Science.gov

Sample records for isotope exchange reactions

  1. The Kinetics of Isotopic Exchange Reactions.

    ERIC Educational Resources Information Center

    Logan, S. R.

    1990-01-01

    Discussed are the kinetic interactions of these chemical processes and the determination of the actual order of such reactions. Included are multiple exchange, catalytic exchange with deuterium, and depletion of the original substrate. (CW)

  2. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, F.P.; Herbst, R.S.

    1995-05-30

    The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

  3. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, Frank P.; Herbst, Ronald S.

    1995-01-01

    The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

  4. Determining Clumped Isotope (Δ47) Signatures of CO2 During Ion-Molecule Isotopic Exchange Reactions

    NASA Astrophysics Data System (ADS)

    Sarna, J.; Priyadarshi, A.; Pourmorady, P.; Tripati, A.; Estaris, J.

    2015-12-01

    The abundance of multiply-substituted isotopologues such as 13C16O18O can be used to understand fundamental mechanisms that controls isotopic fractionation in chemical reactions. Knowledge of the energy-dependent ion-molecule isotopic exchange rate for 13C16O18O may also provide important insights into the CO2 ion-molecular exchange that occurs in the source of the mass spectrometer. It may offer an explanation for the recently observed nonlinearities associated with clumped isotope measurements. We designed a controlled set of laboratory experiments to investigate variations in the abundance of 13C16O18O associated with different ion-molecular isotopic exchange reactions. In our experiments, we characterize the effects of changing ionization energy, reaction time, CO2 amount, the presence of different compounds, and reaction chamber temperature on the clumped isotopic composition of CO2.

  5. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields

    NASA Astrophysics Data System (ADS)

    Tomza, Michał

    2015-08-01

    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.

  6. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields.

    PubMed

    Tomza, Michał

    2015-08-01

    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. PMID:26296115

  7. Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution: Possibly a Termolecular Liquid Phase Reaction.

    PubMed

    Gabričević, Mario; Lente, Gábor; Fábián, István

    2015-12-24

    This work reports an experimental study of the hydrogen/deuterium exchange in the basic aqueous solutions of trichloroethylene, trans-1,2-dichloroethylene, and cis-1,2-dichloroethylene using (1)H NMR as a monitoring method. 1,1-Dichlorethylene was also investigated but found not to exchange hydrogen isotopes with water. The kinetics of isotope exchange features two different pathways, the first is first order with respect to hydroxide ion, whereas the second is second order. The first pathway is interpreted as a straightforward bimolecular reaction between chloroethylene and hydroxide ion, which leads to the deprotonation of chloroethylene. The second pathway involves a transition state with the association of one molecule of the chloroethylene and two hydroxide ions. It is shown that the second pathway could involve the formation of a precursor complex composed of one chloroethylene molecule and one hydroxide ion, but a direct termolecular elementary reaction is also feasible, which is shown by deriving a theoretical highest limit for the rate constants of termolecular reactions in solution. PMID:26618984

  8. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

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

    1976-01-01

    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.

  9. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.

    PubMed

    Rustad, James R; Casey, William H

    2012-03-01

    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. PMID:22231599

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

    SciTech Connect

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2010-01-29

    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.

  11. The non-statistical dynamics of the 18O + 32O2 isotope exchange reaction at two energies

    NASA Astrophysics Data System (ADS)

    Van Wyngarden, Annalise L.; Mar, Kathleen A.; Quach, Jim; Nguyen, Anh P. Q.; Wiegel, Aaron A.; Lin, Shi-Ying; Lendvay, Gyorgy; Guo, Hua; Lin, Jim J.; Lee, Yuan T.; Boering, Kristie A.

    2014-08-01

    The dynamics of the 18O(3P) + 32O2 isotope exchange reaction were studied using crossed atomic and molecular beams at collision energies (Ecoll) of 5.7 and 7.3 kcal/mol, and experimental results were compared with quantum statistical (QS) and quasi-classical trajectory (QCT) calculations on the O3(X1A') potential energy surface (PES) of Babikov et al. [D. Babikov, B. K. Kendrick, R. B. Walker, R. T. Pack, P. Fleurat-Lesard, and R. Schinke, J. Chem. Phys. 118, 6298 (2003)]. In both QS and QCT calculations, agreement with experiment was markedly improved by performing calculations with the experimental distribution of collision energies instead of fixed at the average collision energy. At both collision energies, the scattering displayed a forward bias, with a smaller bias at the lower Ecoll. Comparisons with the QS calculations suggest that 34O2 is produced with a non-statistical rovibrational distribution that is hotter than predicted, and the discrepancy is larger at the lower Ecoll. If this underprediction of rovibrational excitation by the QS method is not due to PES errors and/or to non-adiabatic effects not included in the calculations, then this collision energy dependence is opposite to what might be expected based on collision complex lifetime arguments and opposite to that measured for the forward bias. While the QCT calculations captured the experimental product vibrational energy distribution better than the QS method, the QCT results underpredicted rotationally excited products, overpredicted forward-bias and predicted a trend in the strength of forward-bias with collision energy opposite to that measured, indicating that it does not completely capture the dynamic behavior measured in the experiment. Thus, these results further underscore the need for improvement in theoretical treatments of dynamics on the O3(X1A') PES and perhaps of the PES itself in order to better understand and predict non-statistical effects in this reaction and in the formation

  12. Kinetic isotope effect of the 16O + 36O2 and 18O + 32O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the 18O + 32O2 and 16O + 36O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  13. Kinetic isotope effect of the (16)O + (36)O2 and (18)O + (32)O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study.

    PubMed

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the (18)O + (32)O2 and (16)O + (36)O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients. PMID:25956105

  14. Quasiclassical trajectory studies of 18O(3P) + NO2 isotope exchange and reaction to O2 + NO on D0 and D1 potentials

    NASA Astrophysics Data System (ADS)

    Fu, Bina; Zhang, Dong H.; Bowman, Joel M.

    2013-07-01

    We report quasiclassical trajectory calculations for the bimolecular reaction 18O(3P) + NO2 on the recent potential energy surfaces of the ground (D0) and first excited (D1) states of NO3 [B. Fu, J. M. Bowman, H. Xiao, S. Maeda, and K. Morokuma, J. Chem. Theory. Comput. 9, 893 (2013)], 10.1021/ct3009792. The branching ratio of isotope exchange versus O2 + NO formation, as well as the product angular distributions and energy and rovibrational state distributions are presented. The calculations are done at the collision energy of relevance to recent crossed beam experiments [K. A. Mar, A. L. Van Wyngarden, C.-W. Liang, Y. T. Lee, J. J. Lin, and K. A. Boering, J. Chem. Phys. 137, 044302 (2012)], 10.1063/1.4736567. Very good agreement is achieved between the current calculations and these experiments for the branching ratio and final translational energy and angular distributions of isotope exchange products 16O(3P) + NO2 and O2 + NO formation products. The reactant 18O atom results in 18O16O but not N18O for the O2 + NO formation product channel, consistent with the experiment. In addition, the detailed vibrational and rotational state information of diatomic molecules calculated currently for the 34O2 + NO formation channel on D0 and D1 states are in qualitative agreement with the previous experimental and theoretical results of the photodissociation of NO3 and are consistent with older thermal bimolecular kinetics measurements.

  15. Investigation of hydrogen isotope exchange reaction rate in mixed gas (H{sub 2} and D{sub 2}) at pressure up to 200 MPa using Raman spectroscopy

    SciTech Connect

    Tikhonov, V.V.; Yukhimchuk, A.A.; Musyayev, R.K.; Gurkin, A.I.

    2015-03-15

    Raman spectroscopy is a relevant method for obtaining objective data on isotopic exchange rate in a gaseous mix of hydrogen isotopes, since it allows one to determine a gaseous mix composition in real time without sampling. We have developed a high-pressure fiber-optic probe to be used for obtaining protium Raman spectra under pressures up to 400 MPa and we have recorded spectral line broadening induced by molecule collisions starting from ∼ 40 MPa. Using this fiber-optic probe we have performed experiments to study isotopic exchange kinetics in a gaseous mix of hydrogen isotopes (protium-deuterium) at pressures up to 200 MPa. Preliminary results show that the dependence of the average isotopic exchange rate related to pressure take unexpected values at the very beginning of the time evolution. More work is required to understand this inconsistency.

  16. Photonuclear reactions on titanium isotopes

    SciTech Connect

    Belyshev, S. S.; Dzhilavyan, L. Z.; Ishkhanov, B. S.; Kapitonov, I. M.; Kuznetsov, A. A. Orlin, V. N.; Stopani, K. A.

    2015-03-15

    The photodisintegration of titanium isotopes in the giant-dipole-resonance energy region is studied by the photon-activation method. Bremsstrahlung photons whose spectrum has the endpoint energy of 55 MeV is used. The yields and integrated cross sections are determined for photoproton reactions on the titanium isotopes {sup 47,48,49,50}Ti. The respective experimental results are compared with their counterparts calculated on the basis of the TALYS code and a combined photonucleon-reaction model. The TALYS code disregards the isospin structure of the giant dipole resonance and is therefore unable to describe the yield of photoproton reactions on the heavy titanium isotopes {sup 49,50}Ti.

  17. Catalytic gasification: Isotopic labeling and transient reaction

    SciTech Connect

    Saber, J.M.; Falconer, J.L.; Brown, L.F.

    1985-01-01

    Temperature-programmed reaction was used with labeled isotopes (/sup 13/C and /sup 18/O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO/sub 2//90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 K and 950 K, and in the presence of gaseous carbon dioxide, the complexes promoted carbon and oxygen exchange between the gas-phase CO/sub 2/ and the surface. Oxygen exchanged between the surface complexes; but carbon did not exchange between the carbonate and the carbon black. As the temperature rose, the complexes decomposed to produce carbon dioxide, and catalytic gasification then began. Elemental potassium formed, and the active catalyst appears to alternate between potassium metal and a potassium-oxygen-carbon complex.

  18. Calculation of individual isotope equilibrium constants for geochemical reactions

    USGS Publications Warehouse

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

    2004-01-01

    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

  19. Isotope exchange in oxide-containing catalyst

    NASA Technical Reports Server (NTRS)

    Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

    1989-01-01

    A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

  20. Highly tritiated water processing by isotopic exchange

    SciTech Connect

    Shu, W.M.; Willms, R.S.; Glugla, M.; Cristescu, I.; Michling, R.; Demange, D.

    2015-03-15

    Highly tritiated water (HTW) is produced in fusion machines and one of the promising technologies to process it is isotopic exchange. 3 kinds of Pt-catalyzed zeolite (13X-APG, CBV-100-CY and HiSiv-1000) were tested as candidates for isotopic exchange of highly tritiated water (HTW), and CBV-100-CY (Na-Y type with a SiO{sub 2}/Al{sub 2}O{sub 3} ratio of ∼ 5.0) shows the best performance. Small-scale tritium testing indicates that this method is efficient for reaching an exchange factor (EF) of 100. Full-scale non-tritium testing implies that an EF of 300 can be achieved in 24 hours of operation if a temperature gradient is applied along the column. For the isotopic exchange, deuterium recycled from the Isotope Separation System (deuterium with 1% T and/or 200 ppm T) should be employed, and the tritiated water regenerated from the Pt-catalyzed zeolite bed after isotopic exchange should be transferred to Water Detritiation System (WDS) for further processing.

  1. Kinetic theory of oxygen isotopic exchange between minerals and water

    USGS Publications Warehouse

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

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  2. Isotopic exchange of hydrogen in aromatic amino acids

    SciTech Connect

    Pshenichnikova, A.B.; Karnaukhova, E.N.; Mitsner, B.I.

    1993-10-20

    The kinetics of the isotopic replacement of hydrogen in the aromatic amino acids L-tryptophan, L-tyrosine, and L-phenylalanine in solutions of deuterochloric and deuterosulfuric acids in deuterium oxide were investigated by PMR spectroscopy. The reactions were shown to be of first orders with respect both to the concentration of the substrate and to the activity of the deuterium ion. The isotopic effects of hydrogen and the values of the activation energy of H-D exchange in different positions of the aromatic ring in tryptophan and tyrosine were determined. The effect of properties of the medium on the rate of the isotopic exchange of hydrogen is discussed. 17 refs., 2 figs., 2 tabs.

  3. Unbiased isotope equilibrium factors from partial isotope exchange experiments in 3-exchange site systems

    NASA Astrophysics Data System (ADS)

    Agrinier, Pierre; Javoy, Marc

    2016-09-01

    Two methods are available in order to evaluate the equilibrium isotope fractionation factors between exchange sites or phases from partial isotope exchange experiments. The first one developed by Northrop and Clayton (1966) is designed for isotope exchanges between two exchange sites (hereafter, the N&C method), the second one from Zheng et al. (1994) is a refinement of the first one to account for a third isotope exchanging site (hereafter, the Z method). In this paper, we use a simple model of isotope kinetic exchange for a 3-exchange site system (such as hydroxysilicates where oxygen occurs as OH and non-OH groups like in muscovite, chlorite, serpentine, or water or calcite) to explore the behavior of the N&C and Z methods. We show that these two methods lead to significant biases that cannot be detected with the usual graphical tests proposed by the authors. Our model shows that biases originate because isotopes are fractionated between all these exchanging sites. Actually, we point out that the variable mobility (or exchangeability) of isotopes in and between the exchange sites only controls the amplitude of the bias, but is not essential to the production of this bias as previously suggested. Setting a priori two of the three exchange sites at isotopic equilibrium remove the bias and thus is required for future partial exchange experiments to produce accurate and unbiased extrapolated equilibrium fractionation factors. Our modeling applied to published partial oxygen isotope exchange experiments for 3-exchange site systems (the muscovite-calcite (Chacko et al., 1996), the chlorite-water (Cole and Ripley, 1998) and the serpentine-water (Saccocia et al., 2009)) shows that the extrapolated equilibrium fractionation factors (reported as 1000 ln(α)) using either the N&C or the Z methods lead to bias that may reach several δ per mil in a few cases. These problematic cases, may be because experiments were conducted at low temperature and did not reach high

  4. Borate Exchanges of Lemna minor L. as Studied with the Help of the Enriched Stable Isotopes and of a (n,α) Nuclear Reaction 1

    PubMed Central

    Thellier, Michel; Duval, Yves; Demarty, Maurice

    1979-01-01

    Despite the lack of a convenient radioisotope of boron, it is possible to measure unidirectional fluxes of borate between cellular systems and their external medium. It was accomplished by using the two purified stable isotopes (10B and 11B), with 10B specifically detected by a (n,α) nuclear reaction. The method was applied to compartmental analysis of borate with intact plants of Lemna minor L. Four compartments were suggested. Three of them apparently correspond to the three classical ones: free space (including easily dissociable borate monoesters), cytoplasm, and vacuole. The fourth one was interpreted as corresponding to very stable borate diesters in the cell walls. The method allows the determination of the borate capacities of the various compartments and of the borate unidirectional fluxes between the different compartments, at borate flux equilibrium. Other physicochemical data (mono and diester mass action constants, turn over numbers) were evaluated. The results are consistent with what is known of pure substances. PMID:16660714

  5. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  6. Separation of uranium isotopes by chemical exchange

    DOEpatents

    Ogle, P.R. Jr.

    1974-02-26

    A chemical exchange method is provided for separating /sup 235/U from / sup 238/U comprising contacting a first phase containing UF/sub 6/ with a second phase containing a compound selected from the group consisting of NOUF/sub 6/, NOUF/sub 7/, and NO/sub 2/UF/sub 7/ until the U Fsub 6/ in the first phase becomes enriched in the /sup 235/U isotope. (Official Gazette)

  7. Heterogeneous catalytic isotopic exchange of benzylic compounds in solution

    SciTech Connect

    Azran, J; Shimoni, M.; Buchman, O. )

    1994-08-01

    Isotopic exchange reactions of bibenzyl and benzylic derivatives with deuterium (D[sub 2]) and tritium (T[sub 2]) gas, catalyzed by Pd/C, have been performed in solution. Catalyst pre-washed with the reacting gas showed improved H/D or H/T exchange. In aprotic solvents such as dioxane, ethyl acetate, and cyclohexane, 3.1 to 3.5 D atoms were exchanged under standard conditions in 1 h, while in benzene 1 D atom was exchanged. D atoms adsorbed on the catalyst surface were rapidly replaced by H from methanol, diluting the D[sub 2] gas phase. Compounds containing O or N atoms enhanced the rate of exchange, while S atoms inhibited the catalyst activity. The H/D exchange obeyed pseudo-first order kinetics when D[sub 2] gas was used in large excess. When T[sub 2] gas replaced D[sub 2], a substantial decrease in rate of exchange was observed, due to the slower dissociative chemisorption of T[sub 2] on the catalyst surface. The results indicated that this exchange process occurred through two simultaneous mechanisms. The breaking of the C-H bond appeared to be the rate-determining step. 22 refs., 1 fig., 5 tabs.

  8. Water-hydrogen isotope exchange process analysis

    SciTech Connect

    Fedorchenko, O.; Alekseev, I.; Uborsky, V.

    2008-07-15

    The use of a numerical method is needed to find a solution to the equation system describing a general case of heterogeneous isotope exchange between gaseous hydrogen and liquid water in a column. A computer model of the column merely outputting the isotope compositions in the flows leaving the column, like the experimental column itself, is a 'black box' to a certain extent: the solution is not transparent and occasionally not fully comprehended. The approximate analytical solution was derived from the ZXY-diagram (McCabe-Thiele diagram), which illustrates the solution of the renewed computer model called 'EVIO-4.2' Several 'unusual' results and dependences have been analyzed and explained. (authors)

  9. Oxygen isotope fractionation in phosphates: the role of dissolved complex anions in isotope exchange.

    PubMed

    Zheng, Yong-Fei

    2016-01-01

    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. PMID:25587823

  10. Multinucleon exchange in quasifission reactions

    NASA Astrophysics Data System (ADS)

    Ayik, S.; Yilmaz, B.; Yilmaz, O.

    2015-12-01

    The nucleon exchange mechanism is investigated in the central collisions of 40Ca+238U and 48Ca+238U systems near the quasifission regime in the framework of the stochastic mean-field (SMF) approach. Sufficiently below the fusion barrier, a dinuclear structure in the collisions is maintained to a large extent. Consequently, it is possible to describe nucleon exchange as a diffusion process familiar from deep-inelastic collisions. Diffusion coefficients for proton and neutron exchange are determined from the microscopic basis of the SMF approach in the semiclassical framework. Calculations show that after a fast charge equilibration the system drifts toward symmetry over a very long interaction time. Large dispersions of proton and neutron distributions of the produced fragments indicate that the diffusion mechanism may help to populate heavy transuranium elements near the quasifission regime in these collisions.

  11. Nucleon exchange in damped nuclear reactions

    SciTech Connect

    Randrup, J.

    1986-04-01

    Starting from the general context of one-body nuclear dynamics, the nucleon-exchange mechanism in damped nuclear reactions is discussed. Some of its characteristic effects on various dinuclear observables are highlighted and a few recent advances are described.

  12. In situ NRA study of hydrogen isotope exchange in self-ion damaged tungsten exposed to neutral atoms

    NASA Astrophysics Data System (ADS)

    Markelj, S.; Založnik, A.; Schwarz-Selinger, T.; Ogorodnikova, O. V.; Vavpetič, P.; Pelicon, P.; Čadež, I.

    2016-02-01

    Isotope exchange was studied in-situ by Nuclear Reaction Analysis in the bulk of self-ion damaged tungsten at 600 K. Both variations of isotope exchange of H by D and of D by H were measured. The deuterium isothermal desorption was also studied and evaluated in order to be able to resolve the self-desorption from the isotope exchange at 600 K. The isotope exchange was also studied on the surface by Elastic Recoil Detection Analysis at 480 K and 380 K. The exchange mechanism was effective both on the surface and in the bulk of damaged tungsten. A simple model was introduced to describe the exchange efficiency on the surface and in the bulk obtaining the exchange cross sections on the surface and in bulk. In both cases an isotope effect was observed, where the exchange of H atoms by D atoms was more efficient than for the reverse sequence.

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

    SciTech Connect

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

    2011-04-01

    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.

  14. Deuterium isotopic exchangeability of resin and amber at low thermal stress under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Gonzalez, G.; Tappert, R.; Wolfe, A. P.; Muehlenbachs, K.

    2012-04-01

    Hydrous deuterium-exchange experiments have shown that a significant fraction of the original D/H composition of bulk kerogens, bitumens and expelled oils may participate in isotopic exchange reactions during burial diagenesis. However, it is unknown to what extent plant-derived secondary metabolites, namely resins and their fossil counterpart amber, exchange hydrogen isotopes following their biosynthesis. This situation hinders the application of resin D/H measurements in paleoenvironmental reconstruction. Here, we assess explicitly hydrogen exchange in resins and ambers using a series of immersion experiments in deuterated (D-enriched) waters over a period of several months at several temperatures. We are especially interested in assessing whether significant H-isotopic exchange occurs between resins and meteoric waters during early thermal maturation and polymerization. At 90°C, equivalent to ~3km of burial in most diagenetic regimes, modern conifer and angiosperm resins have an average post-metabolic H exchange of 4.6%, compared to only 1.1% for mature, polymerized ambers. At 55°C the degree of exchange is considerably lower: 1.9% for resins and 0.6% for ambers. These results indicate that most D/H isotopic exchange occurs prior to polymerization reactions, thereby confirming that D/H measurements from amber constitute a potentially sensitive proxy for environmental change.

  15. Observation of large enhancements of charge exchange cross sections with neutron-rich carbon isotopes

    NASA Astrophysics Data System (ADS)

    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.

    2016-04-01

    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.

  16. Process for exchanging hydrogen isotopes between gaseous hydrogen and water

    DOEpatents

    Hindin, Saul G.; Roberts, George W.

    1980-08-12

    A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

  17. Charge exchange reactions and applications to astrophysics

    NASA Astrophysics Data System (ADS)

    Cheoun, Myung-Ki; Ha, Eunja; Kajino, T.

    2012-11-01

    Neutrino-induced reactions have been known to play important roles as the neutrino process on the nucleosynthesis in core collapsing supernovae (SNe) explosions because expected neutrino flux and energy are sufficiently high enough to excite many relevant nuclei in spite of small cross sections of the weak interaction. However, we do not have enough data for the neutrino reaction to be exploited in the network calculation. Only a sparse data in the relevant energy range is known, in specific, for 12C. Therefore we have to rely on theoretical estimation of the reaction, which has two different modes, charge current (CC) and neutral current (NC). In particular, CC reactions are closely related to charge exchange reactions (CEXRs) which are feasible in the experiment, such as, (p,n) or (n,p) reactions. These CEXRs are usually dominated by the Gamow-Teller (GT) transition in the lower energy region. In this respect, any theoretical approaches for the neutrino reaction should be investigated for the CEXR because we have and expect more useful experimental data. After confirming our models to the GT strength deduced from the CEXR, we calculated neutrino-induced reactions in the energy range below the quasielastic region for nuclei of astrophysical importance. Our calculations are carried out with the Quasi-particle Random Phase Approximation (QRPA), which successfully described the nuclear beta decays of relevant nuclei. To describe neutrino-nucleus reactions, general multipole transitions by the weak interaction are considered for CC and NC reactions. Both reactions are described in a theoretical framework. Our results are shown to well reproduce the data from CEXRs and the sparse experimental data related to the neutrino-induced reaction, and further extended for neutrino reactions on various nuclear targets. Parts of the results are reported in this talk.

  18. Isotope exchange as a probe of the kinetic mechanism of pyrophosphate-dependent phosphofructokinase

    SciTech Connect

    Cho, Y.K.; Matsunaga, T.O.; Kenyon, G.I.; Bertagnolli, B.L.; Cook, P.F.

    1988-05-03

    Data obtained from isotope exchange at equilibrium, exchange of inorganic phosphate against forward reaction flux, and positional isotope exchange of /sup 18/O from the bridge position of pyrophosphate to a nonbridge position all indicate that the pyrophosphate-dependent phosphofructokinase fromPropionibacterium freudenreichii has a rapid equilibrium random kinetic mechanism. The maximum rates of isotope exchange at equilibrium for the (/sup 14/C)fructose 1,6-bisphosphate in equilibrium fructose 6-phosphate, (/sup 32/P)P/sub i/ in equilibrium MgPP/sub i/, and Mg(/sup 32/P)PP/sub i/ in equilibrium fructose, 1,6-bisphosphate exchange reactions increasing all four possible substrate-product pairs in constant ratio are identical, consistent with a rapid equilibrium mechanism. All exchange reactions are strongly inhibited at high concentrations of the fructose 6-phosphate (F6P)P/sub i/ and MgPP/sub i/P/sub i/ substrate-product pairs and weakly inhibited at high concentrations of the MgPP/sub i/fructose 1,6-bisphosphate (FBP) pair suggesting three dead-end complexes, E:F6P:P/sub i/, E:MgPP/sub i/:P/sub i/, and E:FBP:MgPP/sub i/, in agreement with initial velocity studies. Neither back-exchange by (/sup 32/P)P/sub i/ nor positional isotope exchange of /sup 18/O-bridge-labeled pyrophosphate was observed under any conditions, suggesting that either the chemical interconversion step or a step prior to it limits the overall rate of the reaction.

  19. Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

    SciTech Connect

    Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.; Scherer, Michelle M.; Spicuzza, Michael J.; Valley, John W.; Johnson, Clark M.

    2015-07-01

    solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸OGth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II)aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.

  20. The Oxygen Isotopic Signature of Nitrous Oxide is Determined by Oxygen Exchange

    NASA Astrophysics Data System (ADS)

    Kool, D. M.; Wrage, N.; Oenema, O.; Harris, D.; van Groenigen, J.

    2008-12-01

    In order to derive accurate budget estimations and effective mitigation strategies for the greenhouse gas nitrous oxide (N2O), it is essential to identify the processes involved in its production. Analyses of the isotopic composition of N2O are increasingly used to characterize the importance of these processes. However, we argue that the reliability of results based on oxygen (O) isotopic analysis of N2O may be questioned due to insufficient consideration of O exchange between H2O and nitrogen oxides. We studied the process of O exchange in 12 widely varying soils using a novel combination of 18O and 15N tracing experiments. Incorporation of O from 18O-enriched H2O into N2O exceeded theoretical maxima based on reaction stoichiometry, revealing the presence of O exchange. Novel methodology based on the retention of the 18O:15N-enrichment ratio of NO3- in N2O allowed to quantify O exchange during denitrification: up to 97% of N2O-O originated from H2O instead of NO3-. Our results show that in soil, the main source of N2O, the conventional assumption that the O isotopic composition of N2O is determined by reaction stoichiometry and isotopic fractionation during its production does not hold. In all cases, the O isotopic signature of N2O was found to be dominated by the effect of O exchange between nitrogen oxides and water. We speculate that the implications of O exchange will extend across terrestrial and aquatic ecosystems, and possibly to other nitrogen oxides as well. Especially, a potential effect of O exchange on the O isotopic signature of NO3- needs to be studied, as this is routinely used for NO3- source determination. Our results may facilitate the development of improved methodology to study and understand the global N cycle.

  1. The use of ion exchange membranes for isotope analyses on soil water sulfate: laboratory experiments.

    PubMed

    Kwon, Jang-Soon; Mayer, Bernhard; Yun, Seong-Taek; Nightingale, Michael

    2008-01-01

    To investigate the potential use of anion exchange membranes (plant root simulator [PRS] probes) for isotope investigations of the soil sulfur cycle, laboratory experiments were performed to examine the sulfate exchange characteristics and to determine the extent of sulfur and oxygen isotope fractionation during sulfate sorption and desorption on the probes in aqueous solutions and simulated soil solutions. The sulfate-exchange tests in aqueous solutions under varying experimental conditions indicated that the amount of sulfate exchanged onto PRS probes increased with increasing reaction time, initial sulfate concentration, and the number of probes used (= surface area), whereas the percentage of removal of available sulfate was constant irrespective of the initial sulfate concentration. The competition of nitrate and chloride in the solution lowered the amount of exchanged sulfate. The exchange experiments in a simulated soil under water-saturated and water-unsaturated conditions showed that a considerable proportion of the soil sulfate was exchanged by the PRS probes after about 10 d. There was no evidence for significant sulfur and oxygen isotope fractionation between soil sulfate and sulfate recovered from the PRS probes. Therefore, we recommend the use of PRS probes as an efficient and easy way to collect soil water sulfate for determination of its isotope composition. PMID:18268314

  2. Hydrogen isotope exchange experiments with Mt Mazama ash

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    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.

  3. Iron isotope fractionation between aqueous Fe(II) and goethite revisited: New insights based on a multi-direction approach to equilibrium and isotopic exchange rate modification

    NASA Astrophysics Data System (ADS)

    Frierdich, Andrew J.; Beard, Brian L.; Reddy, Thiruchelvi R.; Scherer, Michelle M.; Johnson, Clark M.

    2014-08-01

    The Fe isotope compositions of naturally occurring Fe oxide minerals provide insights into biogeochemical processes that occur in modern and ancient environments. Key to understanding isotopic variations in such minerals is knowledge of the equilibrium Fe isotope fractionation factors between common minerals and aqueous Fe species. Because experimental measurements of isotopic fractionation may reflect a combination of kinetic and equilibrium fractionations during rapid dissolution and precipitation, even in experiments that employ the three-isotope method, assessment of the attainment of equilibrium is often difficult. Here, we re-examine Fe isotope exchange, via a 57Fe tracer, and natural mass-dependent fractionation, through changes in initial 56Fe/54Fe ratios, between aqueous Fe(II) (Fe(II)aq) and goethite. This approach uses the three-isotope method, but is distinct in its evaluation of kinetic isotope fractionation and the attainment of equilibrium by: (i) employing a multi-direction approach to equilibrium at 22 °C via reaction of three Fe(II)aq solutions that had different initial 56Fe/54Fe ratios, (ii) conducting isotopic exchange experiments at elevated temperature (50 °C), and (iii) modifying the rate of isotopic exchange through a combination of trace-element substitutions and particle coarsening to evaluate corresponding temporal changes in fractionation trajectories that may reflect changing instantaneous fractionation factors. We find that rapid isotopic exchange produces kinetic isotope effects between Fe(II)aq and goethite, which shifts the 56Fe/54Fe ratios of Fe(II)aq early in reactions toward that of goethite, indicating that the instantaneous Fe(II)aq-goethite fractionation factor under kinetic conditions is small. Importantly, however, this kinetic fractionation is “erased” with continued reaction, and this is evident by the congruence for multiple-exchange trajectories of distinct initial Fe(II)aq solutions toward the same final value

  4. Aspartate beta-decarboxylase from Alcaligenes faecalis: carbon-13 kinetic isotope effect and deuterium exchange experiments

    SciTech Connect

    Rosenberg, R.M.; O'Leary, M.H.

    1985-03-26

    The authors have measured the /sup 13/C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D/sub 2/O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D/sub 2/O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The /sup 13/C kinetic isotope effect, with a value of 1.0099 +/- 0.0002 at pH 5.0, is less than the intrinsic isotope effect for the decarboxylation step, indicating that the decarboxylation step is not entirely rate limiting. The authors have been able to estimate probable values of the relative free energies of the transition states of the enzymatic reaction up to and including the decarboxylation step from the /sup 13/C kinetic isotope effect and the rate of D-H exchange of alpha-H. The pH dependence of the kinetic isotope effect reflects the pKa of the pyridine nitrogen of the coenzyme pyridoxal 5'-phosphate but not that of the imine nitrogen. A mechanism is proposed for the exchange of aspartate beta-H that is consistent with the stereochemistry suggested earlier.

  5. Position-specific measurement of oxygen isotope ratios in cellulose: Isotopic exchange during heterotrophic cellulose synthesis

    NASA Astrophysics Data System (ADS)

    Waterhouse, John S.; Cheng, Shuying; Juchelka, Dieter; Loader, Neil J.; McCarroll, Danny; Switsur, V. Roy; Gautam, Lata

    2013-07-01

    We describe the first reported method for the measurement of oxygen isotope ratios at each position in the glucose units of the cellulose molecule. The overall process comprises a series of synthetic organic sequences, by which α-cellulose is hydrolysed to glucose, and oxygen atoms at specific positions in the glucose molecule are removed in samples of benzoic acid for measurement of δ18O. Values of δ18O at specific positions in cellulose are calculated from these δ18O values and the overall δ18O value of the cellulose. We apply the method to determine the degree to which oxygen atoms at each position undergo isotopic exchange with water during heterotrophic cellulose synthesis, such as occurs in the cambium of trees. To do this we extract α-cellulose from wheat seedlings germinated in the dark in aqueous media of differing oxygen isotope ratios. Results indicate that oxygen atoms at positions 5 and 6 (O-5 and O-6 respectively) undergo around 80% exchange with medium water, O-3 undergoes around 50% exchange, and O-2 and O-4 do not undergo isotopic exchange. The results have important implications for extracting palaeoclimatic records from oxygen isotope time series obtained from tree ring cellulose. As O-5 and O-6 undergo significant exchange with medium water during heterotrophic cellulose synthesis, oxygen isotopes at these positions in tree ring cellulose should carry a predominantly trunk (source) water signal. On the other hand, O-2 and O-4 should retain the isotopic signature of leaf water in tree ring cellulose. Our method therefore potentially enables the separate reconstruction of past temperature and humidity data from oxygen isotope ratios of tree ring cellulose - something that has hitherto not been possible. The measured degrees of isotopic exchange are to some extent unexpected and cannot be fully explained using current biochemical mechanisms, suggesting that knowledge of these processes is incomplete.

  6. Development of an analytical hydrogen isotope exchange model in fusion relevant plasma facing components

    NASA Astrophysics Data System (ADS)

    Barton, Joseph; Wang, Yongquang; Doerner, Russell; Tynan, George

    2014-10-01

    A simple model for H isotope retention depth profiles in W is developed, which can easily be extended to other plasma facing components (PFCs). This retention model is subsequently used to model how the depth profile changes after H isotope exchange. We calculate how trapping defects in W trap D (or H) inventory as W is being exposed to plasma. The model characterizes each trapping site by a trapping rate and a release rate, where the only free parameters are the distribution of these trapping sites in the material. The filled trap concentrations for each trap type are modeled as a diffusion process because post-mortem D depth profiles indicate that traps are filled well beyond the ion implantation zone (3--4 nm with 100 eV ions). Using this retention model, an isotope exchange rate is formulated. The retention model and isotope exchange rate are compared to low temperature (100 °C) isotope exchange experiments in W with good agreement. Experimental retention profiles were measured using the D(3He,p) α nuclear reaction after plasma treatment. We additionally discuss how a uniform damage profile up to 1 micron in W induced by Cu ions using incident energies of 0.5, 2, and 5 MeV affect retention in W and the retention model.

  7. Isotopic exchange of carbon-bound hydrogen over geologic timescales

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

    2004-04-01

    The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 10 4 to 10 8 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ˜75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D 2O

  8. Kinetic isotope effects for fast deuterium and proton exchange rates

    PubMed Central

    Mammoli, Daniele; Kadeřávek, Pavel; Pelupessy, Philippe; Bodenhausen, Geoffrey

    2016-01-01

    By monitoring the effect of deuterium decoupling on the decay of transverse 15N magnetization in D–15N spin pairs during multiple-refocusing echo sequences, we have determined fast D–D exchange rates k D and compared them with fast H–H exchange rates k H in tryptophan to determine the kinetic isotope effect as a function of pH and temperature. PMID:27009684

  9. PEP Carboxykinase Exchange Reaction in Photosynthetic Bacteria 1

    PubMed Central

    Cooper, T. G.; Benedict, C. R.

    1968-01-01

    This paper describes some new characteristics of the phosphoenolpyruvate carboxykinase CO2-oxaloacetate exchange reaction in purified preparations of Rhodospirillum rubrum. The enzymatic activity has been purified 169-fold. Nucleotide diphosphates substitute for nucleotide triphosphates in the exchange reaction. Nucleotide diphosphates will not support the synthesis of phosphoenolpyruvate from oxaloacetate. This reaction differs significantly from the CO2-oxaloacetate exchange reaction in higher plants and animals. PMID:5661493

  10. Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Kendrick, B. K.; Hazra, Jisha; Balakrishnan, N.

    2015-10-01

    Quantum reactive scattering calculations for the hydrogen exchange reaction H +H2 (v =4 ,j =0 )→H +H2 (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.

  11. Practically convenient and industrially-aligned methods for iridium-catalysed hydrogen isotope exchange processes.

    PubMed

    Cochrane, A R; Idziak, C; Kerr, W J; Mondal, B; Paterson, L C; Tuttle, T; Andersson, S; Nilsson, G N

    2014-06-14

    The use of alternative solvents in the iridium-catalysed hydrogen isotope exchange reaction with developing phosphine/NHC Ir(I) complexes has identified reaction media which are more widely applicable and industrially acceptable than the commonly employed chlorinated solvent, dichloromethane. Deuterium incorporation into a variety of substrates has proceeded to deliver high levels of labelling (and regioselectivity) in the presence of low catalyst loadings and over short reaction times. The preparative outputs have been complemented by DFT studies to explore ligand orientation, as well as solvent and substrate binding energies within the catalyst system. PMID:24756541

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

    SciTech Connect

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

    2015-03-01

    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.

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

    SciTech Connect

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

    2011-05-01

    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. Influence of the isotope effect on the charge exchange in slow collisions of Li, Be, and C ions with H, D, and T

    SciTech Connect

    Tolstikhina, Inga Yu.; Shevelko, V. P.; Kato, Daiji

    2011-07-15

    The influence of the isotope effect (mass dependence) on the charge-exchange process in low-energy collisions of light ions with hydrogen isotopes (H, D, and T) is studied using the adiabatic theory of transitions in slow collisions developed by E. Solov'ev [Sov. Phys. Usp. 32, 228 (1989)]. Results of the numerical calculations are presented for the charge-exchange probabilities and cross sections of Li, Be, and C ions colliding with hydrogen isotopes and for the inverse reactions.

  15. Upper limit on the rate constant for isotope exchange between molecular oxygen and ozone at 298 K

    NASA Technical Reports Server (NTRS)

    Anderson, S. M.; Morton, J.; Mauersberger, K.

    1987-01-01

    The gas phase bimolecular isotope exchange reaction between molecular oxygen and ozone has been investigated directly for the first time. Its rate coefficient is found to be less than 2 x 10 to the -25th cu cm/sec at 298 K, over six orders of magnitude below recent estimates. Much faster exchange was observed over condensed ozone at 77 K, suggesting isotopic scrambling is catalyzed under these conditions. The low rate coefficient implies that homogeneous exchange between ground state oxygen and ozone molecules cannot play a significant role in heavy ozone chemistry.

  16. Isotope exchange by Ion Cyclotron Wall Conditioning on JET

    NASA Astrophysics Data System (ADS)

    Wauters, T.; Douai, D.; Kogut, D.; Lyssoivan, A.; Brezinsek, S.; Belonohy, E.; Blackman, T.; Bobkov, V.; Crombé, K.; Drenik, A.; Graham, M.; Joffrin, E.; Lerche, E.; Loarer, T.; Lomas, P. L.; Mayoral, M.-L.; Monakhov, I.; Oberkofler, M.; Philipps, V.; Plyusnin, V.; Sergienko, G.; Van Eester, D.

    2015-08-01

    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 × 10-3 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 H2-ICWC at ITER half field conditions on the JET-ILW preloaded by D2 tokamak operation is estimated to be 7.3 × 1022 hydrogenic atoms, and may be exchanged within 400 s of cumulated ICWC discharge time.

  17. Isotope dilution study of exchangeable oxygen in premium coal samples

    SciTech Connect

    Finseth, D.

    1987-01-01

    A difficulty with improving the ability to quantitate water in coal is that truly independent methods do not always exist. The true value of any analytical parameter is always easier to determine if totally independent methods exist to determine that parameter. This paper describes the possibility of using a simple isotope dilution technique to determine the water content of coal and presents a comparison of these isotope dilution measurements with classical results for the set of Argonne coals from the premium coal sample program. Isotope dilution is a widely used analytical method and has been applied to the analysis of water in matrices as diverse as chicken fat, living humans, and coal. Virtually all of these applications involved the use of deuterium as the diluted isotope. This poses some problems if the sample contains a significant amount of exchangeable organic hydrogen and one is interested in discriminating exchangeable organic hydrogen from water. This is a potential problem in the coal system. To avoid this potential problem /sup 18/O was used as the diluted isotope in this work.

  18. Oxygen isotope exchange and isotopic fractionation during N2O production by denitrification

    NASA Astrophysics Data System (ADS)

    Lewicka-Szczebak, Dominika; Well, Reinhard; Kaiser, Jan

    2014-05-01

    Stable isotopic analyses of N2O may help in quantification of soil denitrification processes. N2O reduction to N2 during denitrification is associated with significant isotopic fractionation. Theoretically, this would allow the product ratio (N2O/(N2+N2O)) to be calculated based on the isotopic signature of the remaining N2O if the isotopic signature of the produced N2O were precisely predictable. Oxygen isotopes are especially useful, in particular the 17O excess, Δ(17O), to quantify any oxygen isotope exchange between soil water and intermediate products (NO2-, NO). This significantly influences the δ(18O) values of the N2O produced. Previous studies showed this exchange to be nearly complete, up to 90% 1,2. However, there are very few studies on the associated oxygen isotopic fractionation and its potential coupling to the magnitude of oxygen isotope exchange with soil water 2,3. We hypothesize that for high oxygen exchange, the oxygen isotopic fractionation will show little variability. In previous experiments, an 18O-enriched tracer was applied to quantify the magnitude of oxygen exchange 1,2. Such an approach does not permit determining any oxygen isotope fractionation. Here, we applied two novel experimental approaches: (1) waters of two different δ(18O) values within the natural range (-1.5 and -14.8 o relative to VSMOW) were used for rewetting the incubated soils and the oxygen exchange was calculated from comparing the relative isotope ratio difference between N2O and H2O for these two water treatments; (2) soils were amended with Chile Saltpeter characterized by a high 17O excess (20.2 o ) and the 17O excess of the N2O product was measured. Both approaches were applied simultaneously on the same soil samples, which allowed quantifying the oxygen isotope exchange with two independent methods at the same time. The N2O reduction was inhibited with acetylene method and δ(18O) values of the N2O produced were measured to determine the oxygen fractionation

  19. Global simulation of the carbon isotope exchange of terrestrial ecosystems

    NASA Astrophysics Data System (ADS)

    Ito, A.; Terao, Y.; Mukai, H.

    2009-12-01

    There remain large uncertainties in our quantification of global carbon cycle, which has close interactions with the climate system and is subject to human-induced global environmental change. Information on carbon isotopes is expected to reduce the uncertainty by providing additional constraints on net atmosphere-ecosystem exchange. This study attempted to simulate the dynamics of carbon isotopes at the global scale, using a process-based terrestrial ecosystem model: Vegetation Integrative SImulator for Trace gases (VISIT). The base-model of carbon cycle (Sim-CYCLE, Ito 2003) has already considered stable carbon isotope composition (13C/12C), and here radioactive carbon isotope (14C) was included. The isotope ratios characterize various aspects of terrestrial carbon cycle, which is difficult to be constrained by sole mass balance. For example, isotopic discrimination by photosynthetic assimilation is closely related with leaf stomatal conductance and composition of C3 and C4 plant in grasslands. Isotopic disequilibrium represents mean residence time of terrestrial carbon pools. In this study, global simulations (spatial resolution 0.5-deg, time-step 1-month) were conducted during the period 1901 to 2100 on the basis of observed and projected atmospheric CO2, climate, and land-use conditions. As anthropogenic CO2 accumulates in the atmosphere, heavier stable carbon isotope (13C) was diluted, while radioactive carbon isotope (14C) is strongly affected by atomic bomb experiments mainly in the 1950s and 1960s. The model simulated the decadal change in carbon isotope compositions. Leaf carbon with shorter mean residence time responded rapidly to the atmospheric change, while plant stems and soil humus showed substantial time-lag, leading to large isotopic disequilibrium. In the future, the isotopic disequilibrium was estimated to augment, due to accelerated rate of anthropogenic CO2 accumulation. Spatial distribution of stable isotope composition (12C/13C, or d13C) was

  20. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    ERIC Educational Resources Information Center

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  1. Hydrogen isotope separation by catalyzed exchange between hydrogen and liquid water

    SciTech Connect

    Butler, J.P.

    1980-04-01

    The discovery, at Chalk River Nuclear Laboratories, of a simple method of wetproofing platinum catalysts so that they retain their activity in liquid water stimulated a concentrated research program for the development of catalysts for the hydrogen-water isotopic exchange reaction. This paper reviews 10 years of study which have resulted in the development of highly active platinum catalysts which remain effective in water for periods greater than a year. The most efficient way to use these catalysts for the separation of hydrogen isotopes is in a trickle bed reactor which effects a continuous separation. The catalyst is packed in a column with hydrogen and water flowing countercurrently through the bed. The overall isotope transfer rate measured for the exchange reaction is influenced by various parameters, such as hydrogen and water flow rates, temperature, hydrogen pressure, and platinum metal loading. The effect of these parameters as well as the improved performance obtained by diluting the hydrophobic catalyst with inert hydrophilic packing are discussed. The hydrophobic catalysts can be effectively used in a variety of applications of particular interest in the nuclear industry. A Combined Electrolysis Catalytic Exchange - Heavy Water Process (CECE-HWP) is being developed at Chalk River with the ultimate aim of producing parasitic heavy water from electrolytic hydrogen streams. Other more immediate applications include the final enrichment of heavy water and the extraction of tritium from light and heavy water. Pilot plant studies on these latter processes are currently in progress.

  2. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1979-01-01

    The heavy isotopic anomalies observed recently in the fractionation and unknown nuclear inclusions from the Allende meteorite are explained by neutron reactions during the explosive carbon burning (ECB). This model produces heavy anomalies in the same zone where Al-26 and O-16 are produced, thus reducing the number of source zones required for the isotopic anomalies. Unlike the classical r-process, the ECB n-process avoids the problem with the Sr anomaly and may resolve the problem of conflicting time scales between Al-26 and the r-process isotopes I-129 and Pu-244. Experimental studies of Zr and Ce isotopic composition are proposed to test this model.

  3. Insights into collisional magmatism from isotopic fingerprints of melting reactions.

    PubMed

    Knesel, Kurt M; Davidson, Jon P

    2002-06-21

    Piston-cylinder experiments in the granite system demonstrate that a variety of isotopically distinct melts can arise from progressive melting of a single source. The relation between the isotopic composition of Sr and the stoichiometry of the observed melting reactions suggests that isotopic signatures of anatectic magmas can be used to infer melting reactions in natural systems. Our results also indicate that distinct episodes of dehydration and fluid-fluxed melting of a single, metapelitic source region may have contributed to the bimodal geochemistry of crustally derived leucogranites of the Himalayan orogen. PMID:12077413

  4. Surface Exchange and Bulk Diffusivity of LSCF as SOFC Cathode: Electrical Conductivity Relaxation and Isotope Exchange Characterizations

    SciTech Connect

    Li, Yihong; Gerdes, Kirk; Horita, Teruhisa; Liu, Xingbo

    2013-05-05

    The oxygen diffusion coefficient (D) and surface exchange coefficient (k) of a typical SOFC cathode material, La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-δ} (LSCF) were characterized by both electrical conductivity relaxation (ECR) and oxygen isotope exchange (IE) methods. Conductivity relaxation experiments were conducted at 800°C for small step changes in partial pressure of oxygen (P{sub O{sub 2}} ), both decreasing and increasing, from 0.02 atm to 0.20 atm. The results revealed P{sub O{sub 2}} dependent hysteresis with the reduction process requiring more equilibration time than oxidation. Analysis of the experimental data indicated that the surface exchange coefficient is a function of the final oxygen partial pressure in an isothermal system. In addition, both forward and backward oxygen reduction reaction constants, which are vital for the fundamental understanding of SOFC cathode reaction mechanisms, are investigated based on the relationship between surface exchange coefficient and P{sub O{sub 2}} . The direct comparisons between the results from both ECR and IE were presented and the possible experimental errors in both methods were discussed.

  5. Probing Isotope Effects in Chemical Reactions Using Single Ions

    SciTech Connect

    Staanum, Peter F.; Hoejbjerre, Klaus; Drewsen, Michael; Wester, Roland

    2008-06-20

    Isotope effects in reactions between Mg{sup +} in the 3p {sup 2}P{sub 3/2} excited state and molecular hydrogen at thermal energies are studied through single reaction events. From only {approx}250 reactions with HD, the branching ratio between formation of MgD{sup +} and MgH{sup +} is found to be larger than 5. From an additional 65 reactions with H{sub 2} and D{sub 2} we find that the overall fragmentation probability of the intermediate MgH{sub 2}{sup +}, MgHD{sup +}, or MgD{sub 2}{sup +} complexes is the same. Our study shows that few single ion reactions can provide quantitative information on ion-neutral reactions. Hence, the method is well suited for reaction studies involving rare species, e.g., rare isotopes or short-lived unstable elements.

  6. Probing Isotope Effects in Chemical Reactions Using Single Ions

    NASA Astrophysics Data System (ADS)

    Staanum, Peter F.; Højbjerre, Klaus; Wester, Roland; Drewsen, Michael

    2008-06-01

    Isotope effects in reactions between Mg+ in the 3p P3/22 excited state and molecular hydrogen at thermal energies are studied through single reaction events. From only ˜250 reactions with HD, the branching ratio between formation of MgD+ and MgH+ is found to be larger than 5. From an additional 65 reactions with H2 and D2 we find that the overall fragmentation probability of the intermediate MgH2+, MgHD+, or MgD2+ complexes is the same. Our study shows that few single ion reactions can provide quantitative information on ion-neutral reactions. Hence, the method is well suited for reaction studies involving rare species, e.g., rare isotopes or short-lived unstable elements.

  7. Carbon dioxide in the atmosphere: isotopic exchange with ozone and its use as a tracer in the middle atmosphere

    NASA Technical Reports Server (NTRS)

    Yung, Y. L.; Lee, A. Y.; Irion, F. W.; DeMore, W. B.; Wen, J.

    1997-01-01

    Atmospheric heavy ozone is enriched in the isotopes 18O and 17O. The magnitude of this enhancement, of the order of 100%, is very large compared with that commonly known in atmospheric chemistry and geochemistry. The heavy oxygen atom in heavy ozone is therefore useful as a tracer of chemical species and pathways that involve ozone or its derived products. As a test of the isotopic exchange reactions, we successfully carry out a series of numerical experiments to simulate the results of the laboratory experiments performed by Wen and Thiemens [1993] on ozone and CO2. A small discrepancy between the experimental and the model values for 17O exchange is also revealed. The results are used to compute the magnitude of isotopic exchange between ozone and carbon dioxide via the excited atom O(1D) in the middle atmosphere. The model for 18O is in good agreement with the observed values.

  8. Using reactive artificial muscles to determine water exchange during reactions

    NASA Astrophysics Data System (ADS)

    Otero, T. F.; Martínez, J. G.; Zaifoglu, B.

    2013-10-01

    Artificial muscles based on films of conducting polymers translate film volume variations, driven by electrochemical reactions (Faradaic motors), into macroscopic movements with generation of mechanical energy. The reaction promotes exchange of counterions (anions here) and solvent molecules with the electrolyte. Attributing here both the film volume variation and the movement originated by these exchanges of ions and solvent, the described angles can be used to quantify the exchanged solvent. Different angles described by bending muscles consuming equal driving charges in electrolytes having the same cation and different anions were measured. The number of exchanged counterions is given by the consumed charge and the ion valence: this is a Faradaic reaction. The described angle fraction due to the exchanged anions is given by the number of anions and the crystallographic radius. Taking as reference the anion giving the shorter angle, whatever the consumed charge, the relative number of solvent molecules exchanged by the polymeric membrane during a reversible reaction was determined. Actuators and artificial muscles can be used as useful tools for, at least, an initial study of the solvent exchange during reactions in reactive gels.

  9. Diffusion, trapping, and isotope exchange of plasma implanted deuterium in ion beam damaged tungsten

    NASA Astrophysics Data System (ADS)

    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

  10. Phospholipid exchange reactions within the liver cell

    PubMed Central

    McMurray, W. C.; Dawson, R. M. C.

    1969-01-01

    1. Isolated rat liver mitochondria do not synthesize labelled phosphatidylcholine from CDP-[14C]choline or any phospholipid other than phosphatidic acid from [32P]phosphate. The minimal labelling of phosphatidylcholine and other phosphoglycerides can be attributed to microsomal contamination. However, when mitochondria and microsomes are incubated together with [32P]phosphate, the phosphatidylcholine, phosphatidylinositol and phosphatidylethanolamine of the reisolated mitochondria become labelled, suggesting a transfer of phospholipids between the two fractions. 2. When liver microsomes or mitochondria containing labelled phosphatidylcholine are independently incubated with the opposite un-labelled fraction, there is a substantial and rapid exchange of the phospholipid between the two membranes. Exchange of phosphatidylinositol also occurs rapidly, whereas phosphatidylethanolamine and phosphatidic acid exchange only slowly. There is no corresponding transfer of marker enzymes. The transfer of phosphatidylcholine does not occur at 0°, and there is no requirement for added substrate, ATP or Mg2+, but the omission of a heat-labile supernatant fraction markedly decreases the exchange. 3. After intravenous injection of [32P]phosphate, short-period labelling experiments of the individual phospholipids of rat liver microsomes and mitochondria in vivo give no evidence for a similar exchange process. However, the incubation of isolated microsomes and mitochondria with [32P]phosphate also fails on reisolation of the fractions to demonstrate a precursor–product relationship between the individual phospholipids of the two membranes. 4. The intraperitoneal injection of [32P]phosphate results in a far greater proportion of the dose entering the liver than does intravenous administration. After intraperitoneal administration of [32P]phosphate the specific radioactivities of the individual phospholipids are in the order microsomes > outer mitochondrial membrane > inner

  11. Novel uses of isotope effects to elucidate enzyme reaction mechanisms

    SciTech Connect

    Hermes, J.D.

    1983-01-01

    A new technique (Multiple Isotope Effects) for determining enzyme reaction mechanisms and intrinsic isotope effects has been developed. By determining the /sup 13/C isotope effect on V/K with both a deuterated and unlabeled substrate, and the deuterium isotope effect on V/K, it is possible to tell whether the /sup 13/C-sensitive and deuterium-sensitive steps are the same or not and, if they are different, to determine which comes first in the mechanism. If the two isotope-sensitive steps are the same, 1) deuteration increases the size of the observed /sup 13/C isotope effect, and 2) the intrinsic /sup 13/C and deuterium isotope effects, and the commitments can be calculated. When the deuterium- and /sup 13/C-sensitive steps are different, deuteration decreases the size of the observed /sup 13/C isotope effect. The data fit the equation (/sup 13/(V/K)/sub H/ - 1)/(/sup 13/(V/K)/sub D/ - 1) = /sup D/(V/K)//sup D/K/sub eq/ when the deuterium-sensitive step comes first, but fit the equation (/sup 13/(V/K)/sub H/ - /sup 13/K/sub eq/)/(/sup 13/(V/K)/sub D/ - /sup 13/K/sub eq/) = /sup D/(V/K) when the /sup 13/C-sensitive step comes first.

  12. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals

    PubMed Central

    2015-01-01

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn2+ and Cd2+) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu2–xSe) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core–shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu+ ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu2–xSe samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  13. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

    PubMed

    Lesnyak, Vladimir; Brescia, Rosaria; Messina, Gabriele C; Manna, Liberato

    2015-07-29

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  14. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds. PMID:18728883

  15. Systematic analysis of reaction cross sections of carbon isotopes

    SciTech Connect

    Horiuchi, W.; Suzuki, Y.; Abu-Ibrahim, B.; Kohama, A.

    2007-04-15

    We systematically analyze total reaction cross sections of carbon isotopes with N= 6-16 on a {sup 12}C target for wide range of incident energy. The intrinsic structure of the carbon isotope is described by a Slater determinant generated from a phenomenological mean-field potential, which reasonably well reproduces the ground-state properties for most of the even N isotopes. We need separate studies not only for odd nuclei but also for {sup 16}C and {sup 22}C to improve their wave functions. The density of the carbon isotope is constructed by eliminating the effect of the center-of-mass motion. For the calculations of the cross sections, we take two schemes, the Glauber approximation and the eikonal model using a global optical potential. Both the reaction models successfully reproduce low and high incident energy data on the cross sections of {sup 12}C, {sup 13}C, and {sup 16}C on {sup 12}C. The calculated reaction cross sections of {sup 15}C are found to be considerably smaller than the empirical values observed at low energy. We find a consistent parametrization of the nucleon-nucleon scattering amplitude, differently from previous ones. Finally, we predict the total reaction cross section of {sup 22}C on {sup 12}C.

  16. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    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

  17. Solvent isotope effects on nucleophilic displacement reactions

    SciTech Connect

    Spiegel, G.W.

    1981-01-01

    The kinetic solvent isotope effect, KSIE, (k/sub H/sub 2/O//k/sub D/sub 2/O/), at 25.0/sup 0/C and ionic strength, I, equal to 0.20 +- 0.02 M was measured for the nucleophilic displacement of iodine ion from iodomethane, iodoacetamide, and iodoacetate ion, thiophene from S-Methylthiophenium ion, and tosylate ion from methyl tosylate by bromide ion, chloride ion, acetate ion, hydroxide ion, water, ammonia, ethylenediamine, n-butylamine, piperazine, piperidine, quinuclidine, and 1,4-Diazabicyclo(2.2.2)octane (DABCO), and the monoprotonated cations of ethylenediamine, piperazine, and DABCO. By means of solvent partition measurements at 25.0/sup 0/C and I = 0.02 M between H/sub 2/O and D/sub 2/O and a common immiscible organic solvent, the ground state activity coefficients in D/sub 2/O, the solution in H/sub 2/O being chosen as the reference state, were determined for the nitrogen-containing nucleophiles (except ammonia) and the substrates methyl tosylate, iodoacetamide, and iodoacetic acid. The solubilities at 25.0/sup 0/C of the picrate and tetraphenylborate salts of the monoprotonated cationic forms of ethylenediamine, piperazine, and DABCO were measured to determine the activity coefficients in D/sub 2/O of these ions relative to an H/sub 2/O reference state. Applying the Eyring equation, the activity coefficients of the transition states in D/sub 2/O, reference state H/sub 2/O, were calculated.

  18. Initial rate and isotope exchange studies of rat skeletal muscle hexokinase

    SciTech Connect

    Ganson, N.J.; Fromm, H.J.

    1985-10-05

    The kinetic mechanism of rat skeletal muscle hexokinase (hexokinase II) was investigated in light of a proposal by Cornish-Bowden and his co-workers. The authors investigated the mechanism of action of hexokinase II by studying initial rate kinetics in the nonphysiological direction and by isotope exchange at chemical equilibrium. The former experiments were carried out in the absence of inhibitors and then with AMP, which is a competitive inhibitor of ADP, and with glucose 1,6-bisphosphate, a competitive inhibitor of glucose-6-P. The findings from these experiments suggest that the kinetic mechanism is rapid equilibrium Random Bi Bi. Isotope exchange at equilibrium studies also supports the random nature of the muscle hexokinase reaction; however, they also suggest that the mechanism is partially ordered, i.e. there is a preferred pathway associated with the branched mechanism. Approximately two-thirds of the flux through the hexokinase reaction involves the glucose on first glucose-6-P off last branch of the Random Bi Bi mechanism. These results imply that the kinetic mechanism is steady state Random Bi Bi. There is some evidence to suggest that glucose-6-P binds to an allosteric site on muscle hexokinase, but none to suppose that ATP binds allosterically.

  19. Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

    USGS Publications Warehouse

    Stoffregen, R.E.; Rye, R.O.; Wasserman, M.D.

    1994-01-01

    Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400??C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from -6.25 moles alkali m-2s-1 at 400??C to - 11.7 moles alkali m-2s-1 at 200??C. The variation in these rates with temperature is given by the equation log k* = -8.17(1000/T(K)) + 5.54 (r2 = 0.987) which yields an activation energy of 37.4 ?? 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ?? 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100??C. Computed hydrogen diffusion coefficients range from -15.7 to -17.3 cm2s-1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause

  20. Direct Measurement of Biosphere-Atmosphere Isotopic Exchange Using the Eddy Covariance Technique

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Quantifying isotopic CO2 exchange between the biosphere and atmosphere presents a significant measurement challenge, but has the potential to provide important constraints on local, regional, and global carbon cycling. Past approaches have indirectly estimated isotopic CO2 exchange using relaxed edd...

  1. Heat exchanger development at Reaction Engines Ltd.

    NASA Astrophysics Data System (ADS)

    Varvill, Richard

    2010-05-01

    The SABRE engine for SKYLON has a sophisticated thermodynamic cycle with heat transfer between the fluid streams. The intake airflow is cooled in an efficient counterflow precooler, consisting of many thousand small bore thin wall tubes. Precooler manufacturing technology has been under investigation at REL for a number of years with the result that flightweight matrix modules can now be produced. A major difficulty with cooling the airflow to sub-zero temperatures at low altitude is the problem of frost formation. Frost control technology has been developed which enables steady state operation. The helium loop requires a top cycle heat exchanger (HX3) to deliver a constant inlet temperature to the main turbine. This is constructed in silicon carbide and the feasibility of manufacturing various matrix geometries has been investigated along with suitable joining techniques. A demonstration precooler will be made to run in front of a Viper jet engine at REL's B9 test facility in 2011. This precooler will incorporate full frost control and be built from full size SABRE engine modules. The facility will incorporate a high pressure helium loop that rejects the absorbed heat to a bath of liquid nitrogen.

  2. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  3. Water Vapor Isotopic Fractionation and Strat/trop Exchange

    NASA Astrophysics Data System (ADS)

    Jucks, K. W.; Johnson, D. G.; Traub, W. A.; Chance, K. V.

    We will present atmospheric observations of the isotopic fractionation for water vapor as observed by the Smithsonian Astrophysical Observatory far-infrared spectrometer (FIRS-2). The stratospheric observations are corrected with a photochemical model to account for methane oxidation to determine the "entry level" isotopic fractionation of water in the stratosphere. These values are then compared to a simple Rayleigh frac- tionation model that includes estimations of convection, radiative heating, and mixing to infer relative contributions to stratosphere/troposphere exchange. The observations of water vapor fractionation are most consistent with a model that mixes air uplifted from roughly 11 km with significantly more air that has been dehydrated by convec- tion to an effective temperature that is much cooler than the tropopause temperature. The water vapor mixing ratio in the stratosphere results from a combination of radia- tive heating, recirculation of stratospheric air, and deep convection that supplies the air to the upper tropical troposphere. We believe that these types of observations could be a powerful tool for constraining circulation models.

  4. An Exchange-Only Qubit in Isotopically Enriched 28Si

    NASA Astrophysics Data System (ADS)

    Gyure, Mark

    2015-03-01

    We demonstrate coherent manipulation and universal control of a qubit composed of a triple quantum dot implemented in an isotopically enhanced Si/SiGe heterostructure, which requires no local AC or DC magnetic fields for operation. Strong control over tunnel rates is enabled by a dopantless, accumulation-only device design, and an integrated measurement dot enables single-shot measurement. Reduction of magnetic noise is achieved via isotopic purification of the silicon quantum well. We demonstrate universal control using composite pulses and employ these pulses for spin-echo-type sequences to measure both magnetic noise and charge noise. The noise measured is sufficiently low to enable the long pulse sequences required for exchange-only quantum information processing. Sponsored by United States Department of Defense. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressly or implied, of the United States Department of Defense or the U.S. Government. Approved for public release, distribution unlimited.

  5. Mass Dependence of Iron Isotope Fractionation in Fe(II)-Fe(III) Electron Exchange Equilibration

    NASA Astrophysics Data System (ADS)

    Fujii, Yasuhiko; Kim, Sang-Ho; Nomura, Masao; Kawakami, Fumiaki

    2013-02-01

    A one hundred meter long ion-exchange chromatograph was used to establish rigorously the mass effects in the iron isotope fractionation in the Fe(II)-Fe(III) electron exchange equilibration.We used a highly porous, strongly basic anion exchange resin packed in glass columns. The abundance ratios of all natural iron isotopes, 54Fe, 56Fe, 57Fe, and 58Fe, in the effluent at the iron adsorption band boundary were measured with a mass spectrometer. The enrichment correlations among these isotopes were analyzed by three-isotope plots. The results clearly showed that the isotope fractionation of Fe(II)-Fe(III) is governed by the normal mass effect; the iron isotope fractionation is not proportional to the nuclear size, but proportional to the reduced mass difference of the pair of iron isotopes.

  6. Pion double charge exchange reactions leading to double pionic atoms

    SciTech Connect

    Nieves, J.; Oset, E.; Vincente-Vacas, M.J. ); Hirenzaki, S.; Toki, H. )

    1992-10-20

    In this paper, the authors study theoretically pion double charge exchange reactions leading to double pionic atoms. The reaction cross-sections with two pions in the deeper bound pionic orbits in [sup 208]Pb are calculated with realistic pionic atom wave functions and distortion effects. The cross-sections are found to be d[sup 2] [sigma]/dEd[Omega] [approx] 10[sup [minus] 3] [minus] 10[sup [minus] 4] [mu]b/srMeV, which are only a small fraction of the double charge exchange.

  7. Individual breathing reactions measured in hemoglobin by hydrogen exchange methods

    SciTech Connect

    Englander, S.W.; Calhoun, D.B.; Englander, J.J.; Kallenbach, N.R.; Liem, R.K.H.; Malin, E.L.; Mandal, C.; Rogero, J.R.

    1980-10-01

    Protein hydrogen exchange is generally believed to register some aspect of internal protein dynamics, but the kind of motion at work is not clear. Experiments are being done to identify the determinants of protein hydrogen exchange and to distinguish between local unfolding and accessibility-penetration mechanisms. Results with small molecules, polynucleotides, and proteins demonstrate that solvent accessibility is by no means sufficient for fast exchange. H-exchange slowing is quite generally connected with intramolecular H-bonding, and the exchange process depends pivotally on transient H-bond cleavage. At least in ..cap alpha..-helical structures, the cooperative aspect of H-bond cleavage mut be expressed in local unfolding reactions. Results obtained by use of a difference hydrogen exchange method appear to provide a direct measurement of transient, cooperative, local unfolding reactions in hemoglobin. The reality of these supposed coherent breathing units is being tested by using the difference H-exchange approach to tritium label the units one at a time and then attempting to locate the tritium by fragmenting the protein, separating the fragments, and testing them for label. Early results demonstrate the feasibility of this approach.

  8. Iridium(I)-catalyzed regioselective C-H activation and hydrogen-isotope exchange of non-aromatic unsaturated functionality.

    PubMed

    Kerr, William J; Mudd, Richard J; Paterson, Laura C; Brown, Jack A

    2014-11-01

    Isotopic labelling is a key technology of increasing importance for the investigation of new CH activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium-catalyzed CH activation and hydrogen-isotope exchange at the β-position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3 )][PF6 ] (cod=1,5-cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β-activation and labelling of a range of α,β-unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading. PMID:25283156

  9. Ab Initio Nuclear Structure and Reaction Calculations for Rare Isotopes

    SciTech Connect

    Draayer, Jerry P.

    2014-09-28

    We have developed a novel ab initio symmetry-adapted no-core shell model (SA-NCSM), which has opened the intermediate-mass region for ab initio investigations, thereby providing an opportunity for first-principle symmetry-guided applications to nuclear structure and reactions for nuclear isotopes from the lightest p-shell systems to intermediate-mass nuclei. This includes short-lived proton-rich nuclei on the path of X-ray burst nucleosynthesis and rare neutron-rich isotopes to be produced by the Facility for Rare Isotope Beams (FRIB). We have provided ab initio descriptions of high accuracy for low-lying (including collectivity-driven) states of isotopes of Li, He, Be, C, O, Ne, Mg, Al, and Si, and studied related strong- and weak-interaction driven reactions that are important, in astrophysics, for further understanding stellar evolution, X-ray bursts and triggering of s, p, and rp processes, and in applied physics, for electron and neutrino-nucleus scattering experiments as well as for fusion ignition at the National Ignition Facility (NIF).

  10. Systematic study of (α ,γ ) reactions for stable nickel isotopes

    NASA Astrophysics Data System (ADS)

    Simon, A.; Beard, M.; Spyrou, A.; Quinn, S. J.; Bucher, B.; Couder, M.; DeYoung, P. A.; Dombos, A. C.; Görres, J.; Kontos, A.; Long, A.; Moran, M. T.; Paul, N.; Pereira, J.; Robertson, D.; Smith, K.; Stech, E.; Talwar, R.; Tan, W. P.; Wiescher, M.

    2015-08-01

    A systematic measurement of the (α ,γ ) reaction for all the stable nickel isotopes has been performed using the γ -summing technique. For two of the isotopes, 60Ni and 61Ni, the α -capture cross sections have been experimentally measured for the first time. For 58,62,64Ni, the current measurement is in excellent agreement with earlier results found in the literature, and additionally extends the energy range of the measured cross sections up to 8.7 MeV. The data provided a tool for testing the cross section predictions of Hauser-Feshbach calculations. The experimental results were compared to the cross sections calculated with the talys 1.6 code and commonly used databases non-smoker and bruslib. For each of the investigated isotopes a combination of input parameter for talys was identified that best reproduces the experimental data, and recommended reaction rate has been calculated. Additionally, a set of inputs for Hauser-Feshbach calculations was given that, simultaneously for all the isotopes under consideration, reproduces the experimental data within the experimental uncertainties.

  11. Investigation of Isotope Effects in Single Ion Reactions

    NASA Astrophysics Data System (ADS)

    Goeders, James; Clark, Craig; Khanyile, Ncamiso; Brown, Kenneth

    2011-05-01

    Cold molecular ions are of great interest for studying chemical reactions. At the ultralow temperatures achievable using laser cooling techniques, chemical reactions are dominated by quantum effects not generally observed at higher temperatures. Studying reactions at these low temperatures allows for probing of the reaction mechanisms and the topology of potential energy surfaces, providing tests of ab initio and reactive- scattering calculations. Many chemical reactions are dominated by isotope effects. Ion beam studies have looked at reactions of alkaline earth ions with HD and observed different patterns of reactivity between Period 2 and Period 3 elements. Magnesium was shown to have a larger reaction cross-section for forming MgD+ than MgH+ by a factor of 2 - 4. Single ion experiments involving reactions between Mg+ in the 3p2P3/2 excited state and HD, utilizing trapped atomic ions, were done by Staanum et al., showing a branching ratio on the order of the results seen in the beam studies. Ion beam experiments have also been done on ground-state 40Ca+ with HD. In those experiments, the ratio of formation of CaH+ to CaD+ was observed to be ~4, opposite and in stark contrast to the magnesium ratio. The current work compares single atomic calcium ion data with molecular beam data, looking at both the 4p2P3/2 and the 4p2P1/2 excited states, similar to the work done with Mg+.

  12. Prediction of Kinetic Isotope Effects for Various Hydride Transfer Reactions Using a New Kinetic Model.

    PubMed

    Shen, Guang-Bin; Xia, Ke; Li, Xiu-Tao; Li, Jun-Ling; Fu, Yan-Hua; Yuan, Lin; Zhu, Xiao-Qing

    2016-03-24

    In this work, kinetic isotope effect (KIEself) values of 68 hydride self-exchange reactions, XH(D) + X(+) → X(+) + XH(D), in acetonitrile at 298 K were determined using a new experimental method. KIE values of 4556 hydride cross transfer reactions, XH(D) + Y(+) → X(+) + YH(D), in acetonitrile were estimated from the 68 determined KIEself values of hydride self-exchange reactions using a new KIE relation formula derived from Zhu's kinetic equation and the reliability of the estimations was verified using different experimental methods. A new KIE kinetic model to explain and predict KIE values was developed according to Zhu's kinetic model using two different Morse free energy curves instead of one Morse free energy curve in the traditional KIE theories to describe the free energy changes of X-H bond and X-D bond dissociation in chemical reactions. The most significant contribution of this paper to KIE theory is to build a new KIE kinetic model, which can be used to not only uniformly explain the various (normal, enormous and inverse) KIE values but also safely prodict KIE values of various chemical reactions. PMID:26938149

  13. Ruthenium(0) nanoparticle-catalyzed isotope exchange between 10B and 11B nuclei in decaborane(14).

    PubMed

    Yinghuai, Zhu; Widjaja, Effendi; Sia, Shirley Lo Pei; Zhan, Wang; Carpenter, Keith; Maguire, John A; Hosmane, Narayan S; Hawthorne, M Frederick

    2007-05-23

    Well dispersed ruthenium(0) nanoparticles, stabilized in the ionic liquid agent, trihexyltetradecylphosphonium dodecylbenzenesulfonate, have been successfully prepared via a reduction reaction of the precursor [CpRuCp*RuCp*]PF6 (Cp* = C5Me5). The ruthenium(0) nanoparticles were shown to catalyze the isotope exchange reaction between 10B enriched diborane and natural abundant B10H14 to produce highly 10B enriched (approximately 90%) decaborane(14) products. The ruthenium(0) nanoparticles were characterized by TEM, XRD, and XPS. The 10B enriched decaborane(14) has been analyzed by Raman spectroscopy, NMR, and high-resolution MS. PMID:17472379

  14. Cross-ligation and exchange reactions catalyzed by hairpin ribozymes.

    PubMed Central

    Komatsu, Y; Koizumi, M; Sekiguchi, A; Ohtsuka, E

    1993-01-01

    The negative strand of the satellite RNA of tobacco ringspot virus (sTobRV(-)) contains a hairpin catalytic domain that shows self-cleavage and self-ligation activities in the presence of magnesium ions. We describe here that the minimal catalytic domain can catalyze a cross-ligation reaction between two kinds of substrates in trans. The cross-ligated product increased when the reaction temperature was decreased during the reaction from 37 degrees C to 4 degrees C. A two-stranded hairpin ribozyme, divided into two fragments between G45 and U46 in a hairpin loop, showed higher ligation activity than the nondivided ribozyme. The two stranded ribozyme also catalyzed an exchange reaction of the 3'-portion of the cleavage site. Images PMID:8441626

  15. Isotopic exchange in mineral-fluid systems. 4. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H{sub 2}O and layer silicate-H{sub 2}O systems

    SciTech Connect

    Cole, D.R.

    2000-03-01

    Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. The author tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H{sub 2}O and layer silicate-H{sub 2}O at 300 and 350 C, respectively. Witherite (BaCO{sub 3}), strontianite (SrCO{sub 3}) and calcite (CaCO{sub 3}) were reacted with pure H{sub 2}O for different lengths of time (271--1,390 H) at 300 C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H{sub 2}O for durations ranging from 132 to 3,282 h at 350 C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. The isotopic rates (ln r) for the carbonate-H{sub 2}O system are {minus}20.75 {+-} 0.44, {minus}18.95 {+-} 0.62 and {minus}18.51 {+-} 0.48 mol O/m{sup 2} s for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H{sub 2}O systems are {minus}23.99 {+-} 0.89, {minus}23.14 {+-} 0.74 and {minus}22.40 {+-} 0.66 mol O/m{sup 2} s for muscovite, biotite and chlorite, respectively.

  16. Calorimetry exchange program amendment to 3rd quarter CY92 report LLNL isotopic data

    SciTech Connect

    Barnett, T.M.

    1996-08-01

    This report is a series of ammendments to the Calorimetry Exchange Quarterly Data Report for third quarter CY1992. The ammendment is needed due to reporting errors encountered in the Lawrence Livermore National Laboratory isotopic data.

  17. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  18. Momentum transfer in relativistic heavy ion charge-exchange reactions

    NASA Technical Reports Server (NTRS)

    Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

    1991-01-01

    Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

  19. [Exchange reactions in brain tissue under chronic ethanol intoxication].

    PubMed

    Gil'miiarova, F N; Radomskaia, V M; Vinogradova, L N

    1982-01-01

    The paper deals with characterization of systems utilizing ethanol and reactions conjugated with its exchange in the brain tissue under chronic alcohol intoxication. The following is established: the absence of the alcoholdehydrogenase pathway of ethanol oxidation in rabbits, unbalanced splitting of carbohydrates under two-months ethanol load, disturbance of oxidative processes in the tricarboxylic acids cycle, a decrease in the pool of oxidized nicotin amide coenzymes. PMID:7036487

  20. The influence of oxygen exchange between sulfite and water on the oxygen isotope composition of sulfate

    NASA Astrophysics Data System (ADS)

    Müller, I. A.; Brunner, B.

    2012-12-01

    Sulfate does not exchange oxygen with the water under most environmental conditions. Therefore, its oxygen isotope composition serves as an archive of past oxidative sulfur cycling. Studies on the oxygen isotope signature of sulfate produced from reduced sulfur compounds show varying relative contributions of two possible oxygen sources; molecular oxygen and water, and variable isotope fractionations relative to these two compounds. These discrepancies could be due to differences in the production and consumption of sulfuroxy intermediates which exchange oxygen with water. Thereby, the rate of oxygen exchange as well as the rate of oxidation depends on the pH. Studies on the oxygen isotope exchange effects between sulfuroxy intermediates and water and on the oxygen isotope effects during the oxidation of sulfuroxy intermediates are scarce, severely limiting the interpretability of oxygen isotope signatures in sulfate. Sulfite is often considered to be the last/final sulfuroxy intermediate in the oxidation of reduced sulfur compounds to sulfate and may, therefore, be pivotal in shaping the oxygen isotope signature of sulfate. We determined the oxygen isotope equilibrium fractionation between sulfite and water and used the obtained equilibrium value to determine the oxygen isotope effects in abiotic sulfite oxidation experiments. Our results demonstrate that natural variations in the oxygen isotope composition of sulfate produced by oxidative processes can be explained by differences in the interplay of the sulfite oxidation rate and oxygen isotope exchange rate between sulfite and water which both depend on pH conditions and availability of oxidizing agents (e.g. molecular oxygen or ferric iron). Our findings contribute to a more detailed mechanistic understanding of the oxidation of reduced sulfur compounds and underline the importance of sulfite as the final sulfuroxy intermediate in oxidative sulfur cycling.

  1. Film diffusion-controlled kinetics of isotopic exchange in a finite bath

    SciTech Connect

    Tsai, F.N.

    1982-07-01

    This paper examines an isotopic exchange process in which the spherical ion-exchange resins are immersed in an agitated solution of finite volume. It assumes an unstirred liquid film of thickness b-a, a nonlinear concentration profile described by Fick's second law, a concentration of radioactive isotopes in a bulk solution that varies with time, and a constant diffusion coefficient in the liquid film. A rate equation, a diffusion equation, and Laplace transforms along with plots of logs are presented.

  2. Reaction cross sections of carbon isotopes incident on a proton

    SciTech Connect

    Abu-Ibrahim, B.; Horiuchi, W.; Kohama, A.; Suzuki, Y.

    2008-03-15

    We systematically study total reaction cross sections of carbon isotopes with N=6-16 on a proton target for wide range of incident energies. An emphasis is put on the difference from the case of a carbon target. The calculations include the reaction cross sections of {sup 19,20,22}C at 40A MeV, the data of which have recently been measured at RIKEN. The Glauber theory is used to calculate the reaction cross sections. To describe the intrinsic structure of the carbon isotopes, we use a Slater determinant generated from a phenomenological mean-field potential, and construct the density distributions. To go beyond the simple mean-field model, we adopt two types of dynamical models: One is a core+n model for odd-neutron nuclei, and the other is a core+n+n model for {sup 16}C and {sup 22}C. We propose empirical formulas which are useful in predicting unknown cross sections.

  3. Modeling of temporal behavior of isotopic exchange between gaseous hydrogen and palladium hydride power

    SciTech Connect

    Melius, C F; Foltz, G W

    1987-01-01

    A parametric rate-equation model is described which depicts the time dependent behavior of the isotopic exchange process occurring between the solid and gas phases in gaseous hydrogen (deuterium) flows through packed-powder palladium deuteride (hydride) beds. The exchange mechanism is assumed to be rate-limited by processes taking place on the surface of the powder. The fundamental kinetic parameter of the model is the isotopic exchange probability, p, which is the probability that an isotopic exchange event occurs during a collision of a gas phase atom with the surface. Isotope effects between the gas and solid phases are explicitly included in terms of the isotope separation factor, ..cap alpha... Results of the model are compared with recent experimental measurements of isotope exchange in the ..beta..-phase hydrogen/palladium system and, using a literature value of ..cap alpha.. = 2.4, a good description of the experimental data is obtained for p approx. 10/sup -7/. In view of the importance of the isotope effects in the hydrogen/palladium system and the range of ..cap alpha.. values reported for the ..beta..-phase in the literature, the sensitivity of the model results to a variation in the value of ..cap alpha.. is examined.

  4. Isotope fractionation of Si in protonation/deprotonation reaction of silicic acid: A new pH proxy

    NASA Astrophysics Data System (ADS)

    Fujii, Toshiyuki; Pringle, Emily A.; Chaussidon, Marc; Moynier, Frédéric

    2015-11-01

    Isotopic fractionation of Si in protonation/deprotonation reactions of monomeric silicic acids was theoretically and experimentally studied. The reduced partition function ratio for Si (as 1000 ln β) complexes was theoretically estimated by ab initio methods. Three permil of isotope fractionation was estimated to be possible for the 28Si-30Si isotope pair. This prediction was experimentally demonstrated by multi-collector inductively coupled plasma mass spectrometer measurements of Si-bearing aqueous solutions, for which equilibrated Si(OH)4 and SiO(OH)3- were separated using an anionic exchange column. The results create a new possibility for the application of Si isotopes as proxies for paleo-pH in the 9 < pH < 12 range.

  5. Oxygen isotopic transport and exchange during fluid flow: One-dimensional models and applications

    SciTech Connect

    Bowman, J.R. ); Willett, S.D. ); Cook, S.J. Environ Corp., Houston, TX )

    1994-01-01

    In this work the authors investigate the consequences of fluid flow and fluid-rock interaction to the isotopic evolution of fluids and rock with one-dimensional transport models of fluid flow and oxygen isotope exchange. Transport models dealing with stable isotopes are well established in recent geochemical literature. The authors extend previous treatments by presenting the derivation of both analytical and numerical solutions to the transport equations incorporating simultaneously advection, diffusion and hydrodynamic dispersion, and kinetics of isotopic exchange. The increased generality of numerical solutions allows the incorporation of other effects which control the spatial patterns of [delta][sup 18]O values developed in rocks and fluids including multiple reactive species and temperature gradients. The authors discuss the effects of flow parameters, conditions of isotopic exchange, and temperature gradients on the spatial patterns of isotopic shifts produced in rock sequences subjected to fluid flow, and on conventionally calculated W/R ratios for these rock sequences. Finally, the authors examine the implications of oxygen isotope transport for two natural systems where isotopic shifts or gradients could be interpreted in terms of unidirectional fluid infiltration. Solutions of one-dimensional transport equations including the mechanisms of advection, diffusion, hydrodynamic dispersion, and non-equilibrium exchange between water and rock indicate that the time-space evolution of oxygen isotopic compositions of rock and infiltrating fluid is dependent on (1) the rate of fluid infiltration, (2) the diffusive and dispersive properties of the rock matrix, (3) the rate of isotopic exchange, and (4) the rock-water mass oxygen ratio in a unit volume of water-saturated, porous rock. 56 refs., 18 figs., 2 tabs.

  6. The kinetics of clumped-isotope reactions in calcite and apatite from natural and experimental samples

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Eiler, J. M.

    2014-12-01

    Measurements of clumped isotopes of carbonate-bearing minerals are a powerful tool for reconstructing past surface temperatures and thermal histories of shallow crustal rocks. Because the clumped-isotope thermometer is based on homogenous-phase equilibrium, a sample's clumped-isotope temperature is susceptible to resetting through, for example, intracrystalline diffusion and redistribution of C and O isotopes during (re)heating or slow cooling. Quantitative knowledge of the kinetics of this resetting have received increasing attention (1-3) and is critical for understanding the meaning of clumped-isotope temperatures of samples with complex burial histories. To better constrain these kinetics and complement previous work (1-3) we performed heating experiments (400-700°C) on optical calcites and carbonate-bearing apatites. As previously observed (2-3), calcites exhibit non-first-order kinetics. The data were fit using a model that incorporates both diffusion and isotope-exchange reactions (4). The kinetics derived with this model using the optical-calcite heating experiments of (2) and those measured here are indistinguishable. The model predicts that subtle changes (>10°C) in measured calcite clumped-isotope temperatures can occur at burial temperatures between 60-100°C on million-year timescales. Though small, such changes may have an impact on clumped-isotope-based reconstructions of past surface temperatures and thermal histories. The derived kinetics were compared to clumped-isotope measurements of cogenetic calcites and apatites from slowly cooled carbonatite intrusions. Apparent temperatures are 70-140°C for apatites and 120-190°C for calcites. Measured temperatures for calcites match modeled temperatures using reasonable geological cooling rates. Natural apatite samples yield lower apparent temperatures than predicted based on the model. We propose that this difference is the result of annealment of structural damage in apatites (e.g., generated by

  7. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H[sub 2] [yields] H[sub 2] + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a 'perfect experiment', measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H[sub 2] reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H[sub 2] molecules. DH molecules formed in the D + H[sub 2] reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10[sup 3] molecules/cc. This thesis does not contain experimental results for the D + H[sub 2] reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  8. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H{sub 2} {yields} H{sub 2} + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a `perfect experiment`, measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H{sub 2} reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H{sub 2} molecules. DH molecules formed in the D + H{sub 2} reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10{sup 3} molecules/cc. This thesis does not contain experimental results for the D + H{sub 2} reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  9. Low temperature equilibrium isotope fractionation and isotope exchange kinetics between U(IV) and U(VI)

    NASA Astrophysics Data System (ADS)

    Wang, Xiangli; Johnson, Thomas M.; Lundstrom, Craig C.

    2015-06-01

    Measurements of the uranium (U) isotope ratio 238U/235U provide an emerging redox proxy in environmental and paleoredox studies, but many key parameters concerning U isotope fractionation are still poorly constrained. Here we report the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI), and rates of isotope exchange between solid-phase U(IV) and dissolved U(VI). We conducted one experiment at high concentration [35 mM U(IV) and 32 mM U(VI)] and low pH (0.2) in hydrochloric acid media at room temperature to determine the equilibrium isotopic fractionation between dissolved U(IV) and dissolved U(VI). Isotopic equilibrium was reached in about 19 days under such experimental conditions. The equilibrium isotope fractionation was determined to be 1.64 ± 0.16‰, with U(IV) being enriched in 238U relative to U(VI). Applicability of the determined equilibrium fractionation is discussed. We also conducted a set of experiments to determine isotopic exchange rates between dissolved U(VI) and nanouraninite U(IV) under conditions closer to those in natural system, with lower concentrations and neutral pH. The exchange rate was found to conform to the rate law R = k[U(VI)]adsorbed, in which R is the isotopic exchange rate (μM day-1); k is the rate constant determined to be 0.21 day-1; and [U(VI)]adsorbed is the concentration of U(VI) adsorbed to nanouraninite (μM). Our results, combined with consideration of the variables controlling U(VI)-U(IV) contact in natural settings, indicate that the timescale for significant isotope equilibration varies depending on environmental conditions, mostly uranium concentrations. In natural uncontaminated sediments with low uranium concentrations, equilibration is expected to occur on a timescale of hundreds to thousands of years. In contrast, in U-contaminated aquifers with high U concentrations, significant equilibration could occur on timescales of weeks to years.

  10. Direct Measurement of Biosphere-Atmosphere Isotopic CO2 Exchange using the Eddy Covariance Technique

    NASA Astrophysics Data System (ADS)

    Griffis, T.; Sargent, S.; Tanner, B.; Greene, J.; Swiatek, E.; Baker, J.; Lee, X.

    2006-12-01

    Quantifying isotopic CO2 exchange between the biosphere and atmosphere presents a significant measurement challenge, but has the potential to provide important constraints on local, regional, and global carbon cycling. Such measurements are rare because of the difficulties quantifying CO2 isotope ratios or individual isotopomer mixing ratios at the precision and frequency required for continuous scalar flux estimation. This limitation has slowed the understanding of key isotope discrimination mechanisms and carbon cycle processes. Past approaches have indirectly estimated isotopic CO2 exchange using relaxed eddy accumulation, the flask-based isoflux method, and flux-gradient techniques. Eddy covariance is an attractive method because it has the fewest theoretical assumptions and the potential to give a direct measurement of isotopic CO2 exchange, but requires a highly sensitive and relatively fast-response instrument. To date, no such field measurements have been reported. Here, we describe the use of a closed- path tunable diode laser absorption spectroscopy system (Trace Gas Analyzer, TGA100A, Campbell Scientific Inc.) and a sampling manifold optimized for eddy covariance isotopic (C16O2, 13CO2, C18O16O) flux measurements. The sampling system was designed to preserve frequency response, to avoid excessive consumption of expensive calibration gases and, more importantly, to avoid bias between the air sample and three calibration gas measurements. Results are presented from an intensive field experiment conducted at the University of Minnesota from July 18 to September 18, 2006. The field experiment was designed to evaluate: 1) the feasibility of making continuous isotopic flux measurement over extended periods of time; 2) differences in isotopic composition of ecosystem respiration and net ecosystem CO2 exchange using the Keeling plot, flux-gradient, and eddy covariance methods, and 3) the potential for isotopic flux partitioning of net ecosystem CO2 exchange.

  11. Ammonium transport and reaction in contaminated groundwater: Application of isotope tracers and isotope fractionation studies

    USGS Publications Warehouse

    Böhlke, J.K.; Smith, R.L.; Miller, D.N.

    2006-01-01

    Ammonium (NH4+) is a major constituent of many contaminated groundwaters, but its movement through aquifers is complex and poorly documented. In this study, processes affecting NH4+ movement in a treated wastewater plume were studied by a combination of techniques including large-scale monitoring of NH4+ distribution; isotopic analyses of coexisting aqueous NH4+, NO3-, N2, and sorbed NH 4+; and in situ natural gradient 15NH 4+ tracer tests with numerical simulations of 15NH4+, 15NO3-, and 15N2 breakthrough data. Combined results indicate that the main mass of NH4+ was moving downgradient at a rate about 0.25 times the groundwater velocity. Retardation factors and groundwater ages indicate that much of the NH4+ in the plume was recharged early in the history of the wastewater disposal. NO3- and excess N2 gas, which were related to each other by denitrification near the plume source, were moving downgradient more rapidly and were largely unrelated to coexisting NH 4+. The ??15N data indicate areas of the plume affected by nitrification (substantial isotope fractionation) and sorption (no isotope fractionation). There was no conclusive evidence for NH 4+-consuming reactions (nitrification or anammox) in the anoxic core of the plume. Nitrification occurred along the upper boundary of the plume but was limited by a low rate of transverse dispersive mixing of wastewater NH4+ and O2 from overlying uncontaminated groundwater. Without induced vertical mixing or displacement of plume water with oxic groundwater from upgradient sources, the main mass of NH4+ could reach a discharge area without substantial reaction long after the more mobile wastewater constituents are gone. Multiple approaches including in situ isotopic tracers and fractionation studies provided critical information about processes affecting NH4+ movement and N speciation.

  12. No oxygen isotope exchange between water and APS-sulfate at surface temperature: Evidence from quantum chemical modeling and triple-oxygen isotope experiments

    NASA Astrophysics Data System (ADS)

    Kohl, Issaku E.; Asatryan, Rubik; Bao, Huiming

    2012-10-01

    In both laboratory experiments and natural environments where microbial dissimilatory sulfate reduction (MDSR) occurs in a closed system, the δ34S ((34S/32S)sample/(34S/32S)standard - 1) for dissolved SO42- has been found to follow a typical Rayleigh-Distillation path. In contrast, the corresponding δ18O ((18O/16O)sample/(18O/16O)standard) - 1) is seen to plateau with an apparent enrichment of between 23‰ and 29‰ relative to that of ambient water under surface conditions. This apparent steady-state in the observed difference between δ18O and δ18OO can be attributed to any of these three steps: (1) the formation of adenosine-5'-phosphosulfate (APS) from ATP and SO42-, (2) oxygen exchange between sulfite (or other downstream sulfoxy-anions) and water later in the MDSR reaction chain and its back reaction to APS and sulfate, and (3) the re-oxidation of produced H2S or precursor sulfoxy-anions to sulfate in environments containing Fe(III) or O2. This study examines the first step as a potential pathway for water oxygen incorporation into sulfate. We examined the structures and process of APS formation using B3LYP/6-31G(d,p) hybrid density functional theory, implemented in the Gaussian-03 program suite, to predict the potential for oxygen exchange. We conducted a set of in vitro, enzyme-catalyzed, APS formation experiments (with no further reduction to sulfite) to determine the degree of oxygen isotope exchange between the APS-sulfate and water. Triple-oxygen-isotope labeled water was used in the reactor solutions to monitor oxygen isotope exchange between water and APS sulfate. The formation and hydrolysis of APS were identified as potential steps for oxygen exchange with water to occur. Quantum chemical modeling indicates that the combination of sulfate with ATP has effects on bond strength and symmetry of the sulfate. However, these small effects impart little influence on the integrity of the SO42- tetrahedron due to the high activation energy required for

  13. Examination of the mechanism of sucrose synthetase by positional isotope exchange

    SciTech Connect

    Singh, A.N.; Hester, L.S.; Raushel, F.M.

    1987-02-25

    The mechanism of the sucrose synthetase reaction has been probed by the technique of positional isotope exchange. (beta-/sup 18/O/sub 2/, alpha beta-/sup 18/O)UDP-Glc has been synthesized starting from oxygen-18-labeled phosphate and the combined activities of carbamate kinase, hexokinase, phosphoglucomutase, and uridine diphosphoglucose pyrophosphorylase. The oxygen-18 at the alpha beta-bridge position of the labeled UDP-Glc has been shown to cause a 0.014 ppm upfield chemical shift in the 31P NMR spectrum of both the alpha- and beta-phosphorus atoms in UDP-Glc relative to the unlabeled compound. The chemical shift induced by each of the beta-nonbridge oxygen-18 atoms was 0.030 ppm. Incubation of (beta-/sup 18/O/sub 2/, alpha beta-/sup 18/O)UDP-Glc with sucrose synthetase in the presence and absence of 2,5-anhydromannitol did not result in any significant exchange of an oxygen-18 from the beta-nonbridge position to the anomeric oxygen of the glucose moiety. It can thus be concluded that either sucrose synthetase does not catalyze the cleavage of the scissile carbon-oxygen bond of UDP-Glc in the absence of fructose or, alternatively, the beta-phosphoryl group of the newly formed UDP is rotationally immobilized.

  14. Isotopic exchange during derivatization of platelet activating factor for gas chromatography-mass spectrometry

    SciTech Connect

    Haroldsen, P.E.; Gaskell, S.J.; Weintraub, S.T.; Pinckard, R.N. )

    1991-04-01

    One approach to the quantitative analysis of platelet activating factor (PAF, 1-O-alkyl-2-acetyl-sn-glycerol-3-phosphocholine; also referred to as AGEPC, alkyl glyceryl ether phosphocholine) is hydrolytic removal of the phosphocholine group and conversion to an electron-capturing derivative for gas chromatography-negative ion mass spectrometry. (2H3)Acetyl-AGEPC has been commonly employed as an internal standard. When 1-hexadecyl-2-(2H3)acetyl glycerol (obtained by enzymatic hydrolysis of (2H3)-C16:0 AGEPC) is treated with pentafluorobenzoyl chloride at 120 degrees C, the resulting 3-pentafluorobenzoate derivative shows extensive loss of the deuterium label. This exchange is evidently acid-catalyzed since derivatization of 1-hexadecyl-2-acetyl glycerol under the same conditions in the presence of a trace of 2HCl results in the incorporation of up to three deuterium atoms. Isotope exchange can be avoided if the reaction is carried out at low temperature in the presence of base. Direct derivatization of (2H3)-C16:0 AGEPC by treatment with pentafluorobenzoyl chloride or heptafluorobutyric anhydride also results in loss of the deuterium label. The use of (13C2)-C16:0 AGEPC as an internal standard is recommended for rigorous quantitative analysis.

  15. Charge-exchange reactions with a radioactive triton beam

    SciTech Connect

    Jaenecke, J.

    1998-12-21

    A high-resolution (t, {sup 3}He) test experiment has been performed recently by making use of a secondary triton beam produced by fragmentation of {alpha}-particles. The purpose of this charge-exchange experiment was to achieve good energy resolution in an (n,p)-type reaction at intermediate bombarding energies. The experiment was carried out with the K1200 cyclotron at the National Superconducting Cyclotron Laboratory using the A1200 beam-analysis system and the S800 magnetic spectrometer. The beam-analysis system was used to transport the energy-dispersed radioactive triton beam from the production target to the target position, and the magnetic spectrometer was used to focus the dispersion-matched {sup 3}He particles from the (t, {sup 3}He) reaction at 0 degree sign onto the focal plane of the spectrometer. An energy resolution of 200-250 keV was achieved.

  16. Reactive Resonances in N+N2 Exchange Reaction

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Stallcop, James R.

    2003-01-01

    Rich reactive resonances are found in a 3D quantum dynamics study of the N + N2 exchange reaction using a recently developed ab initio potential energy surface. This surface is characterized by a feature in the interaction region called Lake Eyring , that is, two symmetric transition states with a shallow minimum between them. An L2 analysis of the quasibound states associated with the shallow minimum confirms that the quasibound states associated with oscillations in all three degrees of freedom in Lake Eyring are responsible for the reactive resonances in the state-to-state reaction probabilities. The quasibound states, mostly the bending motions, give rise to strong reasonance peaks, whereas other motions contribute to the bumps and shoulders in the resonance structure. The initial state reaction probability further proves that the bending motions are the dominating factors of the reaction probability and have longer life times than the stretching motions. This is the first observation of reactive resonances from a "Lake Eyring" feature in a potential energy surface.

  17. Epitactic ion-exchange reactions into vanadyl(IV) arsenate

    SciTech Connect

    Martinez-Lara, M.; Bruque, S.; Moreno, L.; Aranda, M.A.G. )

    1991-03-01

    The synthesis, structural characterization, thermal stability, and spectroscopic (IR, UV-vis-diffuse reflectance) properties of three vanadyl arsenates are described. Vanadyl(IV) bis(dihydrogenarsenate), (VO(H{sub 2}AsO{sub 4}){sub 2}) (1), lithium vanadyl arsenate, (Li{sub 4}VO(AsO{sub 4}){sub 2}{center dot}0.5H{sub 2}O) (2), and nickel(II) and lithium vanadyl arsenate, ((Li{sub 2.4}Ni){sub 0.8}VO(AsO{sub 4}){sub 2}{center dot}4H{sub 2}O) (3), have been prepared. (1) Tetragonal ({alpha} = 9.128 {angstrom}; c = 8.128 {angstrom}) is prepared by reduction with isobutanol or ethanol from vanadyl(V) arsenate. (2) Cubic (a = 9.024 {angstrom}) is obtained from (1) by lithium ion-exchange, and (3) tetragonal (a = 9.106 {angstrom}; c = 8.454 {angstrom}) is made from (2) by Ni{sup 2+} ion-exchange. These exchange reactions are epitactic and the overall result is a topotactic transformation.

  18. Mechanism of the Exchange Reaction in HRAS from Multiscale Modeling

    PubMed Central

    Kapoor, Abhijeet; Travesset, Alex

    2014-01-01

    HRAS regulates cell growth promoting signaling processes by cycling between active (GTP-bound) and inactive (GDP-bound) states. Understanding the transition mechanism is central for the design of small molecules to inhibit the formation of RAS-driven tumors. Using a multiscale approach involving coarse-grained (CG) simulations, all-atom classical molecular dynamics (CMD; total of 3.02 µs), and steered molecular dynamics (SMD) in combination with Principal Component Analysis (PCA), we identified the structural features that determine the nucleotide (GDP) exchange reaction. We show that weakening the coupling between the SwitchI (residues 25–40) and SwitchII (residues 59–75) accelerates the opening of SwitchI; however, an open conformation of SwitchI is unstable in the absence of guanine nucleotide exchange factors (GEFs) and rises up towards the bound nucleotide to close the nucleotide pocket. Both I21 and Y32, play a crucial role in SwitchI transition. We show that an open SwitchI conformation is not necessary for GDP destabilization but is required for GDP/Mg escape from the HRAS. Further, we present the first simulation study showing displacement of GDP/Mg away from the nucleotide pocket. Both SwitchI and SwitchII, delays the escape of displaced GDP/Mg in the absence of GEF. Based on these results, a model for the mechanism of GEF in accelerating the exchange process is hypothesized. PMID:25272152

  19. Alloyed Copper Chalcogenide Nanoplatelets via Partial Cation Exchange Reactions

    PubMed Central

    2014-01-01

    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide–sulfide (CZSeS), copper tin selenide–sulfide (CTSeS), and copper zinc tin selenide–sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide–sulfide (Cu2–xSeyS1–y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2–xSeyS1–y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV–vis–NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps. PMID:25050455

  20. Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

    PubMed

    Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

    2015-09-15

    Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. PMID:25769515

  1. Use of micrometeorological techniques to study the isotopic exchange in ecosystems

    NASA Astrophysics Data System (ADS)

    Santos, E.; Wagner-Riddle, C.; Brown, S. E.; Stropes, K.

    2015-12-01

    The combination of micrometeorological techniques with high frequency concentration measurements of stable isotopes are a powerful tool to study the temporal dynamics of isotope signatures at the ecosystem level. The objective of this study was to study the isotopic composition of the net CO2 exchange (NEE) above and with corn and tall grass canopies. Profiles of stable isotopes of CO2 (12C-CO2, 13C-CO2 and 18O-CO2) were measured using tunable diode laser trace gas analyzers and multiport sampling systems in corn (12C-CO2 and 13C-CO2, only) and tall grass canopies. These measurements were combined with the flux gradient method and Lagrangian dispersion analysis to estimate the isotopic signatures of the net CO2 flux. The use of a gradient of a concentration threshold to screen half hourly period improved the estimates of flux signatures by the isotope flux ratio approach. The Langrangian dispersion analysis and the isotope flux ratio method estimates showed good agreement above the corn canopy, indicating that the former method can be a viable alternative to study the isotopic exchange within plant canopies. The 13CO2 composition of NEE showed a downward trend near the end of the growing season, which may be related to a reduction of autotrophic respiration in the soil.

  2. First observation of a mass independent isotopic fractionation in a condensation reaction

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

    1994-01-01

    Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

  3. Hydrogen isotope exchange in beryllium co-deposits: modelling and experiment

    NASA Astrophysics Data System (ADS)

    Kogut, D.; Douai, D.; Baldwin, M. J.; Doerner, R. P.; Sinelnikov, D.; Mamedov, N.; Kurnaev, V.; Becker, H. W.; Schwarz-Selinger, T.

    2016-02-01

    In order to understand the interaction mechanisms between hydrogenic species and beryllium co-deposits, a 1D Diffusion Trapping Model of Isotopic eXchange in Be (DITMIX) is developed. Hydrogen depth profiles from DITMIX are in good agreement with those measured by 15N-NRA on pre-characterised 600 nm thick Be:H layers (H/Be = 0.04), which were irradiated by D ions with a low flux of 1017 m-2 s-1 and an energy of 5 keV D-1, for different fluences and surface temperatures. Hence DITMIX provides a qualitative understanding of the isotope exchange mechanisms, although modelled versus measured D profiles show less agreement in the bulk, casting some doubt on the processes involved. For such low fluxes, DITMIX shows that the main factors determining isotopic exchange are the irradiation fluence and the surface temperature.

  4. The NO+O{sub 3} reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

    SciTech Connect

    Savarino, J.; Morin, S.; Baroni, M.; Bhattacharya, S. K.; Doussin, J.-F.

    2008-05-21

    Atmospheric nitrate shows a large oxygen isotope anomaly ({delta} {sup 17}O), characterized by an excess enrichment of {sup 17}O over {sup 18}O, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NO{sub x}=NO+NO{sub 2}). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NO{sub x}, greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO+O{sub 3}. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8{+-}5)%({+-}2{sigma}) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O{sub 3} to NO{sub 2}, which is described by the linear relationship {delta} {sup 17}O(NO{sub 2})=Ax{delta} {sup 17}O(O{sub 3})+B, with A=1.18{+-}0.07({+-}1{sigma}) and B=(6.6{+-}1.5) per mille ({+-}1{sigma}). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

  5. The NO +O3 reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly

    NASA Astrophysics Data System (ADS)

    Savarino, J.; Bhattacharya, S. K.; Morin, S.; Baroni, M.; Doussin, J.-F.

    2008-05-01

    Atmospheric nitrate shows a large oxygen isotope anomaly (ΔO17), characterized by an excess enrichment of O17 over O18, similar to the ozone molecule. Modeling and observations assign this specific isotopic composition mainly to the photochemical steady state that exists in the atmosphere between ozone and nitrate precursors, namely, the nitrogen oxides (NOx=NO+NO2). However, this transfer is poorly quantified and is built on unverified assumptions about which oxygen atoms of ozone are transferred to NOx, greatly weakening any interpretation of the nitrate oxygen isotopic composition in terms of chemical reaction pathways and the oxidation state of the atmosphere. With the aim to improve our understanding and quantify how nitrate inherits this unusual isotopic composition, we have carried out a triple isotope study of the reaction NO +O3. Using ozone intramolecular isotope distributions available in the literature, we have found that the central atom of the ozone is abstracted by NO with a probability of (8±5)%(±2σ) at room temperature. This result is at least qualitatively supported by dynamical reaction experiments, the non-Arrhenius behavior of the kinetic rate of this reaction, and the kinetic isotope fractionation factor. Finally, we have established the transfer function of the isotope anomaly of O3 to NO2, which is described by the linear relationship ΔO17(NO2)=A ×ΔO17(O3)+B, with A =1.18±0.07(±1σ) and B =(6.6±1.5)‰(±1σ). Such a relationship can be easily incorporated into models dealing with the propagation of the ozone isotope anomaly among oxygen-bearing species in the atmosphere and should help to better interpret the oxygen isotope anomaly of atmospheric nitrate in terms of its formation reaction pathways.

  6. Charge-exchange reaction by Reggeon exchange and W{sup +}W{sup −}-fusion

    SciTech Connect

    Schicker, R.

    2015-04-10

    Charge-exchange reactions at high energies are examined. The existing cross section data on the Reggeon induced reaction pp → n + Δ{sup ++} taken at the ZGS and ISR accelerators are extrapolated to the energies of the RHIC and LHC colliders. The interest in the charge-exchange reaction induced by W{sup ±}-fusion is presented, and the corresponding QCD-background is examined.

  7. Nitrogen isotope exchange between NO and NO2 and its implications for δ15N variations in tropospheric NOx and atmospheric nitrate

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Simonini, Damian S.; Michalski, Greg

    2016-01-01

    The nitrogen (N) isotope exchange between nitric oxide (NO) and nitrogen dioxide (NO2) has been previously suggested to influence N stable isotope compositions (δ15N) of these molecules. However, there is disagreement in the magnitude of the N isotopic fractionation (αNO2>/NO) resulting from this exchange process between previous experimental and theoretical studies. To this end, we measured αNO2>/NO associated with this exchange reaction at various temperatures. Our results indicate αNO2>/NO to be 1.0403 ± 0.0015, 1.0356 ± 0.0015, and 1.0336 ± 0.0014 at 278 K, 297 K, and 310 K, respectively. These measured values are within experimental error of the values we calculated using a modified version of the Bigeleisen-Mayer equation corrected for accurate zero-point energies, indicating an agreement between experiment and theory. Modeling of this exchange reaction demonstrates that δ15N-NO2 may exhibit a diurnal and seasonal profile if N isotopic equilibrium is achieved.

  8. Isotopic exchange processes in cold plasmas of H2/D2 mixtures.

    PubMed

    Jiménez-Redondo, Miguel; Carrasco, Esther; Herrero, Víctor J; Tanarro, Isabel

    2011-05-28

    Isotope exchange in low pressure cold plasmas of H(2)/D(2) mixtures has been investigated by means of mass spectrometric measurements of neutrals and ions, and kinetic model calculations. The measurements, which include also electron temperatures and densities, were performed in a stainless steel hollow cathode reactor for three discharge pressures: 1, 2 and 8 Pa, and for mixture compositions ranging from 100% H(2) to 100% D(2). The data are analyzed in the light of the model calculations, which are in good global agreement with the experiments. Isotope selective effects are found both in the surface recombination and in the gas-phase ionic chemistry. The dissociation of the fuel gas molecules is followed by wall recycling, which regenerates H(2) and D(2) and produces HD. Atomic recombination at the wall is found to proceed through an Eley-Rideal mechanism, with a preference for reaction of the adsorbed atoms with gas phase D atoms. The best fit probabilities for Eley-Rideal abstraction with H and D are: γ(ER H) = 1.5 × 10(-3), γ(ER D) = 2.0 × 10(-3). Concerning ions, at 1 Pa the diatomic species H(2)(+), D(2)(+) and HD(+), formed directly by electron impact, prevail in the distributions, and at 8 Pa, the triatomic ions H(3)(+), H(2)D(+), HD(2)(+) and D(3)(+), produced primarily in reactions of diatomic ions with molecules, dominate the plasma composition. In this higher pressure regime, the formation of the mixed ions H(2)D(+) and HD(2)(+) is favoured in comparison with that of H(3)(+) and D(3)(+), as expected on statistical grounds. The model results predict a very small preference, undetectable within the precision of the measurements, for the generation of triatomic ions with a higher degree of deuteration, which is probably a residual influence at room temperature of the marked zero point energy effects (ZPE), relevant for deuterium fractionation in interstellar space. In contrast, ZPE effects are found to be decisive for the observed distribution of

  9. Determination of the hydrogen isotopic composition of bone collagen and correction for hydrogen exchange

    SciTech Connect

    Cormie, A.B.; Schwarcz, H.P. ); Gray, J. )

    1994-01-01

    The hydrogen isotopic measurement ([delta]D) of the non-exchangeable hydrogens in herbivore bone collagen has potential for paleoclimate research. The authors have developed the methodology for extracting the hydrogen from collagen for isotopic analysis and correcting the [delta]D results for hydrogen exchange. Preparations of whole bone powders, demineralized bone, or gelatin extracts from fresh bone samples all give reliable [delta]D results and have isotopic results, yields, and proportions of exchangeable hydrogens consistent with that expected for collagen. Gelatin extraction for removal of contaminants remains a valuable option for the study of fossil bone samples. Vacuum preheating under good vacuum at 150[degrees]C for two days for whole bone powders and at 100[degrees]C for one day for gelatins is an important step to remove all adsorbed water before samples are oxidized for isotopic analysis. Of the remaining hydrogens released following oxidation, 20.5% in whole bone powders and 23.1% in gelatin extracts exchange with laboratory atmospheric water vapor within 48 hours. The [delta]D results can be corrected for this exchange and for minor effects of sample preparation by using a calibration bone standard to determine the [delta]D value of laboratory water vapor.

  10. Population of 13Be with a Nucleon-Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Marks, Bradon; Deyoung, Paul; Smith, Jenna; Thoennessen, Michael; MoNA Collaboration

    2015-10-01

    Neutron-unbound nuclei are traditionally formed by the removal of one or more nucleons from a fast beam of ions. This method often results in a background, which is difficult to separate from the particle of interest. Nucleon-removal entrance-channels also require the ion beam to be more massive than the particle of interest, which presents the additional challenges of the beam being difficult to make. The present work was done with a nucleon-exchange entrance channel. At the National Superconducting Cyclotron Laboratory, a 71 MeV/u 13B beam impinged on a 47 mg/cm2 thick target of 9Be. As a result numerous reactions occurred, including the population of 13Be through the nucleon-exchange entrance-channel. The 13Be nuclei decayed to 12Be and one neutron in approximately 10-21 seconds. The resulting neutrons were detected by either the Modular Neutron Array (MoNA) or the Large multi-Institution Scintillator Array (LISA), while the 12Be nuclei were directed through an array of charged particle detectors by a 4T superconducting sweeper magnet. The four-momentum vectors of the fragment nucleus and the neutron were calculated to determine the decay energy of 13Be. Monte-Carlo simulations consistent with results from previous analyses of 13Be were satisfactorily fit to the decay-energy spectrum. Additionally, the cross-section for the nucleon-exchange entrance-channel is consistent with a theoretical prediction. This material is based upon work supported by the National Science Foundation under Grant No. PHY-1306074.

  11. Dual pressure-dual temperature isotope exchange process

    DOEpatents

    Babcock, D.F.

    1974-02-12

    A liquid and a gas stream, each containing a desired isotope, flow countercurrently through two liquid-gas contacting towers maintained at different temperatures and pressures. The liquid is enriched in the isotope in one tower while the gas is enriched within the other and a portion of at least one of the enriched streams is withdrawn from the system for use or further enrichment. The tower operated at the lower temperature is also maintained at the lower pressure to prevent formation of solid solvates. Gas flow between the towers passes through an expander-compressor apparatas to recover work from the expansion of gas to the lower pressure and thereby compress the gas returning to the tower of higher pressure. (Official Gazette)

  12. Spin-Isospin responses via charge exchange reactions of RI beams at SHARAQ

    SciTech Connect

    Shimoura, Susumu

    2012-11-12

    Nuclear spectroscopy via direct reactions of RI beams is discussed focusing on characteristics of charge-exchange reactions of RI beams. Recent experiments using the SHARAQ spectrometer at the RIBF are presented, where isovector spin monopole and spin-non-flip monopole responses are studied by charge exchange reaction of RI beams. Some experimental plans and perspectives are also presented.

  13. EXPERIMENTAL RESULTS FOR THE ISOTOPIC EXCHANGE OF A 1600 LITER TITANIUM HYDRIDE STORAGE VESSEL

    SciTech Connect

    Klein, J.

    2010-12-14

    Titanium is used as a low pressure tritium storage material. The absorption/desorption rates and temperature rise during air passivation have been reported previously for a 4400 gram prototype titanium hydride storage vessel (HSV). A desorption limit of roughly 0.25 Q/M was obtained when heating to 700 C which represents a significant residual tritium process vessel inventory. To prepare an HSV for disposal, batchwise isotopic exchange has been proposed to reduce the tritium content to acceptable levels. A prototype HSV was loaded with deuterium and exchanged with protium to determine the effectiveness of a batch-wise isotopic exchange process. A total of seven exchange cycles were performed. Gas samples were taken nominally at the beginning, middle, and end of each desorption cycle. Sample analyses showed the isotopic exchange process does not follow the standard dilution model commonly reported. Samples taken at the start of the desorption process were lower in deuterium (the gas to be removed) than those taken later in the desorption cycle. The results are explained in terms of incomplete mixing of the exchange gas in the low pressure hydride.

  14. Hydrogen isotope exchange between n-alkanes and water under hydrothermal conditions: implications for abiotic and thermogenic hydrocarbons in vent fluids

    NASA Astrophysics Data System (ADS)

    Reeves, E. P.; Seewald, J.; Sylva, S.

    2010-12-01

    Stable isotopes are extensively utilized in studies of hydrocarbons in naturals fluids. However, factors controlling the hydrogen isotope (2H/1H) composition of dissolved hydrocarbons in hydrothermal fluids are still poorly understood despite interest in their 2H/1H signatures as indicators of abiogenesis. Due to its high activation energy for exchange, alkyl-bound hydrogen (H) is typically considered to be isotopically conservative. Incorporation of water-derived H under hydrothermal conditions may, however, obscure any primary signatures associated with abiotic polymerization. To examine this process, we conducted experiments to investigate 2H/1H exchange between aqueous n-alkanes and water using a Au-TiO2 flexible cell hydrothermal apparatus. C1-C5 n-alkanes were heated at 325°C and 350 bar in aqueous solutions of varying initial 2H/1H ratios (δ2H) in the presence of a pyrite-pyrrhotite-magnetite (PPM) mineral redox buffer. Extensive incorporation of water-derived H into C2-C5 n-alkanes was observed on timescales of months. In contrast, relatively minor incorporation was observed for CH4. Isotopic exchange is facilitated by reversible equilibration of n-alkanes and their corresponding alkenes by the reaction: CnH2n+2(aq) = CnH2n(aq) + H2(aq) Where H2(aq) is derived from water. The lack of substantial n-alkane decomposition on the timescale of observation, combined with an approach to steady-state isotopic compositions, indicate that n-alkane δD values likely reflect an approach to isotopic equilibrium rather than kinetically-controlled fractionation effects associated with degradation reactions. Substantially lower amounts of exchange were observed for ethane relative to C3-C5 n-alkanes, which suggests that alkene isomerization reactions may enhance incorporation of water-derived H in these compounds. Thus, reaction mechanisms exist in hydrothermal fluids that allow rapid 2H/1H exchange of alkyl-H with water on timescales comparable to crustal residence times

  15. DETERMINING CARBON ISOTOPE SIGNATURES FROM MICROMETEOROLOGICAL MEASUREMENTS: IMPLICATIONS FOR STUDYING BIOSPHERE-ATMOSPHERE EXCHANGE PROCESSES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In recent years considerable effort has been focused on combining micrometeorological and stable isotope techniques to elucidate and study biosphere-atmosphere exchange processes. At the ecosystem scale, these methods are increasingly being used to address a number of challenging problems, including...

  16. Anion effects to deliver enhanced iridium catalysts for hydrogen isotope exchange processes.

    PubMed

    Kennedy, Alan R; Kerr, William J; Moir, Rory; Reid, Marc

    2014-10-28

    Synthesis of a series of iridium(I) complexes of the type [(COD)Ir(IMes)(PPh3)]X (X = BF4, OTf, and BArF) has been established. Application of these species in mild hydrogen isotope exchange processes revealed more efficient catalysis and, further, a wider solvent scope when employing larger, more weakly coordinating counterions. PMID:25208265

  17. ISOTOPIC EXCHANGE BETWEEN CARBON DIOXIDE AND OZONE VIA O('D) IN THE STRATOSPHERE

    EPA Science Inventory

    We propose a novel mechanism for isotopic exchange between CO2 and O3 via O(1D) + CO2 - CO3 followed by CO3 - CO2 + O(3P). ne dimensional model calculation shows that mechanism can account for the enrichment in 18 O in the stratospheric CO2 observed by Gamo et al. [1989], using t...

  18. Isotope Fractionation of chlorine in Aqueous System: One Study on Anion-Exchange Chromatography.

    NASA Astrophysics Data System (ADS)

    Musashi, M.; Oi, T.; Eggenkamp, H.; Van Cappellen, P.

    2001-05-01

    Stable chlorine isotopes such as 37Cl and 35Cl have been paid attention as useful tool identifying the source, and monitoring the transport process and natural fate of chlorinated organic pollutants in air and groundwater. However, it is not established yet whether any isotope effects accompany biodegradation or reductive dehalogenation of the pollutants (Clark and Fritz, 1997). Here we first present an experimental determination of isotope fractionation factor of chlorine in aqueous system by using anion-exchange chromatographic technique. Into the Cl-free anion exchange resin (Muromac, OH- form) packed in a 30 cm long pyrex glass column and controlled temperature at 25 oC, hydrochloric solution was fed with controlling the flow rate constant. Effluent from the column was recovered by an automatic fraction collector and prepared for Cl isotope analysis. The Cl isotope ratio (δ 37Cl vs. SMOC) was measured by IR-MS at the Utrecht University with precision of 0.06 per-mil. Magnitude of the factor obtained was 1.00035 at 25 oC. The result indicates that the lighter isotope (35Cl) was preferably fractionated into the resin phase, while the heavier one (37Cl) was enriched into the aqueous phase. This trend suggests that molecular structure of hydrolysis with Cl in aqueous phase may be more stable than that of Cl ionically bonding with the resin. This result may offer physico-chemical insights into behavior and fate of the pollutants.

  19. Charge-exchange reactions and electron-capture rates for presupernova stellar evolution

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but

  20. Oxygen isotope variations in granulite-grade iron formations: constraints on oxygen diffusion and retrograde isotopic exchange

    USGS Publications Warehouse

    Sharp, Z.D.; O'Neil, J.R.; Essene, E.J.

    1988-01-01

    The oxygen isotope ratios of various minerals were measured in a granulite-grade iron formation in the Wind River Range, Wyoming. Estimates of temperature and pressure for the terrane using well calibrated geothermometers and geobarometers are 730??50?? C and 5.5??0.5 kbar. The mineral constraints on fluid compositions in the iron formation during retrogression require either very CO2-rich fluids or no fluid at all. In the iron formation, isotopic temperature estimates from quartz-magnetite fractionations are controlled by the proximity to the enclosing granitic gneiss, and range from 500?? C (??qz - mt=10.0???) within 2-3 meters of the orthogneiss contact to 600?? C (??qz - mt=8.0???) farther from the contact. Temperature estimates from other isotopic thermometers are in good agreement with those derived from the quartz-magnetite fractionations. During prograde metamorphism, the isotopic composition of the iron formation was lowered by the infiltration of an external fluid. Equilibrium was achieved over tens of meters. Closed-system retrograde exchange is consistent with the nearly constant whole-rock ??18Owr value of 8.0??0.6???. The greater ??qz-mt values in the iron formation near the orthogneiss contact are most likely due to a lower oxygen blocking temperature related to greater exchange-ability of deformed minerals at the contact. Cooling rates required to preserve the quartz-magnetite fractionations in the central portion of the iron formation are unreasonably high (???800?? C/Ma). In order to preserve the 600?? C isotopic temperature, the diffusion coefficient D (for ??-quartz) should be two orders of magnitude lower than the experimentally determined value of 2.5??10-16 cm2/s at 833 K. There are no values for the activation energy (Q) and pre-exponential diffusion coefficient (D0), consistent with the experimentally determined values, that will result in reasonable cooling rates for the Wind River iron formation. The discrepancy between the diffusion

  1. Preliminary evaluation of oxygen isotopic exchange between chlorite and water

    SciTech Connect

    Cole, D.R.

    1985-01-01

    Variations in the oxygen isotopic composition of biotites altering to chlorite have been monitored as a function of time from 16 hydrothermal granite-water experiments conducted at the following conditions: T = 170/sup 0/ - 300/sup 0/C; P = 100-300 bars; mNaCl = 0.1-1.0; water/biotite mass ratio = 1-60 for periods up to 900 hours. The magnitude of delta/sup 18/O depletion in biotite increased with increasing temperature and time. Detailed thin section, x-ray and SEM studies demonstrated that biotite is altered exclusively to chlorite in 11 of the 16 experiments. The amounts of chlorite formed in these experiments increased with increasing temperature as well as time. The isotopic compositions of chlorite were calculated from mass balance, and compared with the final measured delta/sup 18/O of the fluids. These fractionations (..delta..Ch1-w) average 0.26, 0.77, and 3.74 per thousand for T = 300/sup 0/, 250/sup 0/, and 200/sup 0/C, respectively. Several lines of evidence will be discussed that suggest these data may represent equilibrium values. A least-squares regression of the data yields the following preliminary equation: 1000 ln ..cap alpha../sub/ Chl-W/ = 08.38 (10/sup 3//T) + 4.81 (10/sup 6//T/sup 2/). The error about this curve is at least +/-0.5 per thousand at 250/sup 0/ and 300/sup 0/C, and +/- 1 per thousand at 200/sup 0/C. There is excellent agreement between this curve and the curve given by Wenner and Taylor (1971) for the temperature range of 250/sup 0/ to 300/sup 0/C. However, below 250/sup 0/C, the new chloride-water results predict consistently higher temperatures compared to previous estimates.

  2. HYDROGEN ISOTOPE RECOVERY USING PROTON EXCHANGE MEMBRANE ELECTROLYSIS OF WATER

    SciTech Connect

    Fox, E; Scott Greenway, S; Amy Ekechukwu, A

    2007-08-27

    A critical component of tritium glovebox operations is the recovery of high value tritium from the water vapor in the glove box atmosphere. One proposed method to improve existing tritium recovery systems is to replace the disposable hot magnesium beds used to separate the hydrogen and oxygen in water with continuous use Proton Exchange Membrane Electrolyzers (PEMEs). This study examines radiation exposure to the membrane of a PEME and examines the sizing difference that would be needed if the electrolyzer were operated with a cathode water vapor feed instead of an anode liquid water feed.

  3. A new approach to quantifying internal diffusion resistances and CO2 isotope exchange in leaves

    NASA Astrophysics Data System (ADS)

    West, Jason; Ogée, Jérôme; Burlett, Régis; Gimeno, Teresa; Genty, Bernard; Jones, Samuel; Wohl, Steven; Bosc, Alexandre; Wingate, Lisa

    2016-04-01

    The oxygen isotopic composition (δ18O) of atmospheric CO2 can constrain the global CO2 budget at a range of scales, offering the potential to partition net CO2 exchanges into their component gross fluxes and provide insights to linkages between C and water cycles. However, there are significant limitations to utilizing the δ18O of CO2 to constrain C budgets because of uncertainties associated with the isotopic exchange of CO2 with terrestrial water pools. Leaf water in particular represents a critical pool with ongoing debates about its enrichment in heavy isotopes during transpiration and the hydration of CO2 and its oxygen isotope exchange with this pool. Isotopic heterogeneity of the leaf water, the spatial distribution and activity of carbonic anhydrase (CA) within leaves, and resistance to diffusion of CO2 from the substomatal cavity to chloroplasts are all key components with important uncertainties. Better constraints on these would significantly improve our ability to understand and model the global C budget as well as yield insights to fundamental aspects of leaf physiology. We report results using a new measurement system that permits the simultaneous measurement of the 13C and 18O composition of CO2 and the 18O isotopic composition of leaf transpiration. As this new approach permits rapid alteration of the isotopic composition of gases interacting with the leaf, key model parameters can be derived directly and simultaneously. Hence, our approach dos not rely on separate measurements shifted in time from the gas exchange measurements or that may not quantify the relevant scale of heterogeneity (e.g., CA enzyme assays or bulk leaf water extraction and analysis). In particular, this new method explicitly distinguishes the leaf mesophyll resistance to CO2 transport relevant for photosynthesis from the resistance required for interpreting the δ18O of CO2 and allows us to derive other relevant parameters directly. This new measurement system and modeling

  4. The formation of Kuiper-belt binaries through exchange reactions.

    PubMed

    Funato, Yoko; Makino, Junichiro; Hut, Piet; Kokubo, Eiichiro; Kinoshita, Daisuke

    2004-02-01

    Recent observations have revealed that an unexpectedly high fraction--a few per cent--of the trans-Neptunian objects (TNOs) that inhabit the Kuiper belt are binaries. The components have roughly equal masses, with very eccentric orbits that are wider than a hundred times the radius of the primary. Standard theories of binary asteroid formation tend to produce close binaries with circular orbits, so two models have been proposed to explain the unique characteristics of the TNOs. Both models, however, require extreme assumptions regarding the size distribution of the TNOs. Here we report a mechanism that is capable of producing binary TNOs with the observed properties during the early stages of their formation and growth. The only required assumption is that the TNOs were initially formed through gravitational instabilities in the protoplanetary dust disk. The basis of the mechanism is an exchange reaction in which a binary whose primary component is much more massive than the secondary interacts with a third body, whose mass is comparable to that of the primary. The low-mass secondary component is ejected and replaced by the third body in a wide but eccentric orbit. PMID:14765188

  5. Stable isotope systematics of medium-grade pelitic rocks of southwestern Maine: Implications of postmetamorphic exchange

    SciTech Connect

    Colucci, M.T. . Stable Isotope Lab.); Dyar, M.D. . Dept. Geological Science); Gregory, R.T.; Holdaway, M.J. . Dept. Geological Science); Guidotti, C.V. . Dept. Geological Science)

    1993-02-01

    Oxygen and hydrogen isotope ratios were determined on coexisting biotite-muscovite-quartz-plagioclase mineral separates from 61 Siluro-Devonian pelitic schists of the Rangeley, Oquossoc, and Bryant Pond quadrangles of western Maine. Contact metamorphic zones range from garnet grade (450 C) through K feldspar-sillimanite grade (650 C) at 3-4Kb. Muscovite and biotite [sup 18]O-fractionations are remarkably constant and independent of metamorphic grade, recording apparent temperatures of 430 [plus minus] 70 C (Javoy, 1977). Multi-phase oxygen isotope isotherms likewise yield low (320 [plus minus] 60 C) temperatures that bear no systematic relation with metamorphic grade. The thermal history of intruding plutons as inferred from [sup 40]Ar/[sup 39]Ar studies (De Yoreo et al., 1989) indicates a 50--100 Ma period of postmetamorphic ambient conditions at 350--400 C. The observed oxygen isotope fractionations across the entire metamorphic complex therefore resulted from prolonged residence at postmetamorphic crustal conditions, obscuring details of isotopic exchange during the earlier polymetamorphism. Apparent equilibrium deuterium fractionations between coexisting mica minerals locally vary (8 < [Delta]D[sub ms-bt] < 25) but bear no systematic relation with mineral chemistry or metamorphic grade. The measured deuterium fractionation factors are generally lower and more variable than those predicted from previous experimental studies. By analogy with shallow-level hydrothermal systems, [delta]D vs. [delta][sup 18]O relations and fluid-rock isotope exchange modeling indicate low integrated fluid-rock ratios (0.05--0.15) during post-peakmetamorphic isotope exchange.

  6. Atmosphere-surface water exchanges from measurements of isotopic composition at a tall tower in Boulder

    NASA Astrophysics Data System (ADS)

    Noone, D. C.; Risi, C.; Raudzens Bailey, A.; Brown, D. P.; Buenning, N. H.; Gregory, S. A.; Nusbaumer, J.; Sykes, J.; Schneider, D. P.; Vanderwende, B. J.; Wong, J.; Wolfe, D. E.

    2010-12-01

    The exchange of water and carbon between the atmosphere and land remains poorly understood, particularly in regions of complex terrain and in the case of stable nighttime boundary layers. Profile measurements of the isotopic composition of water vapor were made at the 300 meter NOAA Boulder Atmospheric Observatory tall tower facility in Erie in February of 2010 to establish how well moisture budgets can be constrained with isotopic information. Measurements were made by placing instruments on the tower elevator and manually controlling the ascent and decent every 15 minutes for a total of 311 profiles. The four-day experiment followed a snow storm that produced 25-50 mm of snow. Temporal variations in the measured isotopic composition are dominated by the synoptic meteorology rather than local processes. Although both the “Keeling plot” approach applied to time series and the mixing lines applied to vertical profiles emerge algebraically from simple turbulence theory, only the latter is successful in estimating end members in good agreement with the known isotopic composition of the source water. However, mixing lines are only formed when conditions are stationary, and the approach generally fails during times of changes in the profile associated with regional advection. Rapid ventilation of the boundary layer during the day is found from the isotopic data because evaporation of the snow melt tags the gas transport. Weak transport at night is determined using CO2 profiles because respiration contrasts with the tropospheric baseline. We find that transport at night is characterized by slow mixing interrupted by fast mixing events. The intermittent exchange appears important for the net exchange and it is not clear that they are captured in turbulence schemes in climate models. Because the mixing line method is not uniformly successful, our results suggest a more complete framework based on boundary layer dynamics is needed for isotopic profiles to be meaningful.

  7. Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

    SciTech Connect

    Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.

    2006-05-09

    99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.

  8. Isotopically sensitive branching and its effect on the observed intramolecular isotope effects in cytochrome P-450 catalyzed reactions: a new method for the estimation of intrinsic isotope effects

    SciTech Connect

    Jones, J.P.; Korzekwa, K.R.; Rettie, A.E.; Trager, W.F.

    1986-10-29

    Two selectively deuterated n-octanes (octane-1-/sup 2/H/sub 3/ and octane-1,2,3-/sup 2/H/sub 7/) were synthesized and subjected to hydroxylation by phenobarbital-induced rat liver microsomes and purified cytochrome P-450b. The results of these experiments provide evidence which clarifies the interplay between a branched reaction pathway and the equilibration of an enzyme-substrate complex, in determining the magnitude of an observed isotope effect. An equation is derived that allows limits to placed on the intrinsic isotope effect. The equation is based on the observed isotope effect and the regioselectivity of a branch reaction pathway, catalyzed by an enzyme that forms two products via a single enzyme-substrate complex. The intrinsic isotope effect for the formation of 1-octanol was determined by this equation to lie between 9.5 and 9.8.

  9. Nuclear orientation of radon isotopes by spin-exchange optical pumping

    SciTech Connect

    Kitano, M.; Calaprice, F.P.; Pitt, M.L.; Clayhold, J.; Happer, W.; Kadar-Kallen, M.; Musolf, M.; Ulm, G.; Wendt, K.; Chupp, T.

    1988-05-23

    This paper reports the first demonstration of nuclear orientation of radon atoms. The method employed was spin exchange with potassium atoms polarized by optical pumping. The radon isotopes were produced at the ISOLDE isotope separator of CERN. The nuclear alignment of /sup 209/Rn and /sup 223/Rn has been measured by observation of ..gamma..-ray anisotropies and the magnetic dipole moment for /sup 209/Rn has been measured by the nuclear-magnetic-resonance method to be chemically bond..mu..chemically bond = 0.838 81(39)..mu../sub N/.

  10. Determination of uranium isotopes in environmental samples by anion exchange in sulfuric and hydrochloric acid media.

    PubMed

    Popov, L

    2016-09-01

    Method for determination of uranium isotopes in various environmental samples is presented. The major advantages of the method are the low cost of the analysis, high radiochemical yields and good decontamination factors from the matrix elements, natural and man-made radionuclides. The separation and purification of uranium is attained by adsorption with strong base anion exchange resin in sulfuric and hydrochloric acid media. Uranium is electrodeposited on a stainless steel disk and measured by alpha spectrometry. The analytical method has been applied for the determination of concentrations of uranium isotopes in mineral, spring and tap waters from Bulgaria. The analytical quality was checked by analyzing reference materials. PMID:27451111

  11. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    PubMed

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations. PMID:25941865

  12. Oxygen isotope effects of enzyme-catalyzed organophosphorus hydrolysis reactions: implications for interpretation of dissolved PO4 δ18O values in natural waters

    NASA Astrophysics Data System (ADS)

    Liang, Y.; Blake, R. E.

    2002-12-01

    The geochemical cycling of P in Earth surface environments is controlled largely by biota. It has been recently demonstrated that intracellular cycling of P in microbial cultures and biological turnover of P in natural waters leads to temperature-dependent O isotope equilibrium between dissolved inorganic PO4 (Pi) and ambient water, and that the δ18O of Pi can be a useful tracer of biological reactions and P cycling in aquatic systems/sediments. Oxygen isotope exchange between Pi and water during biological turnover of P is catalyzed by enzymes at low-temperature. Phosphoenzymes play a crucial role in the intracellular functions of all living organisms and also have important extracellular functions in aquatic ecosystems such as regeneration of Pi from organophosphorus compounds (e.g., phosphoesters). Laboratory experiments indicate that extracellular enzyme reactions may result in incomplete Pi turnover and non-equilibrium Pi-water O isotope exchange. Determination of the O isotope effects of phosphoenzyme-catalyzed reactions is fundamental to the understanding of mechanisms of PO4-water O isotope exchange, pathways of biogeochemical P cycling, and interpretation of PO4 δ18O values from natural systems. Here we report on the O isotope fractionation between enzymatically-released Pi and water, in cell-free abiotic systems. Alkaline phosphatase (Apase) is a non-specific phosphohydrolase commonly found in fresh and marine coastal waters that catalyzes the hydrolysis of Pi from phosphomonoesters. We examined the O isotope effects of Apase derived from both microbial and eukaryotic sources and acting on different phosphomonoester substrates (e.g., α-D-Glucose 1-Phosphate, β-Glycerophosphate, AMP) in 18O-labeled waters. Oxygen isotope ratios of Pi released by Apase indicate that only 1 of the 4 O atoms in PO4 is incorporated from water with little or no apparent O isotopic fractionation at the site of incorporation. This observation is consistent with

  13. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    SciTech Connect

    Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2014-10-15

    Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10{sup −2} s{sup −1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 °C.

  14. 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

    PubMed Central

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

    1996-01-01

    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 radioisotopes, inhibitors (chloroform and fluoroacetate), and methane flux were used to provide independent estimates of acetate turnover. Pore water acetate pool sizes were determined by gas chromatography with a flame ionization detector, and stable isotope-labeled acetate was determined by gas chromatography-mass spectrometry. The appearance of acetates with a different isotope labeling pattern from that initially added demonstrated that isotopic exchange occurred during methanogenic acetate metabolism. The predominant exchange processes were (i) D-H exchange in the methyl group and (ii) (sup13)C-(sup12)C exchange at the carboxyl carbon. These exchanges are most probably caused by the activity of the enzyme complex carbon monoxide dehydrogenase and subsequent methyl group dehydrogenation by tetrahydromethanopterine or a related enzyme. The methyl carbon was not subject to exchange during transformation to methane, and hence acetate with the methyl carbon labeled will provide the most reliable estimate of acetate turnover to methane. Acetate turnover rate estimates with these labels were consistent with independent estimates of acetate turnover (acetate accumulation after inhibition and methane flux). Turnover rates from either radioisotope- or stable isotope-labeled methyl carbon isotopes are, however, dependent on accurate determination of the acetate pool size. The additions of large amounts of stable isotope-labeled acetate elevate the acetate pool size, stimulating acetate consumption and causing deviation from steady-state kinetics. This can, however, be overcome by the application of a non-steady-state model. Isotopic exchange in sediments dominated by sulfate reduction

  15. Position-specific isotope modeling of organic micropollutants transformation through different reaction pathways.

    PubMed

    Jin, Biao; Rolle, Massimo

    2016-03-01

    The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. PMID:26708763

  16. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    SciTech Connect

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times higher than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.

  17. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    DOE PAGESBeta

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H2 + PdD and D2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H2/atm cm2 s is found for H2 + PdD at 298 K, 1.4 times highermore » than that for D2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

  18. Probing Aluminum Reactions in Combustion and Explosion Via the Kinetic Isotope Effect

    NASA Astrophysics Data System (ADS)

    Tappan, Bryce

    2015-06-01

    The mechanism that controls the reaction speed of aluminum in explosion and combustion is poorly understood, and experimentally difficult to measure. Recently, work in our laboratory has demonstrated that during the combustion of nanoparticulate aluminum with H2O or D2O, different reaction rates due to the kinetic isotope effect are observed. This result is the first-ever observed kinetic isotope effect in a metal combustion reaction and verifies that chemical reaction kinetics play a major role in determining the global burning rate. During or shortly after a detonation, however, the reaction rates are dramatically faster and the physical mechanism controlling Al reaction is likely different than during combustion events. To utilize the kinetic isotope effect to probe Al reactions in detonation, formulations were produced that contain powdered Al in deuterated high explosives and high-fidelity detonation velocity were determined along with PDV measurements to observe early wall velocity expansion measurements. The JWL equation of state was solved to determine temperature, pressure and energies at specific time periods, in addition of Gurney energies, which enables the elucidation of Al reaction extent. By comparison of the Al oxidation with LiF, data indicate that Al oxidation occurs on an extremely fast time scale and isotope effects in both the HE detonation and post-detonation Al reactions are discussed.

  19. Using MASHA+TIMEPIX Setup for Registration Beta Decay Isotopes Produced in Heavy Ion Induced Reactions

    NASA Astrophysics Data System (ADS)

    Rodin, A. M.; Belozerov, A. V.; Chernysheva, E. V.; Dmitriev, S. N.; Gulyaev, A. V.; Gulyaeva, A. V.; Itkis, M. G.; Novoselov, A. S.; Oganessian, Yu. Ts.; Salamatin, V. S.; Stepantsov, S. V.; Vedeneev, V. Yu.; Yukhimchuk, S. A.; Krupa, L.; Granja, C.; Pospisil, S.; Kliman, J.; Motycak, S.; Sivacek, I.

    2015-06-01

    Radon and mercury isotopes were produced in multi nucleon transfer (48Ca + 232Th) and complete fusion (48Ca + naturalNd) reactions, respectively. The isotopes with given masses were detected using two detectors: a multi-strip detector of the well-type (made in CANBERRA) and a position-sensitive quantum counting hybrid pixel detector of the TIMEPIX type. The isotopes implanted into the detectors then emit alpha- and betaparticles until reaching the long lived isotopes. The position of the isotopes, the tracks, the time and energy of beta-particles were measured and analyzed. A new software for the particle recognition and data analysis of experimental results was developed and used. It was shown that MASHA+ TIMEPIX setup is a powerful instrument for investigation of neutron-rich isotopes far from stability limits.

  20. Isotope effects and O-exchange with water during N2O production by denitrifying fungi

    NASA Astrophysics Data System (ADS)

    Rohe, Lena; Braker, Gesche; Well, Reinhard; Giesemann, Anette; Anderson, Traute-Heidi; Wrage-Mönnig, Nicole; Flessa, Heinz

    2013-04-01

    N2O from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. In pure culture studies, bacterial and fungal denitrification showed differences in isotopomer ratios of N2O. Isotopomer ratios of N2O can be expressed as 15N site preference (SP), i.e. the difference between δ15N of the central and terminal N-position of the asymmetric N2O molecule and might be suitable to distinguish between bacterial and fungal N2O under denitrifying soil conditions. Oxygen exchange takes place between H2O and intermediates during the denitrification process. Several studies showed that O-exchange of bacterial denitrifiers varies, but information about fungal O-exchanges is lacking. The objectives of the study presented are i) to verify SP of fungal N2O reported for two strains from pure culture studies and ii) to analyze the oxygen exchange between intermediates and H2O during denitrification in fungal pure cultures. Six different fungal pure cultures known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analysed for concentration and isotopic signatures (SP, average δ15N, δ18O) of N2O. To investigate the oxygen exchange, both treatments were also established in a tracer experiment where 18O-labelled water was used in the medium. The fungal strains evaluated so far indicate similar SP as reported previously. Concerning the amount of N2O produced, the nitrite led to a higher yield than nitrate. O-exchange with 18O-labelled water during fungal denitrification was visible. Using nitrite, the exchange ranged amounted from 39% to full exchange while nitrate led to exchange rates between 13% and full exchange. Detailed results will be presented.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    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. Mass-dependent and -independent fractionation of isotopes in Ni and Pb chelate complex formation reactions

    SciTech Connect

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

    2013-11-13

    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.

  3. Isotopic anomalies from neutron reactions during explosive carbon burning

    NASA Technical Reports Server (NTRS)

    Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

    1978-01-01

    The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

  4. OXYGEN ISOTOPIC COMPOSITIONS OF THE ALLENDE TYPE C CAIs: EVIDENCE FOR ISOTOPIC EXCHANGE DURING NEBULAR MELTING AND ASTEROIDAL THERMAL METAMORPHISM

    SciTech Connect

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

    2008-02-21

    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.

  5. Direct measurement of biosphere-atmosphere isotopic CO2 exchange using the eddy covariance technique

    NASA Astrophysics Data System (ADS)

    Griffis, T. J.; Sargent, S. D.; Baker, J. M.; Lee, X.; Tanner, B. D.; Greene, J.; Swiatek, E.; Billmark, K.

    2008-04-01

    Quantifying isotopic CO2 exchange between the biosphere and atmosphere presents a significant measurement challenge, but has the potential to provide important constraints on local, regional, and global carbon cycling. Past approaches have indirectly estimated isotopic CO2 exchange using relaxed eddy accumulation, the flask-based isoflux method, and flux-gradient techniques. Eddy covariance (EC) is an attractive method because it has the fewest theoretical assumptions and the potential to give a direct measure of isotopic CO2 flux, but it requires a highly sensitive and relatively fast response instrument. To date, no such field measurements have been reported. Here we describe the use of a closed-path tunable diode laser absorption spectroscopy and eddy covariance (EC-TDL) system for isotopic (C16O2, 13CO2, C18O16O) flux measurements. Results are presented from an intensive field experiment conducted over a soybean canopy from 18 July to 20 September 2006. This experiment represents a rigorous field test of the EC-TDL technique because the transport was dominated by relatively high frequency eddies. Net ecosystem CO2 exchange (FN) measured with the EC-TDL system showed strong correlation (r2 = 0.99) in the half-hourly fluxes with an EC open-path infrared gas analyzer (EC-IRGA) over the 60-d period. Net CO2 flux measured with the EC-IRGA and EC-TDL systems agreed to within 9%. Flux loss associated with diminished frequency response beyond 1 Hz for the EC-TDL system was approximately 8% during daytime windy (>4 m s-1) conditions. There was no significant evidence of a kinetic-type fractionation effect related to a phase shift among isotopologues due to tube attenuation. Investigation of isotopic spectral similarity in the flux ratio (δNx) for both 13CO2 and C18O16O transport showed that δNx was relatively independent of eddy scale for this ecosystem type. Flux loss, therefore, did not significantly bias δNx. There was excellent agreement between isofluxes (F

  6. A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

    USGS Publications Warehouse

    Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

    2011-01-01

    Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of

  7. Estimating groundwater exchange with lakes: 1. The stable isotope mass balance method

    USGS Publications Warehouse

    Krabbenhoft, David P.; Bowser, Carl J.; Anderson, Mary P.; Valley, John W.

    1990-01-01

    Groundwater inflow and outflow contributions to the hydrologic budget of lakes can be determined using a stable isotope (18O/16O) mass balance method. The stable isotope method provides a way of integrating the spatial and temporal complexities of the flow field around a lake, thereby offering an appealing alternative to the traditional time and labor intensive methods using seepage meters and an extensive piezometer network. In this paper the method is applied to a lake in northern Wisconsin, demonstrating that it can be successfully applied to lakes in the upper midwest where thousands of similar lakes exist. Inflow and outflow rates calculated for the Wisconsin lake using the isotope mass balance method are 29 and 54 cm/yr, respectively, which compare well to estimates, derived independently using a three-dimensional groundwater flow and solute transport model, of 20 and 50 cm/yr. Such a favorable comparison lends confidence to the use of the stable isotope method to estimate groundwater exchange with lakes. In addition, utilization of stable isotopes in studies of groundwater-lake systems lends insight into mixing processes occurring in the unsaturated zone and in the aquifer surrounding the lake and verifies assumed flow paths based on head measurements in piezometers.

  8. Effect of previous fertilization on phosphorus adsorption. Measurement of surface phosphorus by isotopic exchange

    SciTech Connect

    Lopez, S.C.; Barbaro, N.O.; De Tramontini, S.R. )

    1990-09-01

    Adsorption properties of a soil with previous additions of different phosphate fertilizers were characterized by means of the Langmuir isotherm. The best correlation with the Langmuir isotherm was obtained for low added-phosphorus concentration and for conditions of different amounts of initial soil phosphorus treatment. The phosphorus initially present in each soil sample was evaluated by isotopic exchange. (The use of different isotopic methodologies is discussed.) Carrier-free {sup 32}P was added to a soil-solution system in adsorption equilibrium after soil agitation with increasing phosphorus concentration solutions for 5 days; this allowed measurement of the adsorbed phosphorus that remained exchangeable phosphorus and equilibrium phosphorus concentration was found. The surface exchangeable phosphorus concentration at 0.3 ppm was used to estimate initial surface soil phosphorus. Taking these corrections into account, the authors found adsorption maximum and the bonding energy constant were similar in spite of the amount and kind of previous fertilizer addition. However, the behavior of superphosphate seemed to be modified in the presence of rock phosphate, especially in relation to exchange ability.

  9. Water on Mars: isotopic constraints on exchange between the atmosphere and surface.

    PubMed

    Kass, D M; Yung, Y L

    1999-12-15

    Using a new measurement of the D/H fractionation efficiency and new estimates of the water loss, we calculate that Mars has the equivalent of a approximately 9 m global water layer in a reservoir that exchanges with the atmosphere. The measured D/H enrichment is about 5 times the terrestrial value, but without exchange, the atmosphere converges on an enrichment of 50 in about 0.5 Ma. Due to the large buffering reservoir and the rapid loss rate (10(-3) pr-micrometers yr-1), the small atmospheric reservoir, averaging 10 pr-micrometers, is unlikely to be in continuous isotopic equilibrium with the full 9 m exchangeable reservoir. Instead, it presumably equilibrates during periods of high obliquity; the atmospheric D/H ratio is expected to be enriched in between such periods. If isotopic exchange with a small (4 mm global layer) reservoir occurs under current conditions, it possible for the atmospheric D/H ratio to be within 10% of its long term equilibrium. PMID:11543401

  10. Continuous-flow IRMS technique for determination of Δ17O in (stratospheric) CO2 using complete oxygen isotope exchange with cerium oxide

    NASA Astrophysics Data System (ADS)

    Mrozek, D. J.; Roeckmann, T.

    2012-12-01

    Isotope studies of carbon dioxide (CO2) play an important role in understanding of the global carbon cycle. Stratospheric CO2 is known to undergo an isotopic exchange reaction with ozone (Yung et all 1991). Therefore, stratosphere CO2 shows a mass independent fractionation (MIF) which is a deviation in the 17O content from a purely mass-dependent pattern (MDF): for MDF processes δ17O = 0.52 δ18O, for MIF phenomena Δ17O = δ17O - 0.52 δ18O ≠ 0. The detailled mechanism that controls the 17O anomalies in stratospheric CO2 is not fully understood. Interest in this field has caused innovations in analytical techniques based on Isotope Ratio Mass Spectrometry (IRMS). Our approach was to design an analytical system that allows analysis of δ17O on nanomolar quantities of CO2 suitable for measuring oxygen isotope anomalies in stratospheric air samples. Based on complete oxygen isotope exchange with CeO2 at 650°C (Assonov et al. 2001) we have established an online measurement system for δ17O in CO2. Due to isotopic equilibration with CeO2 the CO2 samples loose their mass independent fractionation information and from the difference between the exchanged and non-exchanged sample Δ17O in the original CO2 can be calculated. The technique is fast and efficient due to its fully automation. A single measurement takes 15 minutes and 2 ml of air (plus flushing of the lines). Analytical precision can be improved by performing multiple measurements on one sample, and the analytical precision for a package of ten measurements is 0.7 ‰ for Δ17O. The new technique is a valuable tool to study the isotopic exchange mechanism between O3 and CO2 in the stratosphere. As a first application, we have determined the isotopic composition of stratospheric CO2 on air samples obtained during the EU project RECONCILE in the Arctic winter/spring season with the high-altitude aircraft Geophysica.

  11. Production of exotic isotopes in complete fusion reactions with radioactive beams

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Zubov, A. S.; Adamian, G. G.; Antonenko, N. V.; Heinz, S.

    2013-11-01

    The isotopic dependence of the complete fusion (capture) cross section is analyzed in the reactions 130,132,134,136,138,140,142,144,146,148,150Xe+48Ca with stable and radioactive beams. It is shown for the first time that the very neutron-rich nuclei 186-191W can be reached with relatively large cross sections by complete fusion reactions with radioactive ion beams at incident energies near the Coulomb barrier. A comparison between the complete fusion and fragmentation reactions for the production of neutron-rich W and neutron-deficient Rn isotopes is performed.

  12. Online, high precision analytical method for determination of Δ17O in stratospheric CO2 with the use of CeO2 isotopic exchange

    NASA Astrophysics Data System (ADS)

    Mrozek, D.; Röckmann, T.

    2012-04-01

    Isotope studies of carbon dioxide (CO2) play an important role in understanding of the global carbon cycle. In the atmosphere CO2 is an important greenhouse gas. Stratospheric CO2 is known to undergo an isotopic exchange reaction with ozone (Yang et all 1991). Therefore, stratosphere CO2 shows a mass independent fractionation (MIF) which is a deviation in the 17O content from a purely mass-dependent pattern (MDF): for MDF phenomena Δ17O = δ17O - 0.52 δ18O=0, for MIF phenomena Δ17O ≠ 0. The detail mechanism that controls the 17O anomalies in stratospheric CO2 is not fully understood. Interest in this field has caused innovations in analytical techniques based on Isotope Rato Mass Spectrometry (IRMS). Our approach was to design an analytical system that allows analysis of 17O on nanomolar quantities of CO2 suitable for measuring oxygen isotope anomalies in the stratospheric air samples. The standard continuous flow-IRMS techniques permit measuring small quantities of CO2 but it is impossible to measure the 17O isotope at mass 45 due to the interference from the much more abundant 13C. Therefore, CO2 has to be either converted to O2 or the oxygen it contains must be exchanged with oxygen of known isotopic composition. Based on complete oxygen isotope exchange with CeO2 at 650°C (Assonov et al. 2001) we have established an online measurement system for δ17O in CO2. The system allows analysis of 17O on nanomolar quantities of CO2 with a good reproducibility of 0.08‰ for δ45CO2. The new technique is a valuable tool to study isotopic exchange mechanism between O3 and CO2 in the stratosphere. We have determined the isotopic composition of stratospheric CO2 on air samples obtained during the EU project RECONCILE in the Arctic winter/spring season with the high-altitude aircraft Geophysica.

  13. Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

    USGS Publications Warehouse

    Morgan, J.W.; Walker, R.J.

    1989-01-01

    A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

  14. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    SciTech Connect

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO, and DTO) using D2 (or H2)

  15. Evaluation of hydrogen isotope exchange methodology on adsorbents for tritium removal

    SciTech Connect

    Morgan, G.A.; Xin Xiao, S.

    2015-03-15

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H{sub 2} (when flowed through the molecular sieves) will exchange with the adsorbed water, D{sub 2}O, leaving H{sub 2}O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T{sub 2}O, HTO, and DTO) using D{sub 2} (or H{sub 2}). (authors)

  16. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    DOE PAGESBeta

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D2O, leaving H2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminated water (T2O, HTO,more » and DTO) using D2 (or H2)« less

  17. Isotopically exchangeable organic hydrogen in coal relates to thermal maturity and maceral composition

    USGS Publications Warehouse

    Mastalerz, Maria; Schimmelmann, A.

    2002-01-01

    Hydrogen isotopic exchangeability (Hex) and ??Dn values of non-exchangeable organic hydrogen were investigated in coal kerogens ranging in rank from lignite to graphite. The relative abundance of Hex is highest in lignite with about 18% of total hydrogen being exchangeable, and decreases to around 2.5% in coals with Ro of 1.7 to ca. 5.7%. At Still higher rank (Ro > 6%), Hex increases slightly, although the abundance of total hydrogen decreases. ??Dn is influenced by original biochemical D/H ratios and by thermal maturation in contact with water. Therefore, ??Dn does not show an overall consistent trend with maturity. ?? 2002 Elsevier Science Ltd. All rights reserved.

  18. Isotope yield ratios of fragments from heavy-ion reactions

    SciTech Connect

    Deak, F.; Kiss, A. ); Seres, Z. ); Galonsky, A.; Heilbronn, L. )

    1991-05-01

    Isotope yield ratios produced in collisions of 35 MeV/nucleon {sup 14}N with targets of C, Ni, Ag, and Ho have an exponential dependence on total neutron-to-proton ratio. A statistical multifragmentation model including particle emission from excited fragments predicted such behavior for yield ratios measured earlier at the higher energy of 84 MeV/nucleon.

  19. Carbon Isotopic Fractionation in Fischer-Tropsch Type Reactions and Relevance to Meteorite Organics

    NASA Technical Reports Server (NTRS)

    Johnson, Natasha M; Elsila, Jamie E.; Kopstein, Mickey; Nuth, Joseph A., III

    2012-01-01

    Fischer-Tropsch-Type (FTT) reactions have been hypothesized to contribute to the formation of organic compounds in the early solar system, but it has been difficult to identify a signature of such reactions in meteoritic organics. The work reported here examined whether temperature-dependent carbon isotopic fractionation of FTT reactions might provide such a signature. Analyses of bulk organic deposits resulting from FTT experiments show a slight trend towards lighter carbon isotopic ratios with increasing temperature. It is unlikely, however, that these carbon isotopic signatures could provide definitive provenance for organic compounds in solar system materials produced through FTT reactions, because of the small scale of the observed fractionations and the possibility that signatures from many different temperatures may be present in any specific grain.

  20. Real-time monitoring of the overall exchange of oxygen isotopes between aqueous CO32- and H2O by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Geisler, Thorsten; Perdikouri, Christina; Kasioptas, Argyrios; Dietzel, Martin

    2012-08-01

    In this contribution we demonstrate that in situ Raman spectroscopy is a powerful tool to study the exchange kinetics of oxygen isotopes between aqueous oxo-anions and water using the CO32--H2O system as an example. In situ exchange experiments have been carried out using a 1 M Na2CO3 solution at 45, 60, 75, and 100 °C in a closed system using an in-house-made Teflon©-based fluid cell. The solution was prepared with H2O enriched with 97 at.% 18O. At the given pH from 10.92 to 9.65 at 45-100 °C, respectively, CO32- is the dominant DIC species (>99% CO32-). At the beginning of the reaction the Raman spectrum of the solution is characterised by an intense band near 1067 cm-1 that has been assigned to the ν1(CO3) symmetric stretching vibration of the CO32- molecule. With increasing reaction time three, well-separated bands successively appear near 1046, 1026, and 1006 cm-1. These bands result from mass-related (isotopic) splitting of the ν1(CO3) mode and reflect the symmetric stretching vibration of the oxygen-related isotopologues C16O3-n18On2- (n = 1, 2, and 3). The relative integrated intensities of these bands are related to the amount of 18O present in the aqueous CO32- molecule, which allowed monitoring the time-dependent distribution of the four isotopologues at each temperature. The measured distributions as a function of time were found to agree well with those modelled on the basis of the overall reactions ΣC18O+3H18O⇌ΣC18O16O+3H16O, where the sum sign represents the sum of all carbonate species in solution and n = 0, 1, and 2. Moreover, the measured equilibrium fractions of 18O agree well with those expected from mass balance and published fractionation factors. After correcting the observed exchange rates for the dependence of the exchange kinetics on OH- and CO2(aq) activities, the observed overall logarithmic oxygen isotope exchange rates describe a linear relationship with the inverse temperature along with published exchange data that were

  1. Lead exchange in teeth and bone--a pilot study using stable lead isotopes.

    PubMed Central

    Gulson, B L; Gillings, B R

    1997-01-01

    Stable lead isotopes and lead concentrations were measured in the enamel and dentine of permanent (n = 37) and deciduous teeth (n = 14) from 47 European immigrants to Australia to determine whether lead exchange occurs in teeth and how it relates to lead exchange in bone. Enamel exhibits no exchange of its European-origin lead with lead from the Australian environment. In contrast, dentine lead exchanges with Australian lead to the extent of approximately 1% per year. In one subject, trabecular bone from the tooth socket exchanged almost all its European lead with Australian lead over a a 15-year period (turnover of approximately 6% per year), similar to the approximately 8% per year proposed for lead turnover in trabecular bone. The repository characteristics of intact circumpulpal dentine were investigated by analyses of four sets of contiguous slices from six teeth: 1) a set consisting of slices with intact circumpulpal dentine and cementum; 2) a set in which these areas were removed; 3) another set consisting of slices with intact circumpulpal dentine and cementum; and 4) a set without cementum. These analyses show relatively small differences in isotopic composition between contiguous slices except that circumpulpal dentine appears to be the dominant control on lead concentration. There is a significant correlation (R2 = 0.19, p = 0.01, n = 34) of dentine lead concentration and rate of exchange with residence time from the country of origin and Australian lead, but there is no such correlation with enamel lead concentration. Analyses of permanent and deciduous teeth of subjects from other countries who have resided in Australia for varying lengths of time should resolve some of the questions arising from this pilot study. Images Figure 1. PMID:9347897

  2. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    NASA Astrophysics Data System (ADS)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

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

    NASA Astrophysics Data System (ADS)

    Nolan, Gary S.; Bindeman, Ilya N.

    2013-06-01

    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

  4. Isotopic trends in capture reactions with radioactive and stable potassium beams

    NASA Astrophysics Data System (ADS)

    Sargsyan, V. V.; Adamian, G. G.; Antonenko, N. V.; Kohley, Z.

    2015-11-01

    The isotopic dependence of the capture cross section is analyzed in the reactions 37,39,41,43,45,46,47K+,208Pb124Sn with stable and radioactive beams. A comparison between the reactions +124Sn,46K,208Pb and and +124Sn,48Co,208Pb is performed. The sub-barrier capture cross sections are larger in the reactions with a stable beam at fixed Ec .m .-Vb .

  5. Neutron Capture Reactions on lu Isotopes at Dance

    NASA Astrophysics Data System (ADS)

    Roig, O.; Meot, V.; Daugas, J.-M.; Morel, P.; Jandel, M.; Vieira, D. J.; Bond, E. M.; Bredeweg, T. A.; Couture, A. J.; Haight, R. C.; Keksis, A. L.; Rundberg, R. S.; Ullmann, J. L.; Wouters, J. M.

    2013-03-01

    The DANCE1 (Detector for Advanced Neutron Capture Experiments) array at LANSCE spallation neutron source in Los Alamos has been used to obtain the neutron radiative capture cross sections for 175Lu and 176Lu with neutron energies from thermal up to 100 keV. Both isotopes are of current interest for the nucleosynthesis s-process.2,3 Three targets were used to perform these measurements. One was natural Lu foil of 31 mg/cm2 and the other two were isotope-enriched targets of 175Lu and 176Lu. Firstly, the cross sections were obtained by normalizing yield to a well-known cross section at the thermal neutron energy. Now, we want to obtain absolute cross sections of radiative capture through a precise neutron flux determination, an accurate target mass measurement and an efficiency determination of the DANCE array.

  6. Solubility, diffusivity, and isotopic exchange rate of hydrogen isotopes in Li-Pb

    SciTech Connect

    Maeda, Y.; Edao, Y.; Yamaguchi, S.; Fukada, S.

    2008-07-15

    The diffusion, solution and permeation coefficients of hydrogen isotopes in liquid Li-Pb which is a candidate liquid blanket material for fusion reactors were determined in the temperature range 573-973 K using an unsteady permeation method. Each coefficients was correlated to temperature as follows: D{sub Li-Pb} = 1.8 x 10{sup -8} exp(-11590/RT) [m{sup 2}/s] (1) K{sub Li-Pb} = 2.1x10{sup -6} exp(-18700/RT) [1/Pa{sup 0.5}] (2) P{sub Li-Pb} = 1.8x10{sup -9} exp(-30290/RT) [mol/msPa{sup 0.5}] (3) The hydrogen permeation flux depends on the square root of pressure at 773-973 K. Although the power of pressure declined below 0.4 when temperature was below 673 K, the effects of surface resistance were neglected above 673 K. The hydrogen solubility in liquid Li-Pb was found to correlate with a Sievert's constant. We calculated a height-equivalent to theoretical-plate of a gas-liquid countercurrent extraction tower for tritium recovery rates in liquid Li-Pb to be H{sub L}= 7.0x10{sup -2} [m] (4). (authors)

  7. A boundary exchange influence on deglacial neodymium isotope records from the deep western Indian Ocean

    NASA Astrophysics Data System (ADS)

    Wilson, David J.; Piotrowski, Alexander M.; Galy, Albert; McCave, I. Nicholas

    2012-08-01

    The use of neodymium (Nd) isotopes to reconstruct past water mass mixing relies upon the quasi-conservative behaviour of this tracer, whereas recent studies in the modern oceans have suggested that boundary exchange, involving the addition of Nd from ocean margin sediments, may be an important process in the Nd cycle. Here we suggest that the relative importance of water mass advection versus boundary exchange can be assessed where the deep western boundary current in the Indian Ocean flows past the Madagascan continental margin; a potential source of highly unradiogenic Nd. Foraminiferal coatings and bulk sediment reductive leachates are used to reconstruct bottom water Nd isotopic composition (εNd) in 8 Holocene age coretops, with excellent agreement between the two methods. These data record spatial variability of ∼4 εNd units along the flow path of Circumpolar Deep Water; εNd≈-8.8 in the deep southern inflow upstream of Madagascar, which evolves towards εNd≈-11.5 offshore northern Madagascar, whereas εNd≈-7.3 where deep water re-circulates in the eastern Mascarene Basin. This variability is attributed to boundary exchange and, together with measurements of detrital sediment εNd, an isotope mass balance suggests a deep water residence time for Nd of ≤400 yr along the Madagascan margin. Considering deglacial changes, a core in the deep inflow upstream of Madagascar records εNd changes that agree with previous reconstructions of the Circumpolar Deep Water composition in the Southern Ocean, consistent with a control by water mass advection and perhaps indicating a longer residence time for Nd in the open ocean away from local sediment inputs. In contrast, sites along the Madagascan margin record offset εNd values and reduced glacial-interglacial variability, underlining the importance of detecting boundary exchange before inferring water mass source changes from Nd isotope records. The extent of Madagascan boundary exchange appears to be unchanged

  8. Massive sulfide deposits and hydrothermal solutions: incremental reaction modeling of mineral precipitation and sulfur isotopic evolution

    SciTech Connect

    Janecky, D.R.

    1986-01-01

    Incremental reaction path modeling of chemical and sulfur isotopic reactions occurring in active hydrothermal vents on the seafloor, in combination with chemical and petrographic data from sulfide samples from the seafloor and massive sulfide ore deposits, allows a detailed examination of the processes involved. This paper presents theoretical models of reactions of two types: (1) adiabatic mixing between hydrothermal solution and seawater, and (2) reaction of hydrothermal solution with sulfide deposit materials. In addition, reaction of hydrothermal solution with sulfide deposit minerals and basalt in feeder zones is discussed.

  9. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    NASA Astrophysics Data System (ADS)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  10. Iron-copper cooperative catalysis in the reactions of alkyl Grignard reagents: exchange reaction with alkenes and carbometalation of alkynes.

    PubMed

    Shirakawa, Eiji; Ikeda, Daiji; Masui, Seiji; Yoshida, Masatoshi; Hayashi, Tamio

    2012-01-11

    Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH═CH(2)) and cyclopentylmagnesium bromide was catalyzed by FeCl(3) (2.5 mol %) and CuBr (5 mol %) in combination with PBu(3) (10 mol %) to give RCH(2)CH(2)MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)(3), CuBr, PBu(3), and N,N,N',N'-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step. PMID:22128888

  11. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

    PubMed

    Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

    2016-06-30

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate. PMID:27232375

  12. Carbon-13 and deuterium isotope effects on the reaction catalyzed by glyceraldehyde-3-phosphate dehydrogenase

    SciTech Connect

    Canellas, P.F.; Cleland, W.W. )

    1991-09-10

    Carbon-13 and deuterium isotope effects have been measured on the reaction catalyzed by rabbit muscle glyceraldehyde-3-phosphate dehydrogenase in an effort to locate the rate-limiting steps. With D-glyceraldehyde 3-phosphate as substrate, hydride transfer is a major, but not the only, slow step prior to release of the first product, and the intrinsic primary deuterium and {sup 13}C isotope effects on this step are 5-5.5 and 1.034-1.040, and the sum of the commitments to catalysis is {approximately} 3. The {sup 13}C isotope effects on thiohemiacetal formation and thioester phosphorolysis are 1.005 or less. With D-glyceraldehyde as substrate, the isotope effects are similar, but the sum of commitments is {approximately} 1.5, so that hydride transfer is more, but still not solely, rate limiting for this slow substrate. The observed {sup 13}C and deuterium equilibrium isotope effects on the overall reaction from the hydrated aldehyde are 0.995 and 1.145, while the {sup 13}C equilibrium isotope effect for conversion of a thiohemiacetal to a thioester is 0.994, and that for conversion of a thioester to an acyl phosphate is 0.997. Somewhat uncertain values for the {sup 13}C equilibrium isotope effects on aldehyde dehydration and formation of a thiohemiacetal are 1.003 and 1.004.

  13. Low-temperature isotopic exchange in obsidian: Implications for diffusive mechanisms.

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Cole, David R; Riciputi, Lee R

    2009-01-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more poorly understood. This paper presents the results of a series of isotopic exchange experiments aimed at further elucidating this process and determining the extent to which a point-by-point analysis of the D/H or 18O/18O isotopic composition across the hydrated rim on a geological or archaeological obsidian sample can be used as a paleoclimatic monitor. Experiments were performed by first hydrating the glass for 5 days in water of one isotopic composition, followed by 5 days in water of a second composition. Because waters of near end-member compositions were used (nearly pure 1H2 16O, 1H2 18O, and D2 16O), the relative migration of each species could be ascertained easily by depth-profiling using secondary ion mass spectrometry (SIMS). Results suggest that, during hydration, both the isotopic composition of the waters of hydration, as well as that of intrinsic water remaining from the initial formation of the glass vary dramatically, and a point-by-point analysis leading to paleoclimatic reconstruction is not feasible.

  14. Low-Temperature Isotopic Exchange in Obsidian: Implications for Diffusive Mechanisms

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Cole, David R; Riciputi, Lee R

    2009-01-01

    While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is much more poorly understood. This paper presents the results of a series of isotopic exchange experiments aimed at further elucidating this process and determining the extent to which a point-by-point analysis of the D/H or 18O/18O isotopic composition across the hydrated rim on a geological or archaeological obsidian sample can be used as a paleoclimatic monitor. Experiments were performed by first hydrating the glass for five days in water of one isotopic composition, followed by five days in water of a second composition. Because waters of near end-member compositions were used (nearly pure 1H2 16O, 1H2 18O, and D2 16O), the relative migration of each species could be ascertained easily by depth-profiling using secondary ion mass spectrometry (SIMS). Results suggest that, during hydration, both the isotopic composition of the waters of hydration, as well as that of intrinsic water remaining from the initial formation of the glass vary dramatically, and a point-by-point analysis leading to paleoclimatic reconstruction is not feasible.

  15. Analysis of positional isotope exchange in ATP by cleavage of the. beta. P-O. gamma. P bond. Demonstration of negligible positional isotope exchange by myosin

    SciTech Connect

    Dale, M.P.; Hackney, D.D.

    1987-12-15

    A method for analysis of positional isotope exchange (PIX) during ATP in equilibrium HOH oxygen exchange is presented that uses a two-step degradation of ATP resulting in cleavage of the ..beta..P-O..gamma..P bond. This cleavage yields P/sub i/ derived from the ..gamma..-phosphoryl of ATP that contains all four of the ..gamma.. oxygens. Both PIX between the ..beta.., ..gamma..-bridge and ..beta..-nonbridge positions and washout of the ..gamma..-nonbridge oxygens can be simultaneously followed by using ATP labeled with /sup 17/O at the ..beta..-nonbridge positions and /sup 18/O at the ..beta..,..gamma..-bridge and ..gamma..-nonbridge positions. Application of this method to ATP in equilibrium HOH exchange during single turnovers of myosin indicates that the bulk of the ATP undergoes rapid washout of ..gamma..-nonbridge oxygens in the virtual absence of PIX. At 25/sup 0/C with subfragment 1 the scrambling rate is at the limit of detectability of approximately 0.001 s/sup -1/, which is 50-fold slower than the steady-state rate. This corresponds to a probability of scrambling for the ..beta..-oxygens of bound ADP of 1 in 10,000 for each cycle of reversible hydrolysis of bound ATP. A fraction of the ATP, however, does not undergo rapid washout. With myosin and stoichiometric ATP at 0/sup 0/C, this fraction correspond to 10% of the ATP remaining at 36 s, or 2% of the initial ATP, and an equivalent level of ATP is found that does not bind irreversibly to myosin in a cold chase experiment. A significant level of apparent PIX is observed with subfragment 1 in the fraction that resists washout, and this apparent PIX is shown to be due to contaminant adenylate kinase activity. This apparent PIX due to adenylate kinase provides a possible explanation for the PIX observed by Geeves et al. with subfragment 1.

  16. Carbon kinetic isotope effect in the reaction of CH4 with HO

    NASA Technical Reports Server (NTRS)

    Davidson, J. A.; Cantrell, C. A.; Tyler, S. C.; Shetter, R. E.; Cicerone, R. J.

    1987-01-01

    The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

  17. Calcium isotope separation by chemical exchange with polymer-bound crown compounds

    SciTech Connect

    Jepson, B.E.

    1990-01-01

    Chromatographic separation of calcium isotopes by chemical exchange with polymer-bound 18-crown-6 was investigated. The breakthrough technique of column chromatography was employed to determine the influence of solvent composition and ligand-tether structure on separation coefficients and heterogeneous calcium complex stability. The separation coefficient, {epsilon}, was found to be strongly dependent upon solvent composition. An {epsilon} of 0. 0025{plus minus}0.0002 (95% C.L.) for the {sup 44}Ca/{sup 40}Ca isotope pair was obtained with a 70/30 (by volume) methanol/chloroform solvent mixture at 20.0{degree}C. Differences in the structure of the tether binding the crown ring to the polymer had no influence on {epsilon} at that solvent composition. 8 refs., 5 figs., 1 tab.

  18. Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Kwak, Dochan (Technical Monitor)

    2002-01-01

    Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

  19. Using radium and carbon isotopes to evaluate the biogeochemical impact of boundary exchanges in the North Sea

    NASA Astrophysics Data System (ADS)

    Burt, William; Thomas, Helmuth; Hagens, Mathilde; Brenner, Heiko; Pätsch, Johannes

    2014-05-01

    The North Sea is one of the most studied coastal regions on the planet, yet inputs of carbon and nutrients from the boundaries of the system remain an area of uncertainty in for both the observational and numerical modeling communities alike. Diagenetic reactions within sediments and subsequent sediment-water column exchange provide inputs of dissolved inorganic carbon (DIC), alkalinity (AT) and nutrients (NO3-, PO43-) to the water column throughout the North Sea. In the shallow parts of the North Sea, additional sedimentary inputs from mudflats combined with freshwater inputs from the adjacent European landmass provide a substantial input of dissolved constituents into the Southern North Sea. This study aims to explore the biogeochemical impacts of such boundary exchanges in the North Sea using an extensive suite of water column samples collected in September, 2011. The dominant controls of the stable carbon isotope signature of DIC (δ13CDIC) are determined and isolated. These include in-situ biological activity, and land-based signals, which can affect the paleo records found in shelf sediment cores. These investigations can guide modelling studies to assess the impacts of changing river loads on the biogeochemistry of coastal waters. The sediments and the coastline are also a well-defined source of Radium isotopes (224Ra, 223Ra, 228Ra). The dispersion of longer-lived 228Ra into the North Sea from the coastline can be used to calculate the offshore transport of numerous carbon, nutrient and metal species. Meanwhile the seafloor provides the dominant source of 224Ra, thus a strong relationship between Ra and Alkalinity provides a signature of sedimentary AT release.

  20. Invited Parallel Talk: Forward pion-nucleon charge exchange reaction and Regge constraints

    NASA Astrophysics Data System (ADS)

    Huang, Fei; Sibirtsev, A.; Krewald, S.; Hanhart, C.; Haidenbauer, J.; Meißner, U.-G.

    2009-12-01

    We present our recent study of pion-nucleon charge exchange amplitudes above 2 GeV. We analyze the forward pion-nucleon charge exchange reaction data in a Regge model and compare the resulting amplitudes with those from the Karlsruhe-Helsinki and George-Washington-University partial-wave analyses. We explore possible high-energy constraints for theoretical baryon resonance analyses in the energy region above 2 GeV. Our results show that for the pion-nucleon charge exchange reaction, the appropriate energy region for matching meson-nucleon dynamics to diffractive scattering should be around 3 GeV for the helicity flip amplitude.

  1. Isotopic air sampling in a tallgrass prairie to partition net ecosystem CO2 exchange

    NASA Astrophysics Data System (ADS)

    Lai, Chun-Ta; Schauer, Andrew J.; Owensby, Clenton; Ham, Jay M.; Ehleringer, James R.

    2003-09-01

    Stable isotope ratios of various ecosystem components and net ecosystem exchange (NEE) CO2 fluxes were measured in a C3-C4 mixture tallgrass prairie near Manhattan, Kansas. The July 2002 study period was chosen because of contrasting soil moisture contents, which allowed us to address the effects of drought on photosynthetic CO2 uptake and isotopic discrimination. Significantly higher NEE fluxes were observed for both daytime uptake and nighttime respiration during well-watered conditions when compared to a drought period. Given these differences, we investigated two carbon-flux partitioning questions: (1) What proportions of NEE were contributed by C3 versus C4 species? (2) What proportions of NEE fluxes resulted from canopy assimilation versus ecosystem respiration? To evaluate these questions, air samples were collected every 2 hours during daytime for 3 consecutive days at the same height as the eddy covariance system. These air samples were analyzed for both carbon isotope ratios and CO2 concentrations to establish an empirical relationship for isoflux calculations. An automated air sampling system was used to collect nighttime air samples to estimate the carbon isotope ratios of ecosystem respiration (δR) at weekly intervals for the entire growing season. Models of C3 and C4 photosynthesis were employed to estimate bulk canopy intercellular CO2 concentration in order to calculate photosynthetic discrimination against 13C. Our isotope/NEE results showed that for this grassland, C4 vegetation contributed ˜80% of the NEE fluxes during the drought period and later ˜100% of the NEE fluxes in response to an impulse of intense precipitation. For the entire growing season, the C4 contribution ranged from ˜68% early in the spring to nearly 100% in the late summer. Using an isotopic approach, the calculated partitioned respiratory fluxes were slightly greater than chamber-measured estimates during midday under well-watered conditions. In addition, time series

  2. Deformation effect on total reaction cross sections for neutron-rich Ne isotopes

    SciTech Connect

    Minomo, Kosho; Sumi, Takenori; Ogata, Kazuyuki; Shimizu, Yoshifumi R.; Yahiro, Masanobu; Kimura, Masaaki

    2011-09-15

    The isotope dependence of measured reaction cross sections in the scattering of {sup 28-32}Ne isotopes from a {sup 12}C target at 240 MeV/nucleon is analyzed by the double-folding model with the Melbourne g matrix. The density of the projectile is calculated by the mean-field model with the deformed Woods-Saxon potential. The deformation is evaluated by antisymmetrized molecular dynamics. The deformation of the projectile enhances calculated reaction cross sections to the measured values.

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

    PubMed

    Pollack, Scott R; Schenk, David J

    2015-01-01

    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. PMID:26380956

  4. RADIATION STABILITY OF NAFION MEMBRANES USED FOR ISOTOPE SEPARATION BY PROTON EXCHANGE MEMBRANE ELECTROLYSIS

    SciTech Connect

    Fox, E

    2009-05-15

    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.

  5. Muonium Addition Reactions and Kinetic Isotope Effects in the Gas Phase: k∞ Rate Constants for Mu + C2H2.

    PubMed

    Arseneau, Donald J; Garner, David M; Reid, Ivan D; Fleming, Donald G

    2015-07-16

    The kinetics of the addition reaction of muonium (Mu) to acetylene have been studied in the gas phase at N2 moderator pressures mainly from ∼800 to 1000 Torr and over the temperature range from 168 to 446 K, but also down to 200 Torr at 168 K and over a much higher range of pressures, from 10 to 44 bar at 295 K, demonstrating pressure-independent rate constants, kMu(T). Even at 200 Torr moderator pressure, the kinetics for Mu + C2H2 addition behave as if effectively in the high-pressure limit, giving k∞ = kMu due to depolarization of the muon spin in the MuC2H2 radical formed in the addition step. The rate constants kMu(T) exhibit modest Arrhenius curvature over the range of measured temperatures. Comparisons with data and with calculations for the corresponding H(D) + C2H2 addition reactions reveal a much faster rate for the Mu reaction at the lowest temperatures, by 2 orders of magnitude, in accord with the propensity of Mu to undergo quantum tunneling. Moreover, isotopic atom exchange, which contributes in a major way to the analogous D atom reaction, forming C2HD + H, is expected to be unimportant in the case of Mu addition, a consequence of the much higher zero-point energy and hence weaker C-Mu bond that would form, meaning that the present report of the Mu + C2H2 reaction is effectively the only experimental study of kinetic isotope effects in the high-pressure limit for H-atom addition to acetylene. PMID:25664674

  6. Electron and energy transfer as probes of interparticle ion-exchange reactions in zeolite Y

    SciTech Connect

    Brigham, E.S.; Snowden, P.T.; Kim, Y.I.; Mallouk, T.E. )

    1993-08-19

    Photoinduced electron transfer and energy transfer reactions of tris(2,2[prime]-bipyridyl)ruthenium(II) (Ru(bpy)[sub 3][sup 2+]) with methylviologen (MV[sup 2+]) and tris(2,2[prime]-bipyridyl)osmium(II) (Os(bpy)[sub 3][sup 2+]) ion-exchanged onto/into separate zeolite Y particles were studied by emission spectroscopy. The kinetics of interparticle exchange were probed by observing the quenching of the MLCT excited state of-Ru(bpy)[sub 3][sup 2+] by mobile MV[sup 2+] or OS(bpy)[sub 3][sup 2+] ions. The exchange reactions occur on time scales of seconds to hours, depending on the ionic strength of the surrounding medium. The time-dependent luminescence data were fitted to a dispersed kinetics model, from which average rate constants for the exchange reactions could be extracted. Time constants for interparticle exchange of MV[sup 2+] and Os(bpy)[sub 3][sup 2+] ions, in the range 10[sup 3]-10[sup 5] s at electrolyte concentrations of 0.1-3 mM, are significantly longer than the time scales (10[sup [minus]7]-10[sup 1] s) of most electrochemical and photochemical intrazeolitic reactions involving these and similar electroactive ions. These results argue for reaction mechanisms that invoke intrazeolite electron transfer, rather than exchange of electroactive ions followed by solution-phase electron transfer, in these systems. 25 refs., 6 figs., 1 tab.

  7. Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention.

    PubMed

    Hodges, James M; Kletetschka, Karel; Fenton, Julie L; Read, Carlos G; Schaak, Raymond E

    2015-07-20

    Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot-injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo-spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape-controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core-shell tetrapod ZnS@CdS heterostructures were readily accessible. PMID:26110653

  8. [Net CO2 exchange and carbon isotope flux in Acacia mangium plantation].

    PubMed

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

    2009-11-01

    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. PMID:20135988

  9. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    USGS Publications Warehouse

    Green, C.T.; Böhlke, J.K.; Bekins, B.A.; Phillips, S.P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field-scale (apparent) estimated reaction rates and isotopic fractionations and local-scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O 2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample-based estimates of "apparent" parameters with "true" (intrinsic) values. For this aquifer, non-Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2 threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport. ?? 2010 by the American Geophysical Union.

  10. Kinetic Isotope Effect on Transport Mediated by Clc-Type H+/CL- Exchangers

    NASA Astrophysics Data System (ADS)

    Picollo, Alessandra; Malvezzi, Mattia; Accardi, Alessio

    2013-01-01

    CLC transporters mediate the stoichiometric exchange of 2 Cl- ions for 1 H+ across the membranes of cellular compartments, mostly endosomes and lysosomes. Despite intense biophysical, structural and electrophysiological scrutiny the H+ transfer mechanism of these exchangers remains largely unknown. Previous work showed that two conserved Glutamates define the extremities of the H+ pathway in CLC exchangers. However, we don't know whether H+ transfer between these residues takes place along a series of protonatable moieties, via a Grotthuss mechanism and by diffusion of an H3+O cation and if at any step H+ tunneling plays a role. To differentiate between these possible mechanisms we measured the deuterium kinetic isotope effect on the transport rate of CLC-ec1 and CLC-5, respectively a prokaryotic and a eukaryotic CLC exchanger. We found that transport mediated by both proteins is slowed by ˜20-40% when H2O is replaced by D2O. This result suggests that the rate limiting step for H+ transport takes place along a hydrogen-bonded pathway, possibly formed by water molecules. However, we found that the voltage dependence of CLC-5 inhibition by extracellular H+ is eliminated by this substitution. This suggests that the voltage dependence of this process arises from a mechanism that is exquisitely sensitive to particle mass such as proton tunneling.

  11. Why Seemingly Trivial Events Sometimes Evoke Strong Emotional Reactions: The Role of Social Exchange Rule Violations

    PubMed Central

    Leary, Mark R.; Diebels, Kate J.; Jongman-Sereno, Katrina P.; Fernandez, Xuan Duong

    2015-01-01

    ABSTRACT People sometimes display strong emotional reactions to events that appear disproportionate to the tangible magnitude of the event. Although previous work has addressed the role that perceived disrespect and unfairness have on such reactions, this study examined the role of perceived social exchange rule violations more broadly. Participants (N = 179) rated the effects of another person’s behavior on important personal outcomes, the degree to which the other person had violated fundamental rules of social exchange, and their reactions to the event. Results showed that perceptions of social exchange rule violations accounted for more variance in participants’ reactions than the tangible consequences of the event. The findings support the hypothesis that responses that appear disproportionate to the seriousness of the eliciting event are often fueled by perceived rule violations that may not be obvious to others. PMID:26331429

  12. Proton exchange in acid-base complexes induced by reaction coordinates with heavy atom motions

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-06-01

    We extend previous work on nitric acid-ammonia and nitric acid-alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid-strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are <400 cm-1. This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm-1. Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  13. Acetic anhydride: an intermediate analogue in the acyl-exchange reaction of citramalate lyase.

    PubMed

    Buckel, W

    1976-04-15

    1. Reactivation of deacetyl citramalate lyase by acetic anhydride proceeds through an enzyme-anhydride complex prior to actual acetylation. The reaction is inhibited by citramalate which is competitive with acetic anhydride. 2. A corresponding complex is an intermediate in the carboxymethylation of deacetyl enzyme by iodoacetate. However, the inhibition of this reaction by S-citramalate appears to be non-competitive with iodoacetate. 3. The results lead to the conclusion that acetic anhydride can be regarded as a structural analogue of citramalic acetic anhydride, the proposed intermediate in the acyl exchange reaction on citramalate lyase. 4. The formation of 6-citryl thiolester from the 1-thiolester via the cyclic citric anhydride provides a chemicla model for enzymic acyl exchange. 5. The data suggest that anhydrides are of general importance in acyl exchange reactions of thiolesters. PMID:1278157

  14. Inclusive measurement of (p,. pi. /sup -/xn) double charge exchange reactions on bismuth from threshold to 800 MeV

    SciTech Connect

    Dombsky, M.; D'Auria, J.M.; Kelson, I.; Yavin, A.I.; Ward, T.E.; Clark, J.L.; Ruth, T.; Sheffer, G.

    1985-07-01

    The energy dependence of the total angle-integrated cross section for the production of astatine isotopes from (p,..pi../sup -/xn) double charge exchange reactions on bismuth (/sup 209/Bi) was measured from 120 to 800 MeV using activation and radiochemical techniques. Chemical yields were estimated by direct radioassaying of /sup 211/At activity in thin (approx.1 mg/cm/sup 2/), irradiated bismuth targets. Calculations of the contributions of secondary (two-step) reactions to these measured astatine yields were performed, based partially upon the observed /sup 211/At activity although even at the highest energies, the contribution to products lighter than /sup 207/At was negligible. These data for products with as many as seven neutrons removed from the doubly coherent product (/sup 210/At) display nearly Gaussian shapes for the mass distributions of the astatine residues, with the maximum occurring for about /sup 204/At. The most probable momentum transfer deduced from these distributions for the initial ..pi../sup -/ production step was 335 MeV/c. The observed excitation functions display a behavior similar to that observed for the yield of /sup 210/Po from a (p,..pi../sup 0/) reaction on /sup 209/Bi, but radically different from that observed for inclusive ..pi../sup -/ reactions on a heavy nucleus. These data are discussed in terms of recent theoretical approaches to negative pion production from bismuth. In addition, a simple, schematic model is developed to treat the rapidly decreasing percentage of the total inclusive ..pi../sup -/ emission which is observed for this double charge exchange reaction. This model reflects the opacity of a nucleus to a source of internal energetic protons.

  15. Hydrogen exchange in some coal-related reactions at 400C

    SciTech Connect

    Benjamin, B.M.; Michalczyk, M.J.; Woody, M.C.

    1980-01-01

    The source of hydrogen in cleavage reactions and the paths of internal hydrogen transfer reactions (''hydrogen shuttling'') during solvent refining of coal were studied with deuterium-labeled model compounds. The reactions of 1,2-diphenylethane (bibenzyl, BB) and diphenylmethane (DPM), in which the dimethylene and methylene linkages, respectively, were completely deuterated with tetralin showed that BB formed toluene by C-C cleavage and hydrogen abstraction from tetralin, that DPM was relatively stable to fragmentation, but that both underwent extensive hydrogen exchange at 400C. The kinetics and possible reaction paths were determined for the reactions BB and DPM with tetralin. Reactions of labeled DPM, which exchanged deuterium readily but was otherwise stable, with Illinois No. 6 coal and North Dakota lignite showed that deuterium exchange was much more rapid with coal than in the tetralin system, probably owing to the larger number of radicals present; and that the deuterium was mainly in the benzylic portions of the products. Separate tests with model compounds showed that some aromatic hydrogen, mainly from polynuclear compounds, also underwent exchange. Reaction paths are discussed.

  16. Indirect Measurements for (p,{alpha}) Reactions Involving Boron Isotopes

    SciTech Connect

    Lamia, L.; Spitaleri, C.; Romano, S.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Pizzone, R. G.; Puglia, S. M. R.; Sergi, M. L.; Tudisco, S.; Tumino, A.; Carlin, N.; Szanto, M. G. del; Liguori Neto, R.; Moura, M. M. de; Munhoz, M. G.; Souza, F. A.; Suaide, A. A. P.; Szanto, E.

    2008-04-06

    Light elements lithium, beryllium and boron (LiBeB) were used in the last years as 'possible probe' for a deeper understanding of some extra-mixing phenomena occurring in young Main-Sequence stars. They are mainly destroyed by (p,{alpha}) reactions and cross section measurements for such channels are then needed. The Trojan Horse Method (THM) allows one to extract the astrophysical S(E)-factor without the experience of tunneling through the Coulomb barrier. In this work a resume of the recent results about the {sup 11}B(p,{alpha}{sub 0}){sup 8}Be and {sup 10}B(p,{alpha}){sup 7}Be reactions is shown.

  17. CO-laser-induced photochemical reaction of UF6 with HCl for the isotope separation of uranium hexafluoride

    NASA Astrophysics Data System (ADS)

    Ding, Hong-Bin; Shen, Z. Y.; Zhang, Cun H.

    1993-05-01

    In this paper, we report the results of CO-laser induced photochemical reaction of UF6 with HCl for the isotope separation of uranium hexafluoride, we also discussed that the molecular collision inducing V-T, V-V relaxation process affects on the selectivity of the isotope separation. The obtained quantum coefficiency of the reaction is about 0.34.

  18. Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Beberwyck, Brandon James

    Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be

  19. Excitation of Δ and N* resonances in isobaric charge-exchange reactions of heavy nuclei

    NASA Astrophysics Data System (ADS)

    Vidaña, I.; Benlliure, J.; Geissel, H.; Lenske, H.; Scheidenberger, C.; Vargas, J.

    2016-01-01

    We present a model for the study of the excitation of Δ(1232) and N*(1440) resonances in isobaric charge-exchange (AZ, A(Z ± 1)) reactions of heavy nuclei. Quasi-elastic and inelastic elementary processes contributing to the double differential cross sections of the reactions are described in terms of the exchange of virtual pions. The inelastic channel includes processes where the resonances are excited both in the target and in the projectile nucleus. We present results for reactions of 112Sn and 124Sn on different targets. Our results confirm that the position of the Δ peak is insensitive to targets with mass number A ≥ 12, and show that the origin of the Δ peak shift towards low excitation energies, with respect to its position in reactions with a proton target, can be easily explained in terms of the superposition of the different excitation mechanisms contributing to the reaction.

  20. Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

    NASA Astrophysics Data System (ADS)

    Jin, Biao; Rolle, Massimo

    2016-04-01

    Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M

  1. Role of the aerosol phase state in ammonia/amines exchange reactions.

    PubMed

    Chan, Lap P; Chan, Chak K

    2013-06-01

    The exchange reaction of ammonia in (NH4)2SO4 with an amine and the corresponding reverse reaction of amines in aminium sulfates with ammonia were investigated using an electrodynamic balance coupled with a Raman spectrometer. The temporal changes in particle mass, chemical composition, and phase state were simultaneously monitored. When the salt particles were in an aqueous state at elevated relative humidities (RHs), the exchange of ammonia/amine vapors in the particle phase was reversible. The exchange rates of aqueous particles were in general higher than those of their corresponding solid counterparts. An aqueous phase was essential for the effective displacement of ammonia and amines. Aminium salts in different phase states and with different evaporation characteristics showed remarkably different reaction behaviors in ammonia vapor. The less compact amorphous aminium sulfate solids were more susceptible to ammonia exchange than the crystalline solids. The aminium salts in a liquid state exhibited substantial amine evaporation at <3% RH and formed acidic bisulfate. Under ammonia exposure, these acidic aminium droplets underwent both neutralization and displacement reactions. Stable solid salts containing ammonium, aminium, sulfate, and bisulfate were formed and hindered further reactions. The result suggests that ambient aminium sulfates may be acidic. Overall, the phase states of the ammonium and aminium salt particles crucially determine the heterogeneous reaction rates and final product properties and identities. PMID:23668831

  2. NN-->NNπ reaction near threshold in a covariant one-boson-exchange model

    NASA Astrophysics Data System (ADS)

    Shyam, R.; Mosel, U.

    1998-04-01

    We calculate the cross sections for the p(p,nπ+)p and p(p,pπ0)p reactions for proton beam energies near threshold in a covariant one-boson-exchange model, which incorporates the exchange of π, ρ, σ and ω mesons, treats both nucleon and delta isobar as intermediate states. The final state interaction effects are included within the Watson's theory. Within this model the ω and σ meson exchange terms contribute significantly at these energies, which, along with other meson exchanges, make it possible to reproduce the available experimental data for the total as well as differential cross sections for both the reactions. The cross sections at beam energies <=300 MeV are found to be almost free from the contributions of the Δ isobar excitation.

  3. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969. As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: that is machine-readable (for checking and indicating possible errors); that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  4. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  5. Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

    NASA Technical Reports Server (NTRS)

    King, C.-C.; Clayton, R. N.; Hayatsu, R.; Studier, M. H.

    1979-01-01

    Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large N-15/N-14 ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in N-15 by only 3 per mil relative to the starting material (NH3). The N-15 enrichment in polymers from the Miller-Urey reaction was 10-12 per mil. Both of these fractionations are small compared to the 80-90 per mil differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds.

  6. Formation of pseudomorphic nanocages from Cu2O nanocrystals through anion exchange reactions.

    PubMed

    Wu, Hsin-Lun; Sato, Ryota; Yamaguchi, Atsushi; Kimura, Masato; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu

    2016-03-18

    The crystal structure of ionic nanocrystals (NCs) is usually controlled through reaction temperature, according to their phase diagram. We show that when ionic NCs with different shapes, but identical crystal structures, were subjected to anion exchange reactions under ambient conditions, pseudomorphic products with different crystal systems were obtained. The shape-dependent anionic framework (surface anion sublattice and stacking pattern) of Cu2O NCs determined the crystal system of anion-exchanged products of CuxS nanocages. This method enabled us to convert a body-centered cubic lattice into either a face-centered cubic or a hexagonally close-packed lattice to form crystallographically unusual, multiply twinned structures. Subsequent cation exchange reactions produced CdS nanocages while preserving the multiply-twinned structures. A high-temperature stable phase such as wurtzite ZnS was also obtained with this method at ambient conditions. PMID:26989249

  7. Identification in primitive basalts of a single melt reaction from an isotopically heterogeneous mantle source region

    NASA Astrophysics Data System (ADS)

    Blondes, M. S.; Brandon, M. T.

    2008-12-01

    Though the broad scale effects of recycled material in the source mantle are seen through isotopic variations in basalts, how this material explicitly contributes to the melting process is less constrained. The Big Pine Volcanic Field, CA, provides an excellent natural laboratory to study processes associated with mantle melting. The monogentic vents there preserve primitive, short-lived (< 100 year) eruptive sequences that show a simple chemical evolution, unrelated to shallow-level processes, that repeats at different vents throughout the volcanic field. Furthermore, these chemical trends are paralleled by an increase in ɛNd and a decrease 87Sr/86Sr, indicating the progressive interaction between a mantle melt from a depleted source with a more isotopically evolved unit. We present new evidence here that show that the chemical evolution of these eruptive sequences are controlled by a single, univariant reaction seen as straight chemical and isotopic trends in log compositional space. Generalized equations for dynamic melting reaction progress indicate that straight trends are only possible for continuous reactions with constant distribution coefficients, modes, and melting modes. This relationship is remarkable given that the eruptive sequences shows clear evidence of an isotopically heterogeneous source region. Inversion of rare earth elements (REEs) using published partition coefficients indicate a non-modal melt reaction involving, at the minimum, garnet and pyroxene. The degree of reaction progress indicates the generation of 12% of new melt from a depleted source, and a melt porosity of 15%. These estimates should be viewed as apparent values since they depend on the geometry of the magmatic plumbing system and the percentage of the actual melt that is in equilibrium with the surrounding solid phases. We consider two models consistent with the inversion: 1) melting of a heterogeneous mantle source, consisting of a "plum pudding" mixture of peridotite and

  8. Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

    NASA Technical Reports Server (NTRS)

    Tsuge, S.; Sagara, K.

    1978-01-01

    The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

  9. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    SciTech Connect

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  10. Scaling Hydrologic Exchange Flows and Biogeochemical Reactions from Bedforms to Basins

    NASA Astrophysics Data System (ADS)

    Harvey, J. W.; Gomez-Velez, J. D.

    2015-12-01

    River water moves in and out of the main channel along pathways that are perpendicular to the channel's main axis that flow across or beneath the ground surface. These hydrologic exchange flows (HEFs) are difficult to measure, yet no less important than a river's downstream flow, or exchanges with the atmosphere and deeper groundwater (Harvey and Gooseff, 2015, WRR). There are very few comprehensive investigations of exchange fluxes to understand patterns with river size and relative importance of specific types of exchanges. We used the physically based model NEXSS to simulate multiple scales of hyporheic flow and their cumulative effects on solute reaction in large basins (on the order of Chesapeake Bay basin or larger). Our goal was to explain where and when particular types of hyporheic flow are important in enhancing key biogeochemical reactions, such as organic carbon respiration and denitrification. Results demonstrate that hyporheic flux (expressed per unit area of streambed) varies surprisingly little across the continuum of first-order streams to eighth-order rivers, and vertical exchange beneath small bedforms dominates in comparison with lateral flow beneath gravel bars and meanders. Also, the river's entire volume is exchanged many times with hyporheic flow within a basin, and the turnover length (after one entire river volume is exchanged) is strongly influenced by hydrogeomorphic differences between physiographic regions as well as by river size. The cumulative effects on biogeochemical reactions were assessed using a the reaction significance factor, RSF, which computes the cumulative potential for hyporheic reactions using a dimensionless index that balances reaction progress in a single hyporheic flow path against overall processing efficiency of river turnover through hyporheic flow paths of that type. Reaction significance appears to be strongly dominated by hydrologic factors rather than biogeochemical factors, and seems to be dominated by

  11. Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

    SciTech Connect

    Jiang, Bin; Guo, Hua

    2013-12-14

    Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

  12. Charge exchange and chemical reactions with trapped Th{sup 3+}

    SciTech Connect

    Churchill, L. R.; DePalatis, M. V.; Chapman, M. S.

    2011-01-15

    We have measured the reaction rates of trapped, buffer gas cooled Th{sup 3+} and various gases and have analyzed the reaction products using trapped ion mass spectrometry techniques. Ion trap lifetimes are usually limited by reactions with background molecules, and the high electron affinity of multiply charged ions such as Th{sup 3+} make them more prone to loss. Our results show that reactions of Th{sup 3+} with carbon dioxide, methane, and oxygen all occur near the classical Langevin rate, while reaction rates with argon, hydrogen, and nitrogen are orders of magnitude lower. Reactions of Th{sup 3+} with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th{sup 3+} and carbon dioxide. Loss rates of Th{sup 3+} in helium are consistent with reaction with impurities in the gas. Reaction rates of Th{sup 3+} with nitrogen and argon depend on the internal electronic configuration of the Th{sup 3+}.

  13. Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

    USGS Publications Warehouse

    Baesman, S.M.; Miller, L.G.

    2005-01-01

    Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

  14. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    NASA Technical Reports Server (NTRS)

    Summers, David P.

    2003-01-01

    One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per

  15. Carbon mass-balance modeling and carbon isotope exchange processes in the Curonian Lagoon

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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.

  16. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    USGS Publications Warehouse

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

    2000-01-01

    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.

  17. Hydrogen isotope exchange and conditioning in graphite limiters used in TFTR

    SciTech Connect

    LaMarche, P.H.; Dylla, H.F.; McCarthy, P.J.; Ulrickson, M.

    1986-02-01

    Isotopic exchange experiments performed in TFTR are used to examine the outgassing and diffusive properties of graphite used as the plasma limiter. Changeover from hydrogen to deuterium for different periods ranges from approx.600 to 60 plasma discharges, which appears to be correlated to the limiter temperature. We present a simple analytical model that predicts a fast transient (approx.10 plasma discharges) changeover where the deuterium fueling dilutes the adsorbed and near-surface hydrogen, and a slowly changing term where bulk hydrogen diffuses to the surface. Using this model we can extract an activation energy for diffusion of 0.15 +- 0.02 eV. We hypothesize that interpore diffusion for this porous (approx.15%) material is consistent with our observations. 19 refs.

  18. Energy-loss cross sections for inclusive charge-exchange reactions at intermediate energies

    NASA Technical Reports Server (NTRS)

    Cucinotta, Francis A.; Townsend, Lawrence W.; Dubey, Rajendra R.

    1993-01-01

    Charge-exchange reactions for scattering to the continuum are considered in a high-energy multiple scattering model. Calculations for (p,n) and (He-3,H-3) reactions are made and compared with experimental results for C-12, O-16, and Al-27 targets. Coherent effects are shown to lead to an important role for inelastic multiple scattering terms when light projectiles are considered.

  19. Kinetic Isotope Effects for the Reactions of Muonic Helium and Muonium with H2

    SciTech Connect

    Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr; Brewer, Jess H.; Mielke, Steven L.; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.; Truhlar, Donald G.

    2011-01-28

    The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 amu (4.1H), because the negative muon screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 K. The experimental rate constants are compared with the predictions of accurate quantum mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 K, and variational transition state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10-2 range.

  20. Hydrogen Isotope Separation by Combined Electrolysis Catalytic Exchange Under Reduced Pressure

    SciTech Connect

    Sugiyama, T.; Asakura, Y.; Uda, T.; Abe, Y.; Shiozaki, T.; Enokida, Y.; Yamamoto, I.

    2005-07-15

    At the National Institute for Fusion Science experimental studies on hydrogen isotope separation by a Combined Electrolysis Catalytic Exchange (CECE) process have been carried out in order to apply it to the system of water detritiation for D-D burning experiments of the Large Helical Device. As an improvement of the CECE process, we have developed a reduced-pressure method as a means of enhancing the separation factor. The feasibility of this method is examined through application to a CECE process using a prototype separation column. Hydrogen-deuterium isotope separation experiments are performed in the two cases where column pressures are 12 and 101 kPa, and the separation factors for hydrogen and deuterium are obtained as 6.8 and 5.6, respectively. It is confirmed that the present method is applicable and useful to the CECE process. The values of Height Equivalent to a Theoretical Plate (HETP) are estimated by analyses with the equilibrium stage model. The HETP values are 15 cm at 12 kPa and 13 cm at 101 kPa. The increase of superficial velocity with decreasing pressure may spoil the efficiency of the mass transfer.

  1. TORUS: Theory of Reactions for Unstable iSotopes - Year 1 Continuation and Progress Report

    SciTech Connect

    Arbanas, G; Elster, C; Escher, J; Mukhamedzhanov, A; Nunes, F; Thompson, I J

    2011-02-24

    The TORUS collaboration derives its name from the research it focuses on, namely the Theory of Reactions for Unstable iSotopes. It is a Topical Collaboration in Nuclear Theory, and funded by the Nuclear Theory Division of the Office of Nuclear Physics in the Office of Science of the Department of Energy. The funding started on June 1, 2010, it will have been running for nine months by the date of submission of this Annual Continuation and Progress Report on March 1, 2011. The extent of funding was reduced from the original application, and now supports one postdoctoral researcher for the years 1 through 3. The collaboration brings together as Principal Investigators a large fraction of the nuclear reaction theorists currently active within the USA. The mission of the TORUS Topical Collaboration is to develop new methods that will advance nuclear reaction theory for unstable isotopes by using three-body techniques to improve direct-reaction calculations, and, by using a new partial-fusion theory, to integrate descriptions of direct and compound-nucleus reactions. This multi-institution collaborative effort is directly relevant to three areas of interest: the properties of nuclei far from stability; microscopic studies of nuclear input parameters for astrophysics, and microscopic nuclear reaction theory.

  2. An Experimental Investigation of the Process of Isotope Exchange that Takes Place when Heavy Water Is Exposed to the Atmosphere

    ERIC Educational Resources Information Center

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

    2009-01-01

    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.)

  3. Modelling non-steady-state isotope enrichment of leaf water in a gas-exchange cuvette environment.

    PubMed

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

    2015-12-01

    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

  4. (4B-3H) NADH-H2O exchange reaction of the mitochondrial NADH dehydrogenase

    SciTech Connect

    Chen, S.; Guillory, R.J.

    1985-06-14

    The purified mitochondrial NADH dehydrogenase enzyme has been shown to catalyze a rapid (4B-/sup 3/H) NADH-H/sub 2/O exchange reaction. When the enzyme is subjected to a single freeze-thaw cycle there is a complete loss of NADH dehydrogenation without a measurable decrease in the (4B-/sup 3/H) NADH-H/sub 2/O exchange. Complete loss of the (4B-/sup 3/H) NADH-H/sub 2/O exchange follows brief exposure to ultraviolet photoirradiation. The differential sensitivity of the water exchange reaction and the dehydrogenase activity suggests a direct involvement of the enzymes flavin cofactor in the catalysis of the (4B-/sup 3/H) NADH-H/sub 2/O exchange. Arylazido-beta-alanyl NAD+ (A3'-0-(3-(N-4-azido-2-nitrophenyl)amino) propionyl)NAD+) is shown to be a potent photodependent inhibitor of the (4B-3H) NADH-H/sub 2/O exchange activity following photoirradiation with visible light. This is consistent with the observed photodependent inhibition of the dehydrogenase activity by this photoprobe.

  5. Asymmetric ligand-exchange reaction of biphenol derivatives and chiral bis(oxazolinyl)phenyl-rhodium complex.

    PubMed

    Inoue, Hiroko; Ito, Jun-ichi; Kikuchi, Makoto; Nishiyama, Hisao

    2008-09-01

    Chiral bis(oxazolinyl)phenyl-rhodium acetate complex can enantioselectively capture 1,1'-binaphthol derivatives by ligand-exchange reaction. The structure of the bis(oxazolinyl)phenyl-rhodium biphenol and binaphthol complexes were confirmed by X-ray analysis. PMID:18496824

  6. Further studies on vinamidinium salt amine exchange reactions, borohydride reductions and subsequent transformations

    PubMed Central

    Gupton, John T.; Telang, Nakul; Jia, Xin; Giglio, Benjamin C.; Eaton, James E.; Barelli, Peter J.; Hovaizi, Mona; Hall, Kayleigh E.; Welden, R. Scott; Keough, Matthew J.; Worrall, Eric F.; Finzel, Kara L.; Kluball, Emily J.; Kanters, Rene P.F.; Smith, Timothy M.; Smith, Stanton Q.; Nunes, Shane R.; Wright, Mathew T.; Birnstihl, Jennifer M.

    2010-01-01

    Studies directed at the amine exchange reaction of vinamidinium salts followed by sodium borohydride reduction to secondary and tertiary allylic amines are described. The tertiary allylic amines were alkylated and subjected to base mediated rearrangement to yield a variety of highly functionalized tertiary homoallylic amines. PMID:21113324

  7. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

  8. Carbon kinetic isotope effect in the reaction of CH4 with Cl atoms

    NASA Astrophysics Data System (ADS)

    Saueressig, G.; Bergamaschi, P.; Crowley, J. N.; Fischer, H.; Harris, G. W.

    1995-05-01

    The carbon kinetic isotope effect in the reaction between Cl and CH4 (KIE(sub Cl)) has been measured using tunable diode laser absorption spectroscopy to determine (13)CH4/(12)CH4 ratios. Cl atoms were generated by the irradition of Cl2 in static mixtures of Cl2/CH4/N2 or Cl2/CH4/N2/O2. Both methods resulted in a (KIE(sub Cl)) of 1.066 +/- 0.002 at 297 K. The KIE(sub Cl) displayed a slight temperature dependence, increasing to 1.075 +/- 0.005 at 223 K. This result suggests a significant influence of the title reaction on the stratospheric CH4 isotopic composition and may help to resolve discrepancies between measurements of stratospheric (13)CH4/(12)CH4 profiles and laboratory measurements of KIE(sub OH).

  9. Multiple isotope effects with alternative dinucleotide substrates as a probe of the malic enzyme reaction

    SciTech Connect

    Weiss, P.M.; Urbauer, J.L.; Cleland, W.W. ); Gavva, S.R.; Harris, B.G.; Cook, P.F. )

    1991-06-11

    Deuterium isotope effects and {sup 13}C isotope effects with deuterium- and protium-labeled malate have been obtained for both NAD- and NADP-malic enzymes by using a variety of alternative dinucleotide substrates. With nicotinamide-containing dinucleotides as the oxidizing substrate, the {sup 13}C effect decreases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data are consistent with a stepwise chemical mechanism in which hydride transfer precedes decarboxylation of the oxalacetate intermediate as previously proposed. When dinucleotide substrates such as thio-NAD, 3-nicotinamide rings are used, the {sup 13}C effect increases when deuterated malate is the substrate compared to the value obtained with protium-labeled malate. These data, at face value, are consistent with a change in mechanism from stepwise to concerted for the oxidative decarboxylation portion of the mechanism. However, the increase in the deuterium isotope effect from 1.5 to 3 with a concomitant decrease in the {sup 13}C isotope effect from 1.034 to 1.003 as the dinucleotide substrate is changed suggests that the reaction may still be stepwise with the non-nicotinamide dinucleotides. A more likely explanation is that a {beta}-secondary {sup 13}C isotope effect accompanies hydride transfer as a result of hyperconjugation of the {beta}-carboxyl of malate as the transition state for the hydride transfer step is approached.

  10. High temperature geospeedometry and oxygen isotopic exchange: an analytical point of view

    NASA Astrophysics Data System (ADS)

    Jaoul, O.; Bejina, F.

    2003-04-01

    The determination of cooling rates of rocks using classical geospeedometry often leads to results with uncertainties of several orders of magnitude, mainly because of the difficulty of choosing appropriate diffusion parameters D_0 and E. With a direct application to the 16O/18O isotopic study made by Edwards and Valley (1998, GCA 62, 2265-2277) in a marble (containing diopside (Di) grains imbedded in calcite (Cc)) from the Adirondacks, we have developed a purely analytical model that relates the isotopic partition between the two exchanging minerals as a function of the diopside grain size, d, the half thickness of flat grains (1-D calculation). In this example, diffusion is the slowest in diopside and thus controls the exchange. Calcite is an infinite isotopic reservoir with relatively rapid diffusion, and with no barrier to diffusion between Di / Cc grains. The system is supposed to be fully equilibrated at the initial temperature T_0 (˜675^oC) and the mean isotopic composition δ of diopside grains evolves during cooling, but less and less efficiently as diffusion slows down. Our analysis allows the determination of the initial cooling rate s of the rock: s=(0.40 RT^2_0 D(T_0)/(dexp_D)^2E)(δ_0-δ_1/δ_0-δexp_1)^2 with D(T_0) = D_0 exp(-E/RT_0). δ_0 and δ_1 are the isotopic values at respectively T_0, and T_1, the room temperature, and correspond to the thermometric equation δ = 21.98-1000A'/T^2, with A' = 2370 K^2. The parameter δ_1exp is to be determined experimentally by extrapolation of the δ data plotted against d toward d = 0. For large enough diopside grains with d > d_Dexp we demonstrate that δ-δ_0=(1.8095(δexp_1-δ_0)(ΔH/E)0.80dexp_D)\\cdot1/d with ΔH=2000 A' R/T_0(δ_0-δ_1exp) at the condition that ΔH/E < 0.20 (which is satisfied in E&V's study). We have derived similar relations for spherical grains. Experimental data δ plotted against 1/d give a straight line with slope p. Data depart from the straight line at the value 1/d >= 1/d