DTDP-CE apparatus was successfully operated and it was confirmed that tritium was separated by the apparatus as significantly distinguishable. A calculation code was developed based on the channeling stage model. The values of separation factors and the effects of some operating parameters were well predicted by the separative analyses with the code.

  14. Sea ice control of water isotope transport to Antarctica and implications for ice core interpretation (United States)

    Noone, David; Simmonds, Ian


    Sea ice in the Southern Ocean is important for Antarctic climate and hydrology. The dependence of water isotope abundance (δ18O and deuterium excess) on the winter sea ice state is examined with the isotopic version of the Melbourne University general circulation model. Reductions in the ice concentration provide warmer temperatures in winter and allow higher precipitation totals further south, while the reverse occurs with increased ice extent. The model shows clear demarcation between the changes in the isotopic conditions over the sea ice pack, where local changes in surface exchange dominate, and those of the continent interior, which depend on the long-ranged transport aloft. While less sensitive to the forcing, the interior response is influenced by changes in turbulent mixing over the ice pack and modification of the vertical transport associated with diabatic heating. The interior deuterium excess response is more strongly affected by sea ice as it captures changes in temperature over the ice rather than just the final vapor mass. Traditional reconstruction of temperature from a single isotopic nuclide would give erroneous interpretation of change in the global mean temperature unless the sea ice changes in parallel; instead, the spatial structure of the sea ice response gives some hope for extracting past sea ice conditions from multicore analysis. This study begins to explore the role of entropy production during transport such that the isotopic interpretation is more closely tied to the dynamics of the atmosphere than is expressed by idealized parcel analysis.

  15. Simulation of charge exchange neutrals interactions with gaps in first wall cladding

    Energy Technology Data Exchange (ETDEWEB)

    Kurnaev, V.A. [Moscow Engineering and Physics Institute, Kashirskoe sh. 31, 115409 Moscow (Russian Federation)]. E-mail:; Matveev, D.I. [Moscow Engineering and Physics Institute, Kashirskoe sh. 31, 115409 Moscow (Russian Federation); Trifonov, N.N. [Moscow Engineering and Physics Institute, Kashirskoe sh. 31, 115409 Moscow (Russian Federation)


    Angular distributions of particles impinging PFC in fusion devices with magnetic confinement are briefly discussed. It is shown that simulation of charge exchange neutrals interaction with the first wall should be made for inclined incidence of particles. Particle reflection coefficients and sputtering yields for gaps in Be, C and W first wall cladding are found with Monte Carlo computer simulations for hydrogen isotopes in the energy range {approx}5-5 x 10{sup 3} eV as well as for the flux integrated over the ITER charge exchange neutrals energy spectrum. Trapping of deuterons by the gap in the W wall increases two times (up to {approx}0.6) as compared with the flat surface, while trapping in the Be gap is close to unity. The influence of isotope mass on trapping and sputtering is shown to follow data for the flat surface. Roughness of gap sidewalls taken into account slightly contributes to calculated data.

  16. Anthropogenic lead isotopes in Antarctica (United States)

    Rosman, K. J. R.; Chisholm, W.; Boutron, C. F.; Candelone, J.-P.; Patterson, C. C.


    We report the first measurements of Pb isotopes in Antarctic snow, which show that even recent snow containing 2.3 pg/g is highly polluted with anthropogenic Pb. This follows from a comparison of isotope abundances of Pb in surface snow and terrestrial dust extracted from ancient Antarctic ice (Dome C, depth 308 m, approximate age 7,500 a BP), the latter being distinctly more radiogenic. This result is dependent of geochemical arguments based on measurements of Al, Na and SO4. South America is suggested as a likely source of this anthropogenic Pb. The presence of significantly less radiogenic Pb in the snow adjacent to two Antarctic base stations indicates that there is contamination from station emissions, although emission from Australia is an alternative explanation for a site 33 km from Dumont d'Urville.

  17. Neodymium associated with foraminiferal carbonate as a recorder of seawater isotopic signatures (United States)

    Tachikawa, Kazuyo; Piotrowski, Alexander M.; Bayon, Germain


    Neodymium isotopic ratios in marine environments have been used as a tracer of water masses and exchange processes between dissolved and particulate phases. The interest in this tracer has been growing with improvement of our knowledge on its chemical behaviour in the modern ocean and the identification of sedimentary phases that preserve past seawater ɛNd values. In the last few decades the Nd isotopic composition measured on Fe-Mn crusts, sediment leachates, bulk carbonate fraction, corals and fish teeth have been increasingly interpreted in the context of understanding the role of the ocean in paleoclimate changes. In particular, calcareous foraminiferal tests (shells) have acquired increasing attention as an archive of seawater Nd isotopic signatures, because it allows continuous high-resolution records to be measured and directly compared to other proxies including stable isotopes and trace metals. The main challenge of interpreting the Nd isotopic composition of foraminifera is determining the origin of the Nd preserved within them. In this review, we present an overview of methodological progress including that of bulk foraminifera and microanalyses within foraminiferal tests, as well as geochemical meaning of extracted Nd concentrations and isotopic compositions. The growing body of evidence suggests that Nd isotopic signatures of sedimentary planktonic foraminifera correspond to bottom water values rather than surface water ones. The Nd-rich phases associated with sedimentary foraminifera are adhesive nano-scale particles of Mn and Fe oxides and hydroxides, and Mn-rich carbonates formed within layers of foraminiferal calcite. Mechanical cleaning to remove clay minerals is likely to be sufficient in most cases to reconstruct past bottom water circulations. Unresolved issues include the potential influence of pore water Nd on ɛNd values extracted from sedimentary foraminiferal tests under different sedimentalogical and oceanographic conditions.

  18. Precise determination of the isotopic composition of potassium: Application to terrestrial rocks and lunar soils (United States)

    Humayun, Munir; Clayton, Robert N.


    We detail a method for the precise and accurate determination of isotopic variations in the 41K/39K ratio with a precision of ±0.5‰ (2 σm). Purified potassium is chemically extracted from rocks, soils, minerals, or solutions by ion exchange chromatography. Complete chemical yields (>99.8%) are achieved in order to avoid laboratory-induced isotopic fractionations. The purified potassium is converted to a glass by melting with barium borate flux, and the resultant bead is mounted for ion probe analysis. The SIMS method utilized by the ion probe produces extremely stable K+ ion beams, with no measurable temporal variability in the isotope ratio. The instrumental fractionation is steady at about -4‰, and is corrected for by measurement of a standard. The measurement of gravimetrically prepared isotopic standards indicates that the method is accurate at the stated level of precision and free of egregious errors. Analysis of terrestrial samples including peridotite, basalts, granites, carbonatite, biotite schists, and seawater, indicate the complete absence of isotopic variations in δ41 1K among terrestrial materials at the 0.5%o level. Application to lunar soils and a regolith breccia confirms previously observed large isotopic fractionation effects (Garner et al., 1975a; Church et al., 1976). Some lunar soils, e.g., 14163, are shown to have large sample heterogeneity (≈7%o), while others, e.g., soils and a regolith breccia at several Apollo 15 sites (Station 7/9), are homogeneous at the level of analytical precision. The presence of potassium isotopic effects in bulk soils (up to +12.7‰ in this study) with magnitudes comparable to the Rayleigh fractionation factor (25‰) indicates that volatility during micrometeorite impact melting played a large role in lunar regolith formation. As much as 15% of the regolith potassium has been lost from the Moon, through the tenuous lunar atmosphere.

  19. Isotope fractionation of cadmium in lunar material (United States)

    Schediwy, S.; Rosman, K. J. R.; de Laeter, J. R.


    The double spike technique has been used to measure the isotope fractionation and elemental abundance of Cd in nine lunar samples, the Brownfield meteorite and the Columbia River Basalt BCR-1, by thermal ionisation mass spectrometry. Lunar soil samples give a tightly grouped set of positive isotope fractionation values of between + 0.42% and + 0.50% per mass unit. Positive isotope fractionation implies that the heavy isotopes are enhanced with respect to those of the Laboratory Standard. A vesicular mare basalt gave zero isotope fractionation, indicating that the Cd isotopic composition of the Moon is identical to that of the Earth. A sample of orange glass from the Taurus-Littrow region gave a negative isotope fractionation of - 0.23 ± 0.06% per mass unit, presumably as a result of redeposition of Cd from the Cd-rich vapour cloud associated with volcanism. Cadmium is by far the heaviest element to show isotope fractionation effects in lunar samples. The volatile nature of Cd is of importance in explaining these isotope fractionation results. Although a number of mechanisms have been postulated to be the cause of isotope fractionation of certain elements in lunar soils, we believe that the most likely mechanisms are ion and particle bombardment of the lunar surface.

  20. Anthropogenic lead isotopes in Antarctica

    Energy Technology Data Exchange (ETDEWEB)

    Rosman, K.J.R.; Chisholm, W. [Curtin Univ. of Technology, Bentley (Australia); Boutron, C.F. [Laboratoire de Glaciologie et Geophysique de l`Environnement du CNRS, St. Martin d`Heres (France)]|[Domaine Universitaire, Grenoble (France); Candelone, J.P. [Laboratoire de Glaciologie et Geophysique de l`Environnement du CNRS, St. Martin d`Heres (France); Patterson, C.C. [California Institute of Technology, Pasadena, CA (United States)


    The authors present results from the first Pb isotopic study of the sources of lead in snow samples from the Antarctic. Samples of recent snow fields were compared with measurements of samples taken from deep cores, and they reveal that recent snows show pronounced influence of anthropogenic sources. These results are independent of geochemical arguments based on influences of Al, Na, or SO{sub 4}.

  1. 78 FR 69910 - Joint Industry Plan; BATS Exchange, Inc., BATS-Y Exchange, Inc., BOX Options Exchange LLC, C2... (United States)


    ... COMMISSION Joint Industry Plan; BATS Exchange, Inc., BATS-Y Exchange, Inc., BOX Options Exchange LLC, C2... LLC, NYSE Arca, Inc. and Topaz Exchange, LLC; Notice of Filing of Proposed National Market System Plan... and Exchange Commission (``Commission'') the proposed National Market System (``NMS'') Plan Governing...

  2. Comparative isotope ecology of African great apes. (United States)

    Oelze, Vicky M; Fahy, Geraldine; Hohmann, Gottfried; Robbins, Martha M; Leinert, Vera; Lee, Kevin; Eshuis, Henk; Seiler, Nicole; Wessling, Erin G; Head, Josephine; Boesch, Christophe; Kühl, Hjalmar S


    The isotope ecology of great apes is a useful reference for palaeodietary reconstructions in fossil hominins. As extant apes live in C3-dominated habitats, variation in isotope signatures is assumed to be low compared to hominoids exploiting C4-plant resources. However, isotopic differences between sites and between and within individuals are poorly understood due to the lack of vegetation baseline data. In this comparative study, we included all species of free-ranging African great apes (Pan troglodytes, Pan paniscus, Gorilla sp.). First, we explore differences in isotope baselines across different habitats and whether isotopic signatures in apes can be related to feeding niches (faunivory and folivory). Secondly, we illustrate how stable isotopic variations within African ape populations compare to other extant and extinct primates and discuss possible implications for dietary flexibility. Using 701 carbon and nitrogen isotope data points resulting from 148 sectioned hair samples and an additional collection of 189 fruit samples, we compare six different great ape sites. We investigate the relationship between vegetation baselines and climatic variables, and subsequently correct great ape isotope data to a standardized plant baseline from the respective sites. We obtained temporal isotopic profiles of individual animals by sectioning hair along its growth trajectory. Isotopic signatures of great apes differed between sites, mainly as vegetation isotope baselines were correlated with site-specific climatic conditions. We show that controlling for plant isotopic characteristics at a given site is essential for faunal data interpretation. While accounting for plant baseline effects, we found distinct isotopic profiles for each great ape population. Based on evidence from habituated groups and sympatric great ape species, these differences could possibly be related to faunivory and folivory. Dietary flexibility in apes varied, but temporal variation was overall

  3. Oxygen- and magnesium-isotope compositions of calcium-aluminum-rich inclusions from CR2 carbonaceous chondrites (United States)

    Makide, Kentaro; Nagashima, Kazuhide; Krot, Alexander N.; Huss, Gary R.; Hutcheon, Ian D.; Bischoff, Addi


    We report both oxygen- and magnesium-isotope compositions measured in situ using a Cameca ims-1280 ion microprobe in 20 of 166 CAIs identified in 47 polished sections of 15 CR2 (Renazzo-type) carbonaceous chondrites. Two additional CAIs were measured for oxygen isotopes only. Most CR2 CAIs are mineralogically pristine; only few contain secondary phyllosilicates, sodalite, and carbonates - most likely products of aqueous alteration on the CR2 chondrite parent asteroid. Spinel, hibonite, grossite, anorthite, and melilite in 18 CAIs have 16O-rich (Δ 17O = -23.3 ± 1.9‰, 2 σ error) compositions and show no evidence for postcrystallization isotopic exchange commonly observed in CAIs from metamorphosed CV carbonaceous chondrites. The inferred initial 26Al/ 27Al ratios, ( 26Al/ 27Al) 0, in 15 of 16 16O-rich CAIs measured are consistent with the canonical value of (4.5-5) × 10 -5 and a short duration (magnesium and lower-than-canonical 26Al abundance. Another 16O-enriched (Δ 17O = -20.3 ± 1.2‰) inclusion, a spinel-melilite CAI fragment Gao-Guenie (b) #3, has highly-fractionated oxygen- and magnesium-isotope compositions (˜11 and 23‰/amu, respectively), a deficit of 26Mg, and a relatively low ( 26Al/ 27Al) 0 = (2.0 ± 1.7) × 10 -5. This could be the first FUN ( Fractionation and Unidentified Nuclear effects) CAI found in CR2 chondrites. Because this inclusion is slightly 16O-depleted compared to most CR2 CAIs and has lower than the canonical ( 26Al/ 27Al) 0, it may have experienced multistage formation from precursors with nonsolar magnesium-isotope composition and recorded evolution of oxygen-isotope composition in the early solar nebula over 0.9+2.2-0.7 My. Eight of the 166 CR2 CAIs identified are associated with chondrule materials, indicating that they experienced late-stage, incomplete melting during chondrule formation. Three of these CAIs show large variations in oxygen-isotope compositions (Δ 17O ranges from -23.5‰ to -1.7‰), suggesting dilution by

  4. Characterizing the dynamics of alpha-synuclein oligomers using hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Betzer, Cristine; Jensen, Poul H


    SN (residues 94-140) underwent isotopic exchange very rapidly, demonstrating a highly dynamic region in the oligomeric state. Three regions (residues 4-17, 39-54, and 70-89) were strongly protected against isotopic exchange in the oligomers, indicating the presence of a stable hydrogen-bonded or solvent...... hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS), we have analyzed the structural dynamics of soluble αSN oligomers. The analyzed oligomers were metastable, slowly dissociating to monomers over a period of 21 days, after excess monomer had been removed. The C-terminal region of α...... analyses performed on αSN fibrils and indicated a possible zipperlike maturation mechanism for αSN aggregates. We find the protected N-terminus (residues 4-17) to be of particular interest, as this region has previously been observed to be highly dynamic for both monomeric and fibrillar αSN. This region...

  5. Liquid/liquid heat exchanger (United States)

    Miller, C. G.


    Conceptual design for heat exchanger, utilizing two immiscible liquids with dissimilar specific gravities in direct contact, is more efficient mechanism of heat transfer than conventional heat exchangers with walls or membranes. Concept could be adapted for collection of heat from solar or geothermal sources.

  6. Educators Exchange: A Program Evaluation. (United States)

    Armstrong, William B.

    The Educators Exchange Program (EEP) was established under a training and educational exchange agreement reached by California's San Diego Community College District (SDCCD) and the republic of Mexico. In the program, the District provided a 4-week technological training program to faculty at Centros de Capacitacion Tecnologica Industrial…

  7. Risk Balance in Exchange Protocols

    NARCIS (Netherlands)

    M.T. Dashti (Mohammad); Y. Wang (Yanjing); I. Cervesato


    htmlabstractWe study the behaviour of rational agents in exchange protocols which rely on trustees. We allow malicious parties to compromise the trustee by paying a cost and, thereby, present a game analysis that advocates exchange protocols which induce balanced risks on the participants. We also

  8. Professional Exchange: Mapping the Future. (United States)

    Dingman, Robert L.


    New associate editor of Professional Exchange section of "Journal of Mental Health Counseling" discusses importance of section. Lists potential topics suggested in 1989, then adds several other topics to the list. Concludes with guidelines for submission to Professional Exchange section. (NB)

  9. WWW Table of Radioactive Isotopes (United States)

    Firestone, R. B.; Ekstrom, L. P.; Chu, S. Y. F.


    An electronic sequel to the Table of Radioactive Isotopes (John Wiley, 1986) is being developed for use on the WWW. Updated adopted and decay data from the Evaluated Nuclear Structure Decay File (ENSDF) and other sources have been combined and edited. Decay scheme normalizations are revised when necessary. Gamma-ray and alpha-particle energies can be searched interactively by energy or parent half-life, mass, and atomic or neutron number. Summary data including half-lives, Q-values, production mode(s), genetic feedings, and a list of references published since the last full evaluation are available. Users can display energy or intensity ordered tables of gamma-rays, K and L x-rays, alpha-particles, and beta endpoints. Spectra of betas and bremsstrahlung, and Auger/conversion electrons can be viewed with an interactive JAVA applet. Decay schemes can be displayed with the JAVA version of Isotope Explorer 3.0. The URL for the Table of Radioactive Isotopes is

  10. Oxygen release and exchange in niobium oxide MEHPPV hybrid solar cells

    DEFF Research Database (Denmark)

    Lira-Cantu, M.; Norrman, K.; Andreasen, J.W.


    exchange was demonstrated using O-18(2)-isotopic labeling in combination with time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging analysis of devices and oxide substrates. TOF-SIMS depth profiling confirmed O-18 incorporation throughout the device in hybrid solar cells. The results...... are discussed in the context of hybrid solar cell stability and illuminate one of the degradation paths....

  11. Heat exchanger leakage problem location

    Directory of Open Access Journals (Sweden)

    Jícha Miroslav


    Full Text Available Recent compact heat exchangers are very often assembled from numerous parts joined together to separate heat transfer fluids and to form the required heat exchanger arrangement. Therefore, the leak tightness is very important property of the compact heat exchangers. Although, the compact heat exchangers have been produced for many years, there are still technological problems associated with manufacturing of the ideal connection between the individual parts, mainly encountered with special purpose heat exchangers, e.g. gas turbine recuperators. This paper describes a procedure used to identify the leakage location inside the prime surface gas turbine recuperator. For this purpose, an analytical model of the leaky gas turbine recuperator was created to assess its performance. The results obtained are compared with the experimental data which were acquired during the recuperator thermal performance analysis. The differences between these two data sets are used to indicate possible leakage areas.

  12. Next Generation Microchannel Heat Exchangers

    CERN Document Server

    Ohadi, Michael; Dessiatoun, Serguei; Cetegen, Edvin


    In Next Generation Microchannel Heat Exchangers, the authors’ focus on the new generation highly efficient heat exchangers and presentation of novel data and technical expertise not available in the open literature.  Next generation micro channels offer record high heat transfer coefficients with pressure drops much less than conventional micro channel heat exchangers. These inherent features promise fast penetration into many mew markets, including high heat flux cooling of electronics, waste heat recovery and energy efficiency enhancement applications, alternative energy systems, as well as applications in mass exchangers and chemical reactor systems. The combination of up to the minute research findings and technical know-how make this book very timely as the search for high performance heat and mass exchangers that can cut costs in materials consumption intensifies.

  13. High Temperature Heat Exchanger Project

    Energy Technology Data Exchange (ETDEWEB)

    Anthony E. Hechanova, Ph.D.


    The UNLV Research Foundation assembled a research consortium for high temperature heat exchanger design and materials compatibility and performance comprised of university and private industry partners under the auspices of the US DOE-NE Nuclear Hydrogen Initiative in October 2003. The objectives of the consortium were to conduct investigations of candidate materials for high temperature heat exchanger componets in hydrogen production processes and design and perform prototypical testing of heat exchangers. The initial research of the consortium focused on the intermediate heat exchanger (located between the nuclear reactor and hydrogen production plan) and the components for the hydrogen iodine decomposition process and sulfuric acid decomposition process. These heat exchanger components were deemed the most challenging from a materials performance and compatibility perspective

  14. Ternary effects on the gas exchange of isotopologues of carbon dioxide. (United States)

    Farquhar, Graham D; Cernusak, Lucas A


    The ternary effects of transpiration rate on the rate of assimilation of carbon dioxide through stomata, and on the calculation of the intercellular concentration of carbon dioxide, are now included in standard gas exchange studies. However, the equations for carbon isotope discrimination and for the exchange of oxygen isotopologues of carbon dioxide ignore ternary effects. Here we introduce equations to take them into account. The ternary effect is greatest when the leaf-to-air vapour mole fraction difference is greatest, and its impact is greatest on parameters derived by difference, such as the mesophyll resistance to CO(2) assimilation, r(m) . We show that the mesophyll resistance to CO(2) assimilation has been underestimated in the past. The impact is also large when there is a large difference in isotopic composition between the CO(2) inside the leaf and that in the air. We show that this partially reconciles estimates of the oxygen isotopic composition of CO(2) in the chloroplast and mitochondria in the light and in the dark, with values close to equilibrium with the estimated oxygen isotopic composition of water at the sites of evaporation within the leaf. © 2012 Blackwell Publishing Ltd.

  15. Fault-Tolerant Heat Exchanger (United States)

    Izenson, Michael G.; Crowley, Christopher J.


    A compact, lightweight heat exchanger has been designed to be fault-tolerant in the sense that a single-point leak would not cause mixing of heat-transfer fluids. This particular heat exchanger is intended to be part of the temperature-regulation system for habitable modules of the International Space Station and to function with water and ammonia as the heat-transfer fluids. The basic fault-tolerant design is adaptable to other heat-transfer fluids and heat exchangers for applications in which mixing of heat-transfer fluids would pose toxic, explosive, or other hazards: Examples could include fuel/air heat exchangers for thermal management on aircraft, process heat exchangers in the cryogenic industry, and heat exchangers used in chemical processing. The reason this heat exchanger can tolerate a single-point leak is that the heat-transfer fluids are everywhere separated by a vented volume and at least two seals. The combination of fault tolerance, compactness, and light weight is implemented in a unique heat-exchanger core configuration: Each fluid passage is entirely surrounded by a vented region bridged by solid structures through which heat is conducted between the fluids. Precise, proprietary fabrication techniques make it possible to manufacture the vented regions and heat-conducting structures with very small dimensions to obtain a very large coefficient of heat transfer between the two fluids. A large heat-transfer coefficient favors compact design by making it possible to use a relatively small core for a given heat-transfer rate. Calculations and experiments have shown that in most respects, the fault-tolerant heat exchanger can be expected to equal or exceed the performance of the non-fault-tolerant heat exchanger that it is intended to supplant (see table). The only significant disadvantages are a slight weight penalty and a small decrease in the mass-specific heat transfer.

  16. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream (United States)

    Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken


    ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying

  17. A Hydrogen Exchange Method Using Tritium and Sephadex: Its Application to Ribonuclease* (United States)

    Englander, S. Walter


    A new method for measuring the hydrogen exchange of macromolecules in solution is described. The method uses tritium to trace the movement of hydrogen, and utilizes Sephadex columns to effect, in about 2 minutes, a separation between tritiated macromolecule and tritiated solvent great enough to allow the measurement of bound tritium. High sensitivity and freedom from artifact is demonstrated and the possible value of the technique for investigation of other kinds of colloid-small molecule interaction is indicated. Competition experiments involving tritium, hydrogen, and deuterium indicate the absence of any equilibrium isotope effect in the ribonuclease-hydrogen isotope system, though a secondary kinetic isotope effect is apparent when ribonuclease is largely deuterated. Ribonuclease shows four clearly distinguishable kinetic classes of exchangeable hydrogens. Evidence is marshaled to suggest the independently measurable classes II, III, and IV (in order of decreasing rate of exchange) to represent “random-chain” peptides, peptides involved in α-helix, and otherwise shielded side-chain and peptide hydrogens, respectively. PMID:14075117

  18. Evaporation from the shallow Lake Massaciuccoli (Tuscany, Italy) studied using stable isotopes and evaporation pan data (United States)

    Baneschi, I.; Gonfiantini, R.; Guidi, M.


    Oxygen and hydrogen isotope variations monitored in Lake Massaciuccoli (7 km2, 2 m deep, seasonally variable water level) during summer 2008, were compared with those observed in a Class A evaporation pan (diameter 120.6 cm, depth 25.4 cm) placed on the lake eastern shore. Air temperature, pressure, relative humidity, wind speed and direction, solar radiation, water temperature in the lake and the pan were also measured. The pluviometer indicated that no precipitation occurred during the study period. The pan was initially filled with groundwater up to the level of 19.2 cm (219 L), depleted in heavy isotopes with respect to tha lake water. Sodium chloride was added up to the concentration of 1 g×L-1, which is assumed do not affect significantly the evaporation rate till the water volume is reduced to less than 10 %. The Cl- concentration was used to provide an estimation of the evaporated water fraction, in addition to the micrometer measuring the water level variations. The pan water was sampled every 2-3 days and Cl- and stable isotopes determined. The set of stable isotope and evaporation data enabled us to compute the parameters governing the evaporation process and the isotopic exchanges with the atmospheric moisture, according to the procedure proposed by Gonfiantini (1986). The values were applied to test three working hypotheses of water balance of Lake Massaciuccoli: (i) surface inflow and outflow of liquid water are negligible and only evaporation is important; (ii) the inflow is negligible and outflow and evaporation are both significant; (iii) the three terms of balance are all important but the losses by evaporation and outflow exceed inflow (as the lake water level was decreasing). Water exchanges with groundwater are considered negligible. The best agreement between lake and pan data was obtained with the second hypothesis, for which the fraction of water removed by evaporation was estimated to be about 40 % ot he total water losses. This residual

  19. Influence of water on clumped-isotope bond reordering kinetics in calcite (United States)

    Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.


    Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external

  20. Electrically switched ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lilga, M.A. [Pacific Northwest National Lab., Richland, WA (United States); Schwartz, D.T.; Genders, D.


    A variety of waste types containing radioactive {sup 137}Cs are found throughout the DOE complex. These waste types include water in reactor cooling basins, radioactive high-level waste (HLW) in underground storage tanks, and groundwater. Safety and regulatory requirements and economics require the removal of radiocesium before these wastes can be permanently disposed of. Electrically Switched Ion Exchange (ESIX) is an approach for radioactive cesium separation that combines IX and electrochemistry to provide a selective, reversible, and economic separation method that also produces little or no secondary waste. In the ESIX process, an electroactive IX film is deposited electrochemically onto a high-surface area electrode, and ion uptake and elution are controlled directly by modulating the potential of the film. For cesium, the electroactive films under investigation are ferrocyanides, which are well known to have high selectivities for cesium in concentrated sodium solutions. When a cathode potential is applied to the film, Fe{sup +3} is reduced to the Fe{sup +2} state, and a cation must be intercalated into the film to maintain charge neutrality (i.e., Cs{sup +} is loaded). Conversely, if an anodic potential is applied, a cation must be released from the film (i.e., Cs{sup +} is unloaded). Therefore, to load the film with cesium, the film is simply reduced; to unload cesium, the film is oxidized.

  1. Isotope Geochemistry for Comparative Planetology of Exoplanets (United States)

    Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.


    Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

  2. Deformation properties of lead isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Tolokonnikov, S. V.; Borzov, I. N.; Lutostansky, Yu. S.; Saperstein, E. E., E-mail: [National Research Center Kurchatov Institute (Russian Federation)


    The deformation properties of a long lead isotopic chain up to the neutron drip line are analyzed on the basis of the energy density functional (EDF) in the FaNDF{sup 0} Fayans form. The question of whether the ground state of neutron-deficient lead isotopes can have a stable deformation is studied in detail. The prediction of this deformation is contained in the results obtained on the basis of the HFB-17 and HFB-27 Skyrme EDF versions and reported on Internet. The present analysis reveals that this is at odds with experimental data on charge radii and magnetic moments of odd lead isotopes. The Fayans EDF version predicts a spherical ground state for all light lead isotopes, but some of them (for example, {sup 180}Pb and {sup 184}Pb) prove to be very soft—that is, close to the point of a phase transition to a deformed state. Also, the results obtained in our present study are compared with the predictions of some other Skyrme EDF versions, including SKM*, SLy4, SLy6, and UNE1. By and large, their predictions are closer to the results arising upon the application of the Fayans functional. For example, the SLy4 functional predicts, in just the same way as the FaNDF{sup 0} functional, a spherical shape for all nuclei of this region. The remaining three Skyrme EDF versions lead to a deformation of some light lead isotopes, but their number is substantially smaller than that in the case of the HFB-17 and HFB-27 functionals. Moreover, the respective deformation energy is substantially lower, which gives grounds to hope for the restoration of a spherical shape upon going beyond the mean-field approximation, which we use here. Also, the deformation properties of neutron-rich lead isotopes are studied up to the neutron drip line. Here, the results obtained with the FaNDF{sup 0} functional are compared with the predictions of the HFB-17, HFB-27, SKM*, and SLy4 Skyrme EDF versions. All of the EDF versions considered here predict the existence of a region where neutron

  3. Isotopic Compositions of the Elements 1997 (United States)

    Rosman, K. J. R.; Taylor, P. D. P.


    The Commission's Subcommittee for the Isotopic Composition of the Elements has carried out its biennial review of isotopic compositions, as determined by mass spectrometry and other relevant methods. This involves a critical evaluation of the published literature, element by element, and forms the basis of the Table of Isotopic Compositions of the Elements as Determined by Mass Spectrometry presented here. New guidelines have been used to arrive at the uncertainties on the isotopic abundances and there are numerous changes to the table since it was last published in 1991. Atomic Weights calculated from this table are consistent with Ar(E) values listed in the Table of Standard Atomic Weights 1997.

  4. Stable isotope labeling methods for DNA. (United States)

    Nelissen, Frank H T; Tessari, Marco; Wijmenga, Sybren S; Heus, Hans A


    NMR is a powerful method for studying proteins and nucleic acids in solution. The study of nucleic acids by NMR is far more challenging than for proteins, which is mainly due to the limited number of building blocks and unfavorable spectral properties. For NMR studies of DNA molecules, (site specific) isotope enrichment is required to facilitate specific NMR experiments and applications. Here, we provide a comprehensive review of isotope-labeling strategies for obtaining stable isotope labeled DNA as well as specifically stable isotope labeled building blocks required for enzymatic DNA synthesis. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Isotopic investigation of an Australian island environment

    Energy Technology Data Exchange (ETDEWEB)

    Groecke, D.R. [Australian National Univ., Canberra, ACT (Australia). Research School of Earth Sciences; Bocherens, H. [Paris-6 Univ., 75 (France)


    Collagen has been extracted from fossil bones of mega-fauna herbivores from Kangaroo Island, South Australia (Australia). Carbon and nitrogen stable isotope analyses of collagen have provided an insight into the palaeo-ecology of these late Pleistocene herbivores. In comparison with continental fossil localities in South Australia, the island herbivores have elevated nitrogen isotopic abundances. Carbon isotopic abundances suggest that browsing species had a mixed diet of grasses and leaves on the island, in contrast to the specimens from mainland Australia. Possible causes regarding elevated nitrogen isotope abundances and dietary shifts in this palaeo-ecology are discussed. (authors). 24 refs., 2 figs., 1 tab.

  6. Custom, contract, and kidney exchange. (United States)

    Healy, Kieran; Krawiec, Kimberly D


    In this Essay, we examine a case in which the organizational and logistical demands of a novel form of organ exchange (the nonsimultaneous, extended, altruistic donor (NEAD) chain) do not map cleanly onto standard cultural schemas for either market or gift exchange, resulting in sociological ambiguity and legal uncertainty. In some ways, a NEAD chain resembles a form of generalized exchange, an ancient and widespread instance of the norm of reciprocity that can be thought of simply as the obligation to “pay it forward” rather than the obligation to reciprocate directly with the original giver. At the same time, a NEAD chain resembles a string of promises and commitments to deliver something in exchange for some valuable consideration--that is, a series of contracts. Neither of these salient "social imaginaries" of exchange--gift giving or formal contract--perfectly meets the practical demands of the NEAD system. As a result, neither contract nor generalized exchange drives the practice of NEAD chains. Rather, the majority of actual exchanges still resemble a simpler form of exchange: direct, simultaneous exchange between parties with no time delay or opportunity to back out. If NEAD chains are to reach their full promise for large-scale, nonsimultaneous organ transfer, legal uncertainties and sociological ambiguities must be finessed, both in the practices of the coordinating agencies and in the minds of NEAD-chain participants. This might happen either through the further elaboration of gift-like language and practices, or through a creative use of the cultural form and motivational vocabulary, but not necessarily the legal and institutional machinery, of contract.

  7. Hydrogen and oxygen isotope values in hydrogen peroxide. (United States)

    Barnette, Janet E; Lott, Michael J; Howa, John D; Podlesak, David W; Ehleringer, James R


    Hydrogen peroxide (H(2)O(2)) is a widely used oxidizer with many commercial applications; unfortunately, it also has terrorist-related uses. We analyzed 97 hydrogen peroxide solutions representing four grades purchased across the United States and in Mexico. As expected, the range of hydrogen (δ(2)H, 230‰) and oxygen (δ(18)O, 24‰) isotope values of the H(2)O(2) solutions was large, reflecting the broad isotopic range of dilution waters. This resulted in predictable linear relationships of δ(2)H and δ(18)O values of H(2)O(2) solutions that were near parallel to the Meteoric Water Line (MWL), offset by the concentration of H(2)O(2) in the solution. By grade, dilute (3 to 35%) H(2)O(2) solutions were not statistically different in slope. Although the δ(2)H values of manufactured H(2)O(2) could be different from those of water, rapid H(2)O(2)-H(2)O exchange of H atoms eliminated any distinct isotope signal. We developed a method to measure the δ(18)O value of H(2)O(2) independent of dilution water by directly measuring O(2) gas generated from a catalase-induced disproportionation reaction. We predicted that the δ(18)O values of H(2)O(2) would be similar to that of atmospheric oxygen (+23.5‰), the predominant source of oxygen in the most common H(2)O(2) manufacturing process (median disproportionated δ(18)O=23.8‰). The predictable H-O relationships in H(2)O(2) solutions make it possible to distinguish commercial dilutions from clandestine concentration practices. Future applications of this work include synthesis studies that investigate the chemical link between H(2)O(2) reagents and peroxide-based explosive products, which may assist law enforcement in criminal investigations. Copyright © 2011 John Wiley & Sons, Ltd.



    Podobeková, Veronika; Peráčková, Jana


    The article discusses utilization of heat from waste water in sewage. During the year, temperature of water in sewage ranges between 10 °C and 20 °C and the heat from sewage could be used for heating, cooling and hot water preparation in building. The heat is extracted through a transfer surface area of the heat exchanger into the heat pump, which is able to utilize the low–potential energy. Different design and types of the heat exchangers in sewage are dealt with: heat exchangers embedded i...

  9. Relational and XML Data Exchange

    CERN Document Server

    Arenas, Marcelo


    Data exchange is the problem of finding an instance of a target schema, given an instance of a source schema and a specification of the relationship between the source and the target. Such a target instance should correctly represent information from the source instance under the constraints imposed by the target schema, and it should allow one to evaluate queries on the target instance in a way that is semantically consistent with the source data. Data exchange is an old problem that re-emerged as an active research topic recently, due to the increased need for exchange of data in various for

  10. Heat exchanger using graphite foam (United States)

    Campagna, Michael Joseph; Callas, James John


    A heat exchanger is disclosed. The heat exchanger may have an inlet configured to receive a first fluid and an outlet configured to discharge the first fluid. The heat exchanger may further have at least one passageway configured to conduct the first fluid from the inlet to the outlet. The at least one passageway may be composed of a graphite foam and a layer of graphite material on the exterior of the graphite foam. The layer of graphite material may form at least a partial barrier between the first fluid and a second fluid external to the at least one passageway.

  11. Deuterium Exchange Kinetics by NMR. (United States)

    Roper, G. C.


    Describes a physical chemistry experiment which allows such concepts as kinetics, catalysis, isotope shifts, coupling constants, and the use of nuclear magnetic resonance (NMR) for quantitative work to be covered in the same exercise. Background information, experimental procedures used, and typical results obtained are included. (JN)

  12. Effects of different water storage procedures on the dissolved Fe concentration and isotopic composition of chemically contrasted waters from the Amazon River Basin. (United States)

    Mulholland, Daniel S; Poitrasson, Franck; Boaventura, Geraldo R


    Although recent studies have investigated the Fe isotopic composition of dissolved, colloidal and particulate phases from continental and oceanic natural waters, few efforts have been made to evaluate whether water sample storage and the separation of different pore-size fractions through filtration can cause any change to the Fe isotopic compositions. The present study investigates the possible biases introduced by different water storage conditions on the dissolved Fe concentration and isotopic composition of chemically different waters. Water samples were collected from an organic-rich river and from mineral particulate-rich rivers. Filtered and unfiltered water samples were stored either at room temperature or frozen at -18°C in order to assess possible biases due to (i) different water storage temperature, and (ii) storage of bulk (unfiltered) vs filtered water. Iron isotope measurements were performed by Multicollector Inductively Coupled Plasma Mass Spectrometry with a Thermo Electron Neptune instrument, after Fe purification using anion-exchange resins. Our data reveal that bulk water storage at room temperature without filtration produces minor changes in the dissolved Fe isotopic composition of mineral particulate-rich waters, but significant isotopic composition changes in organic-rich waters. In both cases, however, the impact of the different procedures on the Fe concentrations was strong. On the other hand, the bulk water stored frozen without filtration produced more limited changes in the dissolved Fe concentrations, and also on isotopic compositions, relative to the samples filtered in the field. The largest effect was again observed for the organic-rich waters. These findings suggest that a time lag between water collection and filtration may cause isotopic exchanges between the dissolved and particulate Fe fractions. When it is not possible to filter the samples in the field immediately after collection, the less detrimental approach is to

  13. δ 18O of carbonate, quartz and phosphate from belemnite guards: implications for the isotopic record of old fossils and the isotopic composition of ancient seawater (United States)

    Longinelli, Antonio; Iacumin, Paola; Ramigni, Michele


    Belemnite guards of Cretaceous and Jurassic age were found to contain varying amounts of quartz deposited both on the external surface and inside the rostrum. The oxygen isotopic composition of coexisting carbonate, quartz and phosphate from the same rostrum was measured according to well-established techniques. None of these compounds showed isotopic values in equilibrium with one another. Assuming δ18O values of the diagenetic water within the range of meteoric waters, the δ18O(SiO2) yield temperatures in agreement with the apparent secondary origin of this phase. The δ18O(CO32-) range, with a certain continuity, between -10.8 and +0.97 PDB-1 with most of the intermediate values being within the range of the carbonate isotopic values of Mesozoic fossils. The most positive isotopic results obtained from phosphate are close to +23/+24‰ (V-SMOW). They can hardly be related to a secondary origin of the phosphate, or to the presence of diagenetic effects, since these results are among the most positive ever measured on phosphate. As far as we know there is no widespread diagenetic process determining an 18O enrichment of phosphate. The very low concentration of phosphate did not allow the determination of its mineralogical composition. All the available δ18O(PO43-) values from belemnite and non-belemnite fossils of marine origin of Tertiary and Mesozoic age are reported along with the newly measured belemnites. The following conclusions may be drawn from the data reported: (1) the pristine oxygen isotope composition of fossil marine organisms (either carbonate or phosphate) may easily undergo fairly large changes because of oxygen isotope exchange processes with diagenetic water; this process is apparent even in the case of geologically recent fossils; (2) the δ18O(PO43-) of belemnite rostra seems to be, at least in the case of the most positive results, in isotopic equilibrium with environmental water because of the similarity between the results from

  14. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis. (United States)

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M


    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a

  15. Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Badcock, C.C.; Hwang, W.C.; Kalsch, J.F.


    Chemical kinetic modeling studies of vibrational-photochemical isotope enrichment have been performed on two systems: Model (I), H/sup 79/Br(H/sup 81/Br) + Cl/sub 2/ and, Model (II), H/sup 37/Cl(H/sup 35/Cl) + Br. Pulsed laser excitation was modeled to the first excited vibrational level of H/sup 79/Br in Model I and the first and second excited vibrational levels of both HCl isotopes in Model II. These are prototype systems of exoergic (Model I) and endoergic (Model II) reactions. The effects on enrichment of varying the external parameters (pressure, laser intensity) and the internal parameters (rate constants for V-V exchange and excited-state reactions) were examined. Studies of these prototype systems indicate that a favorable reaction for enrichment, with isotopically-specific excitation and a significantly accelerated vibrationally-excited-state reaction should have the following properties: the reaction from v = 0 should be only moderately exoergic, and the most favorable coreactant should be a polyatomic species, such as alkyl radical. Direct excitation of the reacting vibrational level is at least an order of magnitude more favorable for enrichment than is population by energy transfer. Enrichment of the minor isotope by these processes is more effective than is major isotope enrichment. Within limits, increased laser intensity is beneficial. However, for sequential excitation of a second vibrational level, major isotope enrichment can be diminished by high populations of the first vibrational level.

  16. Exploring the isotopic niche: isotopic variance, physiological incorporation, and the temporal dynamics of foraging

    Directory of Open Access Journals (Sweden)

    Justin Douglas Yeakel


    Full Text Available Consumer foraging behaviors are dynamic, changing in response to prey availability, seasonality, competition, and even the consumer's physiological state. The isotopic composition of a consumer is a product of these factors as well as the isotopic `landscape' of its prey, i.e. the isotopic mixing space. Stable isotope mixing models are used to back-calculate the most likely proportional contribution of a set of prey to a consumer's diet based on their respective isotopic distributions, however they are disconnected from ecological process. Here we build a mechanistic framework that links the ecological and physiological processes of an individual consumer to the isotopic distribution that describes its diet, and ultimately to the isotopic composition of its own tissues, defined as its `isotopic niche’. By coupling these processes, we systematically investigate under what conditions the isotopic niche of a consumer changes as a function of both the geometric properties of its mixing space and foraging strategies that may be static or dynamic over time. Results of our derivations reveal general insight into the conditions impacting isotopic niche width as a function of consumer specialization on prey, as well as the consumer's ability to transition between diets over time. We show analytically that moderate specialization on isotopically unique prey can serve to maximize a consumer's isotopic niche width, while temporally dynamic diets will tend to result in peak isotopic variance during dietary transitions. We demonstrate the relevance of our theoretical findings by examining a marine system composed of nine invertebrate species commonly consumed by sea otters. In general, our analytical framework highlights the complex interplay of mixing space geometry and consumer dietary behavior in driving expansion and contraction of the isotopic niche. Because this approach is established on ecological mechanism, it is well-suited for enhancing the

  17. SWING - The Stable Water Isotope Intercomparison Group (United States)

    Werner, M.; Barras, V.; Brown, J.; Gourcy, L.; Henderson-Sellers, A.; Hoffmann, G.; Ichiyanagi, K.; Kelley, M.; Noone, D.; Roads, J.; Schmidt, G.; Sturm, K.; Tindall, J.; Valdes, P.; Yoshimura, K.; Zakharov, V.


    For more than four decades the isotopic composition of water stored in various archives (e.g. ice cores, ground water) has been used to study changes in the hydrological cycle on timescales from glacial-interglacial to short term variations. However, the interpretation of isotopic variations in terms of climate change is often handicapped by a lack of other relevant observational climate parameters (e.g. temperature, relative humidity, precipitation) both in space and time. Modeling the isotopic composition of water within the hydrological cycle of general circulation models (GCM) may help to overcome this deficit on available climate data. Isotope GCMs simulate the 18O/16O (and/or 2H/1H) relation as an independent quantity within a closed "model world" where all other relevant climate parameters are known, too. This enables an improved analysis of (simulated) isotope variability in terms of climate change and during the last decade several state-of-the-art GCM models (GISS, ECHAM, LMD, GENESIS and others) have been enhanced by the capability to simulate the atmospheric and/or ocean cycle of H218O and 1H2H16O. To ensure isotope GCM reliability, any isotope GCM simulation must pass a rigorous comparison of simulated versus observed isotope data (model-data-intercomparison). In addition, artifacts in isotope simulations based on a specific GCM model parameterization or set-up have to be identified by comparing simulation results of several different isotope GCMs (model-model intercomparison). In our presentation we will give an overview and first results of the SWING project, founded in 2004. This initiative serves as a community platform for experts from the various isotope research groups and has the following objectives: (1) enable an overview about ongoing isotope GCM modeling capabilities; (2) define and perform future common GCM isotope simulation experiments of the various research groups; (3) identify the most important need of new observational isotope data

  18. Analysis of hydrogen isotope ratios by SIMS, and application to determining mineral-fluid isotope fractionation factors

    Energy Technology Data Exchange (ETDEWEB)

    Riciputi, L.R.; Chacko, T.; Cole, D.R.; Horita, J.


    Due to the large mass difference between the two isotopes, D/H ratios can be strongly affected by chemical processes. Thus, they can be sensitive monitors of fluid source, temperature, and fluid-rock interactions in geologic settings. The lack of confidence in fractionation factors has significantly hindered realization of the potential of D/H ratios in geochemical studies. The authors describe a new experimental method, relying on SIMS analysis, that allows the precise determination of mineral-water D/H fractionation factors, and the analytical considerations that are required to make both precise and accurate measurements. The development of this method is based on the fact that diffusion rates are markedly anisotropic in many hydrous minerals, varying by over five orders of magnitude depending on the crystallographic orientation. The diffusion rates can be determined by conducting controlled exchange experiments of fixed duration using isotopically labeled waters that are enriched (strongly) with D, and then measuring the depth profile by SIMS.

  19. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, K. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    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.

  20. Liquid droplet heat exchanger studies (United States)

    Bruckner, A. P.; Hedges, D. E.; Yungster, S.


    Recent analytical and experimental investigations of the liquid droplet heat exchanger (LDHX) concept for space power applications are described. The performance of the LDHX is compared to that of a conventional heat exchanger for heat rejection applications in a Brayton cycle, using the mass-specific heat exchanger effectiveness as a figure of merit. It is shown that the LDHX has an order of magnitude advantage over the conventional heat exchanger. Furthermore, significant improvement in cycle efficiency and power to mass ratio is possible. Two-phase flow experiments in a laboratory scale LDHX, using air and water as the two media, show very good agreement with the quasi-one-dimensional model used in the parametric studies.

  1. Estimating Foreign Exchange Reserve Adequacy

    Directory of Open Access Journals (Sweden)

    Abdul Hakim


    Full Text Available Accumulating foreign exchange reserves, despite their cost and their impacts on other macroeconomics variables, provides some benefits. This paper models such foreign exchange reserves. To measure the adequacy of foreign exchange reserves for import, it uses total reserves-to-import ratio (TRM. The chosen independent variables are gross domestic product growth, exchange rates, opportunity cost, and a dummy variable separating the pre and post 1997 Asian financial crisis. To estimate the risky TRM value, this paper uses conditional Value-at-Risk (VaR, with the help of Glosten-Jagannathan-Runkle (GJR model to estimate the conditional volatility. The results suggest that all independent variables significantly influence TRM. They also suggest that the short and long run volatilities are evident, with the additional evidence of asymmetric effects of negative and positive past shocks. The VaR, which are calculated assuming both normal and t distributions, provide similar results, namely violations in 2005 and 2008.

  2. VLER Health Exchange by Area (United States)

    Department of Veterans Affairs — “Connect Your Docs” through the Virtual Lifetime Electronic Record (VLER) Health Exchange program. This program gives VA and community health care providers secure...

  3. Counterflow Regolith Heat Exchanger Project (United States)

    National Aeronautics and Space Administration — The counterflow regolith heat exchanger (CoRHE) is a device that transfers heat from hot regolith to cold regolith. The CoRHE is essentially a tube-in-tube heat...

  4. Selected scientific topics of the 11th International Isotope Symposium on the Synthesis and Applications of Isotopes and Isotopically Labeled Compounds. (United States)

    Atzrodt, Jens; Derdau, Volker


    This micro-review describes hot topics and new trends in isotope science discussed at the 11th International Isotope Symposium on the Synthesis and Applications of Isotopes and Isotopically Labeled Compounds from a personal perspective. Copyright © 2013 John Wiley & Sons, Ltd.

  5. Ca isotope fingerprints of early crust-mantle evolution (United States)

    Kreissig, K.; Elliott, T.


    The utility of 40Ca/ 44Ca as a tracer of pre-existing crustal contributions in early Archaean cratons has been explored to identify traces of Hadean crust and to assess the style of continental growth. The relatively short half-life of 40K (˜1.3 Gy) means that its decay to 40Ca occurs dominantly during early Earth History. If Archaean crust had a significant component derived from a more ancient protolith, as anticipated by "steady state" crustal evolution models, this should be clearly reflected in radiogenic 40Ca/ 44Ca ratios (or positive initial ɛ Ca) in different Archaean cratons. A high precision thermal ionisation technique has been used to analyse the 40Ca/ 44Ca ratios of plagioclase separates and associated whole rocks in ˜3.6 Ga (early Archaean) samples from Zimbabwe and West Greenland. Three out of four tonalite, trondhjemite, granodiorite (TTG) suite samples from Zimbabwe display initial 40Ca/ 44Ca ratios indistinguishable from our measured modern MORB value (i.e., ɛ Ca(3.6) ˜ 0). Greenland samples, however, are very diverse ranging from ɛ Ca(3.7) = 0.1 in mafic pillow lavas and felsic sheets from the Isua supracrustal belt, up to very radiogenic signatures (ɛ Ca(3.7) = 2.9) in both mafic rocks of the Akilia association and felsic TTG from the coastal Amîtsoq gneisses. At face value, these results imply the Zimbabwe crust is juvenile whereas most Greenland samples include an earlier crustal component. Yet the west Greenland craton, as with many Archaean localities, has experienced a complex geological history and the interpretation of age-corrected initial isotope values requires great care. Both felsic and mafic samples from Greenland display ɛ Ca(3.7) so radiogenic that they are not readily explained by crustal growth scenarios. The presence of such radiogenic 40Ca/ 44Ca found in low K/Ca plagioclases requires Ca isotope exchange between plagioclase and whole rock during later metamorphic event(s). In addition the unexpectedly radiogenic Ca

  6. International Prices and Exchange Rates


    Gopinath, Gita; Burstein, Ariel


    We survey the recent empirical and theoretical developments in the literature on the relation between prices and exchange rates. After updating some of the major findings in the empirical literature we present a simple framework to interpret this evidence. We review theoretical models that generate insensitivity of prices to exchange rate changes through variable markups, both under flexible prices and nominal rigidities, first in partial equilibrium and then in general equilibrium.

  7. Exchange rate determination in Vietnam


    Thai-Ha Le


    This study investigates the determinants of the exchange rate in Vietnam and suggests policy implications. Gregory-Hansen cointegration tests and generalised variance decomposition (VDC) analysis were applied to monthly data from July 2004 to December 2013. The model was built based on the three popular approaches to exchange rate determination, which are purchasing power parity (PPP) approach, balance of payment (BOP) approach, and monetary and portfolio approach. This study finds that the p...

  8. Shared Year Exchange in Nursing

    DEFF Research Database (Denmark)

    Vedsegaard, Helle Wendner; Wederkinck, Elisabeth


    Beskrivelse af Shared Year Exchange in Nursing, et udviklingsporjekt omhandlende udvikling, beskrivelse og implementering af et fælles studieår for sygeplejerskestuderende ved Metropol og La Trobe University Australien.......Beskrivelse af Shared Year Exchange in Nursing, et udviklingsporjekt omhandlende udvikling, beskrivelse og implementering af et fælles studieår for sygeplejerskestuderende ved Metropol og La Trobe University Australien....

  9. Overview of the mechanisms that could explain the `Boundary Exchange' at the land-ocean contact (United States)

    Jeandel, Catherine


    Land to ocean transfer of material largely controls the chemical composition of seawater and the global element cycles. Oceanic isotopic budgets of chemical species, macro- and micronutrients (e.g. Nd, Sr, Si, Mg, Zn, Mo and Ni) have revealed an imbalance between their sources and sinks. Radiogenic isotope budgets underlined the importance of taking into account continental margins as a source of elements to oceans. They also highlighted that the net land-ocean inputs of chemical species probably result from particle-dissolved exchange processes, named `Boundary Exchange'. Yet, locations where `Boundary Exchange' occurs are not clearly identified and reviewed here: discharge of huge amount of freshly weathered particles at the river mouths, submarine weathering of deposited sediments along the margins, submarine groundwater discharges and subterranean estuaries. As a whole, we conclude that all of them might contribute to `Boundary Exchange'. Highlighting their specific roles and the processes at play is a key scientific issue for the second half of GEOTRACES. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

  10. Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite (United States)

    Mavromatis, Vasileios; Purgstaller, Bettina; Dietzel, Martin; Buhl, Dieter; Immenhauser, Adrian; Schott, Jacques


    reacting fluid easily converts to Mg-rich calcite via exchange and/or dissolution/precipitation reactions. The results of this study provide new insights on the acquisition of the Mg chemical and isotopic signatures by the skeletal marine carbonates precipitated in confined media from strongly supersaturated fluids. They also offer new guides for the interpretation of the isotopic signature of these organisms for paleo-environmental reconstructions.

  11. physico-chemical and stable isotopes

    African Journals Online (AJOL)

    This paper details the mineralogical, chemical and stable isotope abundances of calcrete in the Letlhakeng fossil valley. The stable isotope abundances (O and C) of calcretes yielded some values which were tested against the nature of the calcretes – pedogenic or groundwater type. The Kgalagadi (Kalahari) is a vast ...

  12. Advanced Mass Spectrometers for Hydrogen Isotope Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Chastagner, P.


    This report is a summary of the results of a joint Savannah River Laboratory (SRL) - Savannah River Plant (SRP) ''Hydrogen Isotope Mass Spectrometer Evaluation Program''. The program was undertaken to evaluate two prototype hydrogen isotope mass spectrometers and obtain sufficient data to permit SRP personnel to specify the mass spectrometers to replace obsolete instruments.

  13. Dual Carbon and Nitrogen Isotope Analysis

    African Journals Online (AJOL)

    According to Hemminga & Mateo. (1996), values of carbon and nitrogen isotope ratios vary considerably between seagrass species. It might also be expected that the remaining seagrass species could have some influence on the shrimp carbon signal. Isotopic evidence for mangroves being a carbon source for shrimps ...

  14. Isotopic niches support the resource breadth hypothesis. (United States)

    Rader, Jonathan A; Newsome, Seth D; Sabat, Pablo; Chesser, R Terry; Dillon, Michael E; Martínez Del Rio, Carlos


    Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges. We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology. We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology. Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies. © 2016 The Authors. Journal of Animal Ecology © 2016 British Ecological Society.

  15. Isotopic niches support the resource breadth hypothesis (United States)

    Rader, Jonathan A.; Newsome, Seth D.; Sabat, Pablo; Chesser, R. Terry; Dillon, Michael E.; Martinez del Rio, Carlos


    Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges.We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology.We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology.Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies.

  16. Atomic lithium vapor laser isotope separation

    CERN Document Server

    Olivares, I E


    An atomic vapor laser isotope separation in lithium was performed using tunable diode lasers. The method permits also the separation of the isotopes between the sup 6 LiD sub 2 and the sup 7 LiD sub 1 lines using a self-made mass separator which includes a magnetic sector and an ion beam designed for lithium. (Author)

  17. The isotopic dipole moment of HDO

    Energy Technology Data Exchange (ETDEWEB)

    Assafrao, Denise; Mohallem, Jose R [Laboratorio de Atomos e Moleculas Especiais, Departamento de Fisica, ICEx, Universidade Federal de Minas Gerais, CP 702, 30123-970, Belo Horizonte, MG (Brazil)


    An adiabatic variational approximation is used to study the monodeuterated water molecule, HDO, accounting for the isotopic effect. The isotopic dipole moment, pointing from D to H, is then calculated for the first time, yielding (1.5 {+-} 0.1) x 10{sup -3} Debye, being helpful in the interpretation of experiments. (fast track communication)

  18. Environmental isotopes investigation in groundwater of Challaghatta ...

    African Journals Online (AJOL)

    Radiogenic isotopes (3H and 14C) and stable isotope (18O) together with TDS, EC and salinity of water were used to discriminate qualitative and quantitative groundwater age, probable recharge time, flow respectively in groundwater of Challaghatta valley, Bangalore. The variations between TDS and EC values of sewage ...

  19. Isotope Program Report June FY2016

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jr, Benjamin E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Egle, Brian [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


    Isotope Program Monthly Highlights are briefly described. These include data on isotopes shipped, updates on equipment fabrication and testing, a potential new approach for nondestructive measurement of the amount of Cf-252 deposited on a surface, and efforts to recover and purify uranium-234 obtained from old PuBe sources.

  20. Use of Isotopes for Studying Reaction Mechanisms

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 2; Issue 8. Use of Isotopes for Studying Reaction Mechanisms-Secondary Kinetic Isotope Effect. Uday Maitra J Chandrasekhar. Series Article Volume 2 Issue 8 August 1997 pp 18-25 ...

  1. Tracing thallium contamination in soils using isotopes (United States)

    Vaněk, Aleš; Grösslová, Zuzana; Mihaljevič, Martin; Ettler, Vojtěch; Trubač, Jakub; Teper, Leslaw; Cabala, Jerzy; Rohovec, Jan; Penížek, Vít; Zádorová, Tereza; Pavlů, Lenka; Holubík, Ondřej; Drábek, Ondřej; Němeček, Karel; Houška, Jakub; Ash, Christopher


    We report the thallium (Tl) isotope record in moderately contaminated soils, which have been historically affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ɛ205Tl -1) naturally occurs. The results show a positive linear relationship (R2 = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ɛ205Tl 0), followed by fly ash (ɛ205Tl between -2.5 and -2.8) and volatile Tl fractions (ɛ205Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistribution, we demonstrate that Tl contamination can be traced in soils, and propose that the isotope data represent a possible tool to aid our understanding of post-depositional Tl dynamics in surface environments for the future. This research was supported by the Czech Science Foundation (grant no. 14-01866S and 17-03211S).

  2. Mercury isotope signatures in contaminated sediments as a tracer for local industrial pollution sources. (United States)

    Wiederhold, Jan G; Skyllberg, Ulf; Drott, Andreas; Jiskra, Martin; Jonsson, Sofi; Björn, Erik; Bourdon, Bernard; Kretzschmar, Ruben


    Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) may cause characteristic isotope signatures of different mercury (Hg) sources and help understand transformation processes at contaminated sites. Here, we present Hg isotope data of sediments collected near industrial pollution sources in Sweden contaminated with elemental liquid Hg (mainly chlor-alkali industry) or phenyl-Hg (paper industry). The sediments exhibited a wide range of total Hg concentrations from 0.86 to 99 μg g(-1), consisting dominantly of organically-bound Hg and smaller amounts of sulfide-bound Hg. The three phenyl-Hg sites showed very similar Hg isotope signatures (MDF δ(202)Hg: -0.2‰ to -0.5‰; MIF Δ(199)Hg: -0.05‰ to -0.10‰). In contrast, the four sites contaminated with elemental Hg displayed much greater variations (δ(202)Hg: -2.1‰ to 0.6‰; Δ(199)Hg: -0.19‰ to 0.03‰) but with distinct ranges for the different sites. Sequential extractions revealed that sulfide-bound Hg was in some samples up to 1‰ heavier in δ(202)Hg than organically-bound Hg. The selectivity of the sequential extraction was tested on standard materials prepared with enriched Hg isotopes, which also allowed assessing isotope exchange between different Hg pools. Our results demonstrate that different industrial pollution sources can be distinguished on the basis of Hg isotope signatures, which may additionally record fractionation processes between different Hg pools in the sediments.

  3. Influences of calcium availability and tree species on Ca isotope fractionation in soil and vegetation (United States)

    Page, B.D.; Bullen, T.D.; Mitchell, M.J.


    The calcium (Ca) isotope system is potentially of great use for understanding biogeochemical processes at multiple scales in forest ecosystems, yet remains largely unexplored for this purpose. In order to further our understanding of Ca behavior in forests, we examined two nearly adjacent hardwood-dominated catchments with differing soil Ca concentrations, developed from crystalline bedrock, to determine the variability of 44Ca/ 40Ca ratios (expressed as ??44Ca) within soil and vegetation pools. For both sugar maple and American beech, the Ca isotope compositions of the measured roots and calculated bulk trees were considerably lighter than those of soil pools at these sites, suggesting that the trees were able to preferentially take up light Ca at the root-soil interface. The Ca isotope compositions of three of four root samples were among the lightest values yet reported for terrestrial materials (??44Ca ???-3.95???). Our results further indicate that Ca isotopes were fractionated along the transpiration streams of both tree species with roots having the least ??44Ca values and leaf litter the greatest. An approximately 2??? difference in ??44Ca values between roots and leaf litter of both tree species suggests a persistent fractionation mechanism along the transpiration stream, likely related to Ca binding in wood tissue coupled with internal ion exchange. Finally, our data indicate that differing tree species demand for Ca and soil Ca concentrations together may influence Ca isotope distribution within the trees. Inter-catchment differences in Ca isotope distributions in soils and trees were minor, indicating that the results of our study may have broad transferability to studies of forest ecosystems in catchments developed on crystalline substrates elsewhere. ?? 2008 Springer Science+Business Media B.V.

  4. Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios (United States)

    Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.


    Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

  5. Correction of MS data for naturally occurring isotopes in isotope labelling experiments. (United States)

    Millard, Pierre; Letisse, Fabien; Sokol, Serguei; Portais, Jean-Charles


    Mass spectrometry (MS) in combination with isotope labelling experiments is widely used for investigations of metabolism and other biological processes. Quantitative applications-e.g., (13)C metabolic flux analysis-require correction of raw MS data (isotopic clusters) for the contribution of all naturally abundant isotopes. This chapter describes how to perform such correction using the software IsoCor. This flexible, user-friendly software can be used to exploit any isotopic tracer, from well-known ((13)C, (15)N, (18)O, etc.) to unusual ((57)Fe, (77)Se, etc.) isotopes. It also provides options-e.g., correction for the isotopic purity of the tracer-to improve the accuracy of quantitative isotopic studies, and allows automated correction of large datasets that can be collected with modern MS methods.

  6. Influence of persistent exchangeable oxygen on biogenic silica δ18O in deep sea cores (United States)

    Menicucci, A. J.; Spero, H. J.


    The removal of exchangeable oxygen from biogenic opal prior to IRMS analysis is critical during sample preparation. Exchangeable oxygen is found in the form of hydroxyl and between defects within the amorphous silicate lattice structure. Typical analytical procedures utilize a variety of dehydroxylation methods to eliminate this exchangeable oxygen, including vacuum dehydroxylation and prefluorination. Such methods are generally considered sufficient for elimination of non-lattice bound oxygen that would obfuscate environmental oxygen isotopic signals contained within the silicate tetrahedra. δ18O data that are then empirically calibrated against modern hydrographic data, and applied down core in paleoceanographic applications. We have conducted a suite of experiments on purified marine opal samples using the new microfluorination method (Menicucci et al., 2013). Our data demonstrate that the amount of exchangeable oxygen in biogenic opal decreases as sample age/depth in core increases. These changes are not accounted for by current researchers. Further, our experimental data indicate that vacuum dehydroxylation does not eliminate all exchangeable oxygen, even after hydroxyl is undetectable. We have conducted experiments to quantify the amount of time necessary to ensure vacuum dehydroxylation has eliminated exchangeable oxygen so that opal samples are stable prior to δ18Odiatom analysis. Our experiments suggest that previously generated opal δ18O data may contain a variable down-core offset due to the presence of exchangeable, non-lattice bound oxygen sources. Our experiments indicate that diatom silica requires dehydroxylation for ≥ 44 hours at 1060oC to quantitatively remove all non-lattice bound oxygen. Further, this variable amount of exchangeable oxygen may be responsible for some of the disagreement between existing empirical calibrations based on core-top diatom frustule remains. Analysis of δ18Odiatom values after this long vacuum dehydroxylation

  7. Circum-Antarctic Nd isotope variability during the last 30 kyrs (United States)

    Struve, T.; van de Flierdt, T.; Hines, S. K.; Burke, A.; Adkins, J. F.; Robinson, L. F.; Crocket, K. C.; Auro, M. E.


    The modern Southern Ocean is a key area for the global ocean circulation as wind-driven mixing, upwelling and redistribution of water masses in the Antarctic Circumpolar Current (ACC) all have a significant impact on the properties and flow patterns of global water masses. It has been suggested that the Southern Ocean plays a critical role in oceanographic and climatic changes observed on glacial-interglacial timescales, in particular with respect to carbon sequestration between the deep ocean and the atmosphere. For the purpose of unravelling Southern Ocean water mass composition at intermediate depth during the past 30 kyrs, we here utilise the Nd isotopic composition of the aragonitic skeletons of solitary deep-sea corals. These corals were collected from two locations, the Drake Passage and the area south of Tasmania, and from water depths between 300 and 1750 m. Modern coral specimen were calibrated against nearby seawater. Neodymium was collected from the wash fraction of the anion-exchange column, which represents the first step in preparing samples for precise U-series dating. Subsequent Nd separation utilised a two-stage ion chromatography (RE-spec/cation exchange and Ln-spec resins). Isotopic analyses were performed as NdO+ on a Triton TIMS using a TaF5 activator on W filaments yielding 2σ external reproducibilities of ~20 ppm. (Sub-) millenial scale deep-sea coral neodymium isotope results from the Drake Passage suggest that the modern homogenous ACC neodymium isotopic composition of ɛNd≈ -8 is a very recent feature. During the past 30 kyrs Nd isotope variability on the order of two epsilon units are observed at intermediate water depths as well as repeated changes in water column stratification. We will discuss our new results in the context of other Southern Ocean records, as well as preliminary Nd isotope data from glacial to deglacial deep-sea corals from south of Tasmania in order to constrain the last glacial to deglacial circum-Antarctic Nd

  8. Second international conference on isotopes. Conference proceedings

    Energy Technology Data Exchange (ETDEWEB)

    Hardy, C.J. [ed.


    The Second International Conference on Isotopes (2ICI) was hosted by the Australian Nuclear Association in Sydney, NSW, Australia. The Theme of the Second Conference: Isotopes for Industry, Health and a Better Environment recognizes that isotopes have been used in these fields successfully for many years and offer prospects for increasing use in the future. The worldwide interest in the use of research reactors and accelerators and in applications of stable and radioactive isotopes, isotopic techniques and radiation in industry, agriculture, medicine, environmental studies and research in general, was considered. Other radiation issues including radiation protection and safety were also addressed. International and national overviews and subject reviews invited from leading experts were included to introduce the program of technical sessions. The invited papers were supported by contributions accepted from participants for oral and poster presentation. A Technical Exhibition was held in association with the Conference. This volume contains the full text or extended abstracts of papers number 61- to number 114

  9. Selected Isotopes for Optimized Fuel Assembly Tags

    Energy Technology Data Exchange (ETDEWEB)

    Gerlach, David C.; Mitchell, Mark R.; Reid, Bruce D.; Gesh, Christopher J.; Hurley, David E.


    In support of our ongoing signatures project we present information on 3 isotopes selected for possible application in optimized tags that could be applied to fuel assemblies to provide an objective measure of burnup. 1. Important factors for an optimized tag are compatibility with the reactor environment (corrosion resistance), low radioactive activation, at least 2 stable isotopes, moderate neutron absorption cross-section, which gives significant changes in isotope ratios over typical fuel assembly irradiation levels, and ease of measurement in the SIMS machine 2. From the candidate isotopes presented in the 3rd FY 08 Quarterly Report, the most promising appear to be Titanium, Hafnium, and Platinum. The other candidate isotopes (Iron, Tungsten, exhibited inadequate corrosion resistance and/or had neutron capture cross-sections either too high or too low for the burnup range of interest.

  10. Near Surface CO2 Triple Oxygen Isotope Composition

    Directory of Open Access Journals (Sweden)

    Sasadhar Mahata


    Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

  11. Oxygen isotope systematics in an evolving geothermal system: Coso Hot Springs, California (United States)

    Etzel, Thomas M.; Bowman, John R.; Moore, Joseph N.; Valley, John W.; Spicuzza, Michael J.; McCulloch, Jesse M.


    Oxygen isotope and clay mineralogy studies have been made on whole rock samples and feldspar separates from three wells along the high temperature West Flank of the Coso geothermal system, California. The reservoir rocks have experienced variable 18O/16O depletion, with δ18O values ranging from primary values of + 7.5‰ down to - 4.6‰. Spatial patterns of clay mineral distributions in the three wells are not closely correlated with the distributions expected from measured, pre-production temperature profiles, but do correlate with spatial patterns of 18O/16O depletion, indicating that the stability of clay minerals in the three wells is a function of fluid-rock interaction in addition to temperature. Detailed δ18O measurements in the three wells identify a limited number of localized intervals of extensive 18O/16O depletion. These intervals document localized zones of higher permeability in the geothermal system that have experienced significant fluid infiltration, water-rock interaction and oxygen isotopic exchange with the geothermal fluids. The local zones of maximum 18O/16O depletion in each well correspond closely with current hot water production zones. Most feldspar separates have measured δ18O values too high to have completely attained oxygen isotope exchange equilibrium with the reservoir fluid at pre-production temperatures. In general, the lower the δ18O value of the feldspar, the closer the feldspar approaches exchange equilibrium with the geothermal fluid. This correlation suggests that fracture-induced increases in permeability increase both fluid infiltration and the surface area of the host rock exposed to geothermal fluid, promoting fluid-rock interaction and oxygen isotope exchange. The two most 18O/16O-depleted feldspar samples have δ18O values too low to be in exchange equilibrium with the pre-production reservoir fluid at pre-production temperatures. These discrepancies suggest that the reservoir fluid in the West Flank of the Coso

  12. Manus Water Isotope Investigation Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Conroy, Jessica L [University of Illinois, Urbana-Champaign; Cobb, Kim M [Georgia Institute of Technology; Noone, David [University of Colorado, Boulder


    The objective of this field campaign was to investigate climatic controls on the stable isotopic composition of water vapor, precipitation, and seawater in the western tropical Pacific. Simultaneous measurements of the stable isotopic composition of vapor and precipitation from April 28 to May 8, 2013, at the Manus Tropical Western Pacific Atmospheric Radiation Measurement site, provided several key insights into the nature of the climate signal archived in precipitation and vapor isotope ratios. We observed a large shift from lower to higher isotopic values in vapor and precipitation because of the passage of a mesoscale convective system west of the site and a transition from a regional stormy period into a more quiescent period. During the quiescent period, the stable isotopic composition of vapor and precipitation indicated the predominance of oceanic evaporation in determining the isotopic composition of boundary-layer vapor and local precipitation. There was not a consistent relationship between intra-event precipitation amount at the site and the stable isotopic composition of precipitation, thus challenging simplified assumptions about the isotopic “amount effect” in the tropics on the time scale of individual storms. However, some storms did show an amount effect, and deuterium excess values in precipitation had a significant relationship with several meteorological variables, including precipitation, temperature, relative humidity, and cloud base height across all measured storms. The direction of these relationships points to condensation controls on precipitation deuterium excess values on intra-event time scales. The relationship between simultaneous measurements of vapor and precipitation isotope ratios during precipitation events indicates the ratio of precipitation-to-vapor isotope ratios can diagnose precipitation originating from a vapor source unique from boundary-layer vapor and rain re-evaporation.

  13. An integrated sulfur isotope model for Namibian shelf sediments (United States)

    Dale, Andrew W.; Brüchert, Volker; Alperin, Marc; Regnier, Pierre


    In this study the sulfur cycle in the organic-rich mud belt underlying the highly productive upwelling waters of the Namibian shelf is quantified using a 1D reaction-transport model. The model calculates vertical concentration and reaction rate profiles in the top 500 cm of sediment which are compared to a comprehensive dataset which includes carbon, sulfur, nitrogen and iron compounds as well as sulfate reduction (SR) rates and stable sulfur isotopes ( 32S, 34S). The sulfur dynamics in the well-mixed surface sediments are strongly influenced by the activity of the large sulfur bacteria Thiomargaritanamibiensis which oxidize sulfide (H 2S) to sulfate ( SO42-) using sea water nitrate ( NO3-) as the terminal electron acceptor. Microbial sulfide oxidation (SOx) is highly efficient, and the model predicts intense cycling between SO42- and H 2S driven by coupled SR and SOx at rates exceeding 6.0 mol S m -2 y -1. More than 96% of the SR is supported by SOx, and only 2-3% of the SO42- pool diffuses directly into the sediment from the sea water. A fraction of the SO42- produced by Thiomargarita is drawn down deeper into the sediment where it is used to oxidize methane anaerobically, thus preventing high methane concentrations close to the sediment surface. Only a small fraction of total H 2S production is trapped as sedimentary sulfide, mainly pyrite (FeS 2) and organic sulfur (S org) (˜0.3 wt.%), with a sulfur burial efficiency which is amongst the lowest values reported for marine sediments (<1%). Yet, despite intense SR, FeS 2 and S org show an isotope composition of ˜5 ‰ at 500 cm depth. These heavy values were simulated by assuming that a fraction of the solid phase sulfur exchanges isotopes with the dissolved sulfide pool. An enrichment in H 2S of 34S towards the sediment-water interface suggests that Thiomargarita preferentially remove H 232S from the pore water. A fractionation of 20-30‰ was estimated for SOx (ɛ SOx) with the model, along with a maximum

  14. Continental-Scale Stable Isotope Measurements at NEON to Address Ecological Processes Across Systems (United States)

    Luo, H.; Goodman, K. J.; Hinckley, E. S.; West, J. B.; Williams, D. G.; Bowen, G. J.


    The National Ecological Observatory Network (NEON) is a national-scale research platform. The overarching goal of NEON is to enable understanding and forecasting of the impacts of climate change, land use change, and invasive species on aspects of continental-scale ecology (such as biodiversity, biogeochemistry, infectious diseases, ecohydrology, etc.). NEON focuses explicitly on questions that relate to grand challenges in environmental science, are relevant to large regions, and would otherwise be very difficult to address with traditional ecological approaches. The use of stable isotope approaches in ecological research has grown steadily during the last two decades. Stable isotopes at natural abundances in the environment trace and integrate the interaction between abiotic and biotic components across temporal and spatial scales. In this poster, we will present the NEON data products that incorporate stable isotope measurements in atmospheric, terrestrial, and aquatic ecosystems in North America. We further outline current questions in the natural sciences community and how these data products can be used to address continental-scale ecological questions, such as the ecological impacts of climate change, terrestrial-aquatic system linkages, land-atmosphere exchange, landscape ecohydrological processes, and linking biogeochemical cycles across systems. Specifically, we focus on the use of stable isotopes to evaluate water availability and residence times in terrestrial systems, as well as nutrient sources to terrestrial systems, and cycling across ecosystem boundaries.

  15. Preliminary isotopic studies of fluids from the Cerro Prieto geothermal field (United States)

    Truesdell, A.H.; Rye, R.O.; Pearson, F.J.; Olson, E.R.; Nehring, N.L.; Whelan, J.F.; Huebner, M.A.; Coplen, T.B.


    Preliminary isotopic studies of Cerro Prieto geothermal fluids and earlier studies of Mexicali Valley ground waters suggest local recharge of the geothermal system from the area immediately to the west. Oxygen isotope exchange of water with reservoir rock minerals at temperatures increasing with depth has produced fluids with oxygen-18 contents increasing with depth, and pressure drawdown in the southeastern part of the field has allowed lower oxygen-18 fluids to invade the production aquifer from above. The contents of tritium and carbon-14 in the fluid suggest only that the age of the fluid is between 50 and 10,000 years. The isotopic compositions of carbon and sulfur are consistent with a magmatic origin of these elements but a mixed sedimentary-organic origin appears more likely for carbon and is also possible for sulfur. Investigations of the isotopic compositions of geothermal and cold ground waters continue and are being expanded as fluids become available and as separation and analysis methods are improved. ?? 1979.

  16. Thermal diversities of two Na+/H+ exchanges in guinea pig red cells. (United States)

    Ji, H L


    To test the effect of hypothermia on Na+/H+ exchange, activated by shrinkage and cytoplasmic acidosis. Amiloride-sensitive Na+ influx in guinea pig red cells was traced with isotope 22Na and intracellular Na+ concentration was measured by emission flame photometry. Amiloride-sensitive Na+ influx decreased linearly as a function of temperatures (about 37 degrees C) in shrunken cells, but increased in acidified cells. The up-regulation of acid-induced Na+/H+ exchange by elevated temperature was enhanced by hypo-osmolarity. Less sensitivity of intracellular H+ site at 41 degrees C may be the mechanism for the inhibition of shrinkage-induced Na+/H+ exchange by elevated temperature. Heating-mediated explosive increase in the activity of acid-induced Na+/H+ exchange may be due to enhanced extracellular Na+ sensitivity and lower intracellular pH caused by acidic metabolites. Acid-induced Na+/H+ exchange contributes to cytoplasmic Na+ accumulation. These two modes of Na+/H+ exchange with different response to elevated temperature may play different roles in the cellular pathogenesis of heatstroke.

  17. A dynamic leaf gas-exchange strategy is conserved in woody ... (United States)

    Rising atmospheric [CO2], ca, is expected to affect stomatal regulation of leaf gas-exchange of woody plants, thus influencing energy fluxes as well as carbon (C), water and nutrient cycling of forests. Researchers have reported that stomata regulate leaf gas-exchange around “set points” that include a constant leaf internal [CO2], ci, a constant drawdown in CO2 (ca - ci), and a constant ci/ca. Because these set points can result in drastically different consequences for leaf gas-exchange, it will be essential for the accuracy of Earth systems models that generalizable patterns in leaf gas-exchange responses to ca be identified if any do exist. We hypothesized that the concept of optimal stomatal behavior, exemplified by woody plants shifting along a continuum of these set point strategies, would provide a unifying framework for understanding leaf gas-exchange responses to ca. We analyzed studies reporting C stable isotope ratio (δ13C) or photosynthetic discrimination (∆13C) from woody plant taxa that grew across ca spanning at least 100 ppm for each species investigated. From these data we calculated ci, and in combination with known or estimated ca, leaf gas-exchange regulation strategies were assessed. Overall, our analyses does not support the hypothesis that trees are canalized towards any of the proposed set points, particularly so for a constant ci. Rather, the results are consistent with the hypothesis that stomatal optimization regulates leaf gas

  18. Geochemical and isotopic data for restricting seawater intrusion and groundwater circulation in a series of typical volcanic islands in the South China Sea. (United States)

    Zhang, Wenjie; Chen, Xi; Tan, Hongbing; Zhang, Yanfei; Cao, Jifu


    The decline of groundwater table and deterioration of water quality related to seawater have long been regarded as a crucial problem in coastal regions. In this work, a hydrogeologic investigation using combined hydrochemical and isotopic approaches was conducted in the coastal region of the South China Sea near the Leizhou peninsular to provide primary insight into seawater intrusion and groundwater circulation. Hydrochemical and isotopic data show that local groundwater is subjected to anthropogenic activities and geochemical processes, such as evaporation, water-rock interaction, and ion exchange. However, seawater intrusion driven by the over-exploitation of groundwater and insufficient recharge is the predominant factor controlling groundwater salinization. Systematic and homologic isotopic characteristics of most samples suggest that groundwater in volcanic area is locally recharged and likely caused by modern precipitation. However, very depleted stable isotopes and extremely low tritium of groundwater in some isolated aquifers imply a dominant role of palaeowater. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction. (United States)

    Kendrick, B K; Hazra, Jisha; Balakrishnan, N


    Quantum reactive scattering calculations for the hydrogen exchange reaction H+H_{2}(v=4,j=0)→H+H_{2}(v^{'}, j^{'}) and its isotopic analogues are reported for ultracold collision energies. Because of the unique properties associated with ultracold collisions, it is shown that the geometric phase effectively controls the reactivity. The rotationally resolved rate coefficients computed with and without the geometric phase are shown to differ by up to 4 orders of magnitude. The effect is also significant in the vibrationally resolved and total rate coefficients. The dynamical origin of the effect is discussed and the large geometric phase effect reported here might be exploited to control the reactivity through the application of external fields or by the selection of a particular nuclear spin state.

  20. Intramolecular stable isotope distributions detect plant metabolic responses on century time scales (United States)

    Schleucher, Jürgen; Ehlers, Ina; Augusti, Angela; Betson, Tatiana


    Plants respond to environmental changes on a vast range of time scales, and plant gas exchanges constitute important feedback mechanisms in the global C cycle. Responses on time scales of decades to centuries are most important for climate models, for prediction of crop productivity, and for adaptation to climate change. Unfortunately, responses on these timescale are least understood. We argue that the knowledge gap on intermediate time scales is due to a lack of adequate methods that can bridge between short-term manipulative experiments (e.g. FACE) and paleo research. Manipulative experiments in plant ecophysiology give information on metabolism on time scales up to years. However, this information cannot be linked to results from retrospective studies in paleo research, because little metabolic information can be derived from paleo archives. Stable isotopes are prominent tools in plant ecophysiology, biogeochemistry and in paleo research, but in all applications to date, isotope ratios of whole molecules are measured. However, it is well established that stable isotope abundance varies among intramolecular groups of biochemical metabolites, that is each so-called "isotopomer" has a distinct abundance. This intramolecular variation carries information on metabolic regulation, which can even be traced to individual enzymes (Schleucher et al., Plant, Cell Environ 1999). Here, we apply intramolecular isotope distributions to study the metabolic response of plants to increasing atmospheric [CO2] during the past century. Greenhouse experiments show that the deuterium abundance among the two positions in the C6H2 group of photosynthetic glucose depends on [CO2] during growth. This is observed for all plants using C3 photosynthesis, and reflects the metabolic flux ratio between photorespiration and photosynthesis. Photorespiration is a major C flux that limits assimilation in C3 plants, which encompass the overwhelming fraction of terrestrial photosynthesis and the

  1. Carbon isotope composition of ambient CO2 and recycling: a matrix simulation model (United States)

    da Silveira Lobo Sternberg, Leonel; DeAngelis, Donald L.


    The relationship between isotopic composition and concentration of ambient CO2 in a canopy and its associated convective boundary layer was modeled. The model divides the canopy and convective boundary layer into several layers. Photosynthesis, respiration, and exchange between each layer can be simulated by matrix equations. This simulation can be used to calculate recycling; defined here as the amount of respired CO2 re-fixed by photosynthesis relative to the total amount of respired CO2. At steady state the matrix equations can be solved for the canopy and convective boundary layer CO2 concentration and isotopic profile, which can be used to calculate a theoretical recycling index according to a previously developed equation. There is complete agreement between simulated and theoretical recycling indices for different exchange scenarios. Recycling indices from a simulation of gas exchange between a heterogeneous vegetation canopy and the troposphere also agreed with a more generalized form of the theoretical recycling equation developed here.

  2. Preparation of starch and soluble sugars of plant material for the analysis of carbon isotope composition: a comparison of methods. (United States)

    Richter, Andreas; Wanek, Wolfgang; Werner, Roland A; Ghashghaie, Jaleh; Jäggi, Maya; Gessler, Arthur; Brugnoli, Enrico; Hettmann, Elena; Göttlicher, Sabine G; Salmon, Yann; Bathellier, Camille; Kodama, Naomi; Nogués, Salvador; Søe, Astrid; Volders, Fillip; Sörgel, Karin; Blöchl, Andreas; Siegwolf, Rolf T W; Buchmann, Nina; Gleixner, Gerd


    Starch and soluble sugars are the major photosynthetic products, and their carbon isotope signatures reflect external versus internal limitations of CO(2) fixation. There has been recent renewed interest in the isotope composition of carbohydrates, mainly for use in CO(2) flux partitioning studies at the ecosystem level. The major obstacle to the use of carbohydrates in such studies has been the lack of an acknowledged method to isolate starch and soluble sugars for isotopic measurements. We here report on the comparison and evaluation of existing methods (acid and enzymatic hydrolysis for starch; ion-exchange purification and compound-specific analysis for sugars). The selectivity and reproducibility of the methods were tested using three approaches: (i) an artificial leaf composed of a mixture of isotopically defined compounds, (ii) a C(4) leaf spiked with C(3) starch, and (iii) two natural plant samples (root, leaf). Starch preparation methods based on enzymatic or acid hydrolysis did not yield similar results and exhibited contaminations by non-starch compounds. The specificity of the acidic hydrolysis method was especially low, and we therefore suggest terming these preparations as HCl-hydrolysable carbon, rather than starch. Despite being more specific, enzyme-based methods to isolate starch also need to be further optimized to increase specificity. The analysis of sugars by ion-exchange methods (bulk preparations) was fast but produced more variable isotope compositions than compound-specific methods. Compound-specific approaches did not in all cases correctly reproduce the target values, mainly due to unsatisfactory separation of sugars and background contamination. Our study demonstrates that, despite their wide application, methods for the preparation of starch and soluble sugars for the analysis of carbon isotope composition are not (yet) reliable enough to be routinely applied and further research is urgently needed to resolve the identified problems

  3. Fair Exchange in Strand Spaces

    Directory of Open Access Journals (Sweden)

    Joshua D. Guttman


    Full Text Available Many cryptographic protocols are intended to coordinate state changes among principals. Exchange protocols coordinate delivery of new values to the participants, e.g. additions to the set of values they possess. An exchange protocol is fair if it ensures that delivery of new values is balanced: If one participant obtains a new possession via the protocol, then all other participants will, too. Fair exchange requires progress assumptions, unlike some other protocol properties. The strand space model is a framework for design and verification of cryptographic protocols. A strand is a local behavior of a single principal in a single session of a protocol. A bundle is a partially ordered global execution built from protocol strands and adversary activities. The strand space model needs two additions for fair exchange protocols. First, we regard the state as a multiset of facts, and we allow strands to cause changes in this state via multiset rewriting. Second, progress assumptions stipulate that some channels are resilient-and guaranteed to deliver messages-and some principals are assumed not to stop at certain critical steps. This method leads to proofs of correctness that cleanly separate protocol properties, such as authentication and confidentiality, from invariants governing state evolution. G. Wang's recent fair exchange protocol illustrates the approach.

  4. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  5. Electrically Switched Cesium Ion Exchange

    Energy Technology Data Exchange (ETDEWEB)

    JPH Sukamto; ML Lilga; RK Orth


    This report discusses the results of work to develop Electrically Switched Ion Exchange (ESIX) for separations of ions from waste streams relevant to DOE site clean-up. ESIX combines ion exchange and electrochemistry to provide a selective, reversible method for radionuclide separation that lowers costs and minimizes secondary waste generation typically associated with conventional ion exchange. In the ESIX process, an electroactive ion exchange film is deposited onto. a high surface area electrode, and ion uptake and elution are controlled directly by modulating the potential of the film. As a result, the production of secondary waste is minimized, since the large volumes of solution associated with elution, wash, and regeneration cycles typical of standard ion exchange are not needed for the ESIX process. The document is presented in two parts: Part I, the Summary Report, discusses the objectives of the project, describes the ESIX concept and the approach taken, and summarizes the major results; Part II, the Technology Description, provides a technical description of the experimental procedures and in-depth discussions on modeling, case studies, and cost comparisons between ESIX and currently used technologies.

  6. A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis (United States)

    Boehme, Susan E.


    A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

  7. Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA). (United States)

    Chew, Gina; Walczyk, Thomas


    Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

  8. Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite (United States)

    Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang


    Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

  9. Atom exchange between aqueous Fe(II) and structural Fe in clay minerals. (United States)

    Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M


    Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

  10. Relative yields of stable tellurium isotopes in neutron-induced fission

    Energy Technology Data Exchange (ETDEWEB)

    De Laeter, J.R.; Rosman, K.J.R. (Western Australian Inst. of Tech., South Bentley); Boldeman, J.W. (Australian Atomic Energy Commission Research Establishment, Lucas Heights. Physics Div.)


    The relative isotopic abundances of four isotopes of tellurium (125, 126, 128 and 130) produced in the thermal neutron fission of /sup 233/U and /sup 235/U have been measured for the first time by solid source mass spectrometry. Samples of /sup 233/U and /sup 235/U were irradiated in a reactor and chemically separated by ion exchange techniques to permit nanogram-sized samples of fission product tellurium to be analysed mass spectrometrically. The results for /sup 235/U are in good agreement with published radiometric values, whereas the results for /sup 233/U are the first experimental measurements in this mass range. The cumulative fission yields determined by mass spectrometry for ruthenium, palladium, cadmium, tin and tellurium show a smooth mass distribution in the symmetric region for both /sup 233/U and /sup 235/U, except for a significant depression in the yield curve in the range 111-14.

  11. Determination of plutonium isotopes in waters and environmental solids: A review

    Energy Technology Data Exchange (ETDEWEB)

    Qiao Jixin [Radiation Research Division, Riso National Laboratory for Sustainable Energy, Technical University of Denmark, DK-4000 Roskilde (Denmark); Hou Xiaolin, E-mail: [Radiation Research Division, Riso National Laboratory for Sustainable Energy, Technical University of Denmark, DK-4000 Roskilde (Denmark); Miro, Manuel, E-mail: [Department of Chemistry, Faculty of Sciences, University of the Balearic Islands, Carretera de Valldemossa km. 7.5, E-07122 Palma de Mallorca, Illes Balears (Spain); Roos, Per [Radiation Research Division, Riso National Laboratory for Sustainable Energy, Technical University of Denmark, DK-4000 Roskilde (Denmark)


    A number of analytical methods have been developed in the past few years for environmental monitoring of plutonium (Pu) isotopes around nuclear facilities within protocols for emergency preparedness as well as for risk assessment of contaminated areas resulting from nuclear weapon tests, nuclear accidents, and the discharge of nuclear waste. This article summarizes and critically compares recently reported methods for determination of Pu isotopes in waters and environmental solid substrates, in which sample pre-treatment is imperative for separation of the target species from matrix ingredients and/or potentially interfering nuclides prior to detection by radiometric or mass spectrometric techniques. Also discussed, via representative examples, is the automation of the entire analytical protocol by on-line extraction chromatography and ion exchange chromatography using flow injection (FI) or sequential injection (SI) approaches.

  12. Design of a nuclear isotope heat source assembly for a spaceborne mini-Brayton power module. (United States)

    Wein, D.; Gorland, S. H.


    Results of a study to develop a feasible design definition of a heat source assembly (HSA) for use in nominal 500-, 1200-, or 2000-W(e) mini-Brayton spacecraft power systems. The HSA is a modular design which is used either as a single unit to provide thermal energy to the 500-W(e) mini-Brayton power module or in parallel with one or two additional HSAs for the 1200- or 2000-W(e) power module systems. Principal components consist of a multihundred watt RTG isotope heat source, a heat source heat exchanger which transfers the thermal energy from the heat source to the mini-Brayton power conversion system, an auxiliary cooling system which provides requisite cooling during nonoperation of the power conversion module and an emergency cooling system which precludes accidental release of isotope fuel in the event of system failure.

  13. The origins of water sources in the region of Annaba: confirmation using isotopic tools

    Directory of Open Access Journals (Sweden)

    L. Ghrieb


    Full Text Available The studied area contains several superficial or deep water tables, which constitute the main sources of groundwater. The complexity of the exchange between groundwater and superficial water, as well as the casting of urban and industrial wastes remain unclear and require the application of isotopic techniques. Hence, a campaign involving 48 samples was conducted. We attempted to find the links between those groundwaters. We noticed that the water levels of oxygen 18 (18O range from –6.5 ‰ in Orelait to 0.12 ‰ in Oued Meboudja. The majority of oxygen-18 values are homogenous and less than –5 ‰. However, some values belong to the evaporated water area, indicating an enrichment of these waters. The isotopic study showed that evaporation is important in the studied region.

  14. Mechanism of the flame ionization detector. II. Isotope effects and heteroatom effects

    DEFF Research Database (Denmark)

    Holm, Torkil


    of 2%. The reason for the small or non-existent isotope effects is that H/2H exchange takes place in the pre-combustion hydrogenolysis in the flame. This was shown by taking samples from the lower part of the flame by means of a fused silica capillary probe. By the same technique the hydrogenolytic......The relative molar flame ionization detecton (FID) response (RMR) for a hydrocarbon does not change when deuterium is substituted for hydrogen. The exception is methane for which an inverse deuterium effect of 3..5% is observed for tetradeuteriomethane. [13C]Methane shows an inverse isotope effect...... reactions in the hydrogen flame of compounds added to the hydrogen gas in low concentrations were followed. Alcohols, ethers, ketones, and esters all produced methane and carbon monoxide, while amines produced methane and hydrogen cyanide, halogen compounds methane and hydrogen halide, etc. The FID response...

  15. Isotopic geochemistry of Panama rivers (United States)

    Harmon, Russell S.; Worner, Gerhard; Pribil, Michael; Kern, Zoltan; Forizs, Istvan; Lyons, W. Berry; Gardner, Christopher B.; Goldsmith, Steven T.


    River water samples collected from 78 watersheds rivers along a 500-km transect across a Late Cretaceous-Tertiary andesitic volcanic arc terrane in west-central Panama provide a synoptic overview of riverine geochemistry, chemical denudation, and CO2 consumption in the tropics. D/H and 18O/16O relationships indicate that bedrock dissolution of andesitic arc crust in Panama is driven by water-rock interaction with meteoric precipitation as it passes through the critical zone, with no evidence of a geothermal or hydrothermal input. Sr-isotope relationships suggest a geochemical evolution for Panama riverine waters that involves mixing of bedrock pore water with water having 87Sr/86Sr ratios between 0.7037-0.7043 and relatively high Sr-contents with waters of low Sr content that enriched in radiogenic Sr that are diluted by infiltrating rainfall to variable extents.

  16. Studies of control materials of isotope transformation

    Energy Technology Data Exchange (ETDEWEB)

    Noda, Tetsuji; Suzuki, Hiroshi; Araki, Hiroshi; Fujita, Mitsutane; Hirano, Toshiyuki; Abe, Fujio; Numazawa, Takenori [National Research Inst. for Metals, Tsukuba, Ibaraki (Japan)


    To control wavelength of laser, the physical properties of control materials of molecular excitation and isotope should be studied. We carried out isotopic enrichment, Si thin film growth, and preparation of boron isotope crystal and to make a calculation code of nuclear transmutation simulation. A gas circulation system for developing isotope laser was produced in order to control of molecular vibration excitation. We developed a single straight system of silicon isotope enrichment and silicon thin film preparation by infrared laser. When laser irradiated Si{sub 2}F{sub 6}, unreacted Si{sub 2}F{sub 6} contained 99.72% of {sup 28}Si at about 956 cm{sup -1} wavelength. When SiF{sub 4} or Si{sub 2}F{sub 6} with enriched isotope were directly decomposed by the plasma CVD method at about from 350 to 450degC, the yield of silicon crystal was about 28%. A homogeneous crystal with 10 mm diameter was obtained as the control material of boron isotope. The computer code for simulation of nuclear transmutation was improved to calculate the displacement damage, change of composition, induced radioactivity and decay heat. (S.Y.)

  17. Si isotope homogeneity of the solar nebula

    Energy Technology Data Exchange (ETDEWEB)

    Pringle, Emily A.; Savage, Paul S.; Moynier, Frédéric [Department of Earth and Planetary Sciences and McDonnell Center for the Space Sciences, Washington University in St. Louis, One Brookings Drive, St. Louis, MO 63130 (United States); Jackson, Matthew G. [Department of Earth Science, University of California, Santa Barbara, CA 93109 (United States); Barrat, Jean-Alix, E-mail:, E-mail:, E-mail:, E-mail:, E-mail:, E-mail: [Université Européenne de Bretagne, Université de Brest, CNRS UMR 6538 (Domaines Océaniques), I.U.E.M., Place Nicolas Copernic, F-29280 Plouzané Cedex (France)


    The presence or absence of variations in the mass-independent abundances of Si isotopes in bulk meteorites provides important clues concerning the evolution of the early solar system. No Si isotopic anomalies have been found within the level of analytical precision of 15 ppm in {sup 29}Si/{sup 28}Si across a wide range of inner solar system materials, including terrestrial basalts, chondrites, and achondrites. A possible exception is the angrites, which may exhibit small excesses of {sup 29}Si. However, the general absence of anomalies suggests that primitive meteorites and differentiated planetesimals formed in a reservoir that was isotopically homogenous with respect to Si. Furthermore, the lack of resolvable anomalies in the calcium-aluminum-rich inclusion measured here suggests that any nucleosynthetic anomalies in Si isotopes were erased through mixing in the solar nebula prior to the formation of refractory solids. The homogeneity exhibited by Si isotopes may have implications for the distribution of Mg isotopes in the solar nebula. Based on supernova nucleosynthetic yield calculations, the expected magnitude of heavy-isotope overabundance is larger for Si than for Mg, suggesting that any potential Mg heterogeneity, if present, exists below the 15 ppm level.

  18. Pervaporation with ion exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Boeddeker, K.W.; Wenzlaff, A.


    Sorption and pervaporation of aqueous-organic solvent systems (water-ethanol; water-carboxylic acids) with commercial ion exchange membranes are compared to obtain information on polymersolvent interaction vs. coupling. Close agreement between sorption selectivity and pervaporation selectivity indicates coupling. If pervaporation is less selective than sorption, polymer-solvent interaction overtakes coupling, the limit of de-coupling being phase separation within the sorbate as signaled by a sudden increase in permeability of the lesser interacting component. As long as sorption and pervaporation operate in parallel, favoring enrichment of the same component, coupling enhances the separation effect. If pervaporation counteracts sorption, coupling is detrimental to the separation effect. Potential applications include the dehydration of pre-concentrated water-ethanol using anion exchange membranes, and the enrichment of acetic acid from dilute aqueous solution by pervaporative removal of water through cation exchange membranes.

  19. Isotopic tracing of perchlorate in the environment (United States)

    Sturchio, Neil C.; Böhlke, John Karl; Gu, Baohua; Hatzinger, Paul B.; Jackson, W. Andrew; Baskaran, Mark


    Isotopic measurements can be used for tracing the sources and behavior of environmental contaminants. Perchlorate (ClO 4 − ) has been detected widely in groundwater, soils, fertilizers, plants, milk, and human urine since 1997, when improved analytical methods for analyzing ClO 4 −concentration became available for routine use. Perchlorate ingestion poses a risk to human health because of its interference with thyroidal hormone production. Consequently, methods for isotopic analysis of ClO 4 − have been developed and applied to assist evaluation of the origin and migration of this common contaminant. Isotopic data are now available for stable isotopes of oxygen and chlorine, as well as 36Cl isotopic abundances, in ClO 4 − samples from a variety of natural and synthetic sources. These isotopic data provide a basis for distinguishing sources of ClO 4 − found in the environment, and for understanding the origin of natural ClO 4 − . In addition, the isotope effects of microbial ClO 4 − reduction have been measured in laboratory and field experiments, providing a tool for assessing ClO 4 − attenuation in the environment. Isotopic data have been used successfully in some areas for identifying major sources of ClO 4 − contamination in drinking water supplies. Questions about the origin and global biogeochemical cycle of natural ClO 4 − remain to be addressed; such work would benefit from the development of methods for preparation and isotopic analysis of ClO 4 − in samples with low concentrations and complex matrices.

  20. Intramolecular Isotopic Studies: Chemical Enhancements and Alternatives (United States)

    Hayes, J. M.


    As mass spectroscopic and NMR-based methods now appropriately flourish, chemical techniques should not be forgotten. First, the methods developed by pioneering intramolecular analysts can be reapplied to new samples. Second, they can be extended. The synthesis of intramolecular isotopic standards is particularly important and straightforward. It requires only that a chemical reaction has no secondary products. An example is provided by the addition of carbon dioxide to a Grignard reagent. The reaction proceeds with an isotope effect. The isotopic composition of the carboxyl group in the acid which is produced is thus not equal to that of the starting carbon dioxide but the unconsumed CO2 can be recovered and analyzed. A simple titration can show that all the rest of the CO2 is in the product acid. The isotopic composition of the carboxyl group can then be calculated by difference. The product is an intramolecular isotopic standard, an organic molecule in which the isotopic composition of a specific carbon position is known accurately. Both analysts and reviewers can thus gain invaluable confidence in the accuracy of instrumental results. A second example: the haloform reaction quantitatively degrades methyl ketones, producing a carboxylic acid which can be decarboxylated to determine the isotopic composition of the parent carbonyl and a haloform (CHI3, for example) that can be combusted to determine the isotopic composition of the methyl group. Ketones thus analyzed can be combined with Grignard reagents to yield carbon skeletons in which the isotopic compositions of internal and terminal -CH2- and -CH3 groups are known accurately. In general, analysts accustomed to demanding quantitative reactions should remember the power of mass balances and recognize that many organic-chemical reactions, while not quantitative, lack side products and can be driven to the total consumption of at least one reactant.