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Sample records for isotope rate effect

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

    Science.gov (United States)

    Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven 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, O2 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 O2threshold 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.

  2. Solvent isotope effects on the rates of alkylation of thiolamine models of papain

    International Nuclear Information System (INIS)

    Wandinger, A.; Creighton, D.J.

    1980-01-01

    As a test of whether it is chemically reasonable to attribute any or all of the observed kinetic solvent deuterium isotope effects reported on papain to the fundamental properties of the tautomerization equilibrium, the magnitudes of the solvent deuterium isotope effects on the rates of alkylation of the tautomeric forms of cysteine and β-mercaptoethylamine were determined for bromo- and chloroacetate, bromo- and chloroacetamide, as well as for methylbromoacetate. These thiolamines are viewed as elementary chemical models of the sulfhydryl group tautomerization equilibrium envisioned in the active site of papain. (Auth.)

  3. Relative rate study of the kinetic isotope effect in the 13CH3D + Cl reaction

    DEFF Research Database (Denmark)

    Joelsson, Lars Magnus Torvald; Forecast, Roslyn; Schmidt, Johan Albrecht

    2014-01-01

    The 13CH3D/12CH4kinetic isotope effect, α13CH3D, of CH4 + Cl is determined for the first time, using the relative rate technique and Fourier transform infrared (FTIR) spectroscopy. α13CH3D is found to be 1.60 ± 0.04. In addition, a quantum chemistry/transition state theory model with tunneling...

  4. Isotopic and chemical dilution effects on the vibrational relaxation rate of some totally symmetric motions of liquid acetonitrile

    International Nuclear Information System (INIS)

    Marri, E.; Morresi, A.; Paliani, G.; Cataliotti, R.S.; Giorgini, M.G.

    1999-01-01

    The vibrational dephasing of the ν 1 (C-H, C-D stretching) and ν 3 (C-H, C-D bending) symmetric motions of liquid acetonitrile in its light and fully deuterated forms has been studied in the frame of the vibrational time correlation functions obtained as Fourier transforms of the isotropic Raman spectral distributions and interpreted within the Kubo theory. In addition, the experimental isotropic profiles have been analysed within the bandshape approach formulated by analytical Fourier transformation of the Kubo vibrational time correlation functions in order to derive the relaxation parameters in the frequency domain. The effects of the isotopic (CH 3 CN/CD 3 CN and vice versa) and chemical (CCl 4 ) dilution on the bandshapes and on the vibrational relaxation parameters have been studied. It was observed that the decay rate of ν 1 mode is insensitive to the isotopic dilution but varies appreciably with chemical (CCl 4 ) dilution. The vibrational dephasing of ν 3 mode is qualitatively, but not quantitatively, affected in the same way by chemical dilution and shows a slower modulation regime than that exhibited by the stretching mode. Unlikely from the latter, the ν 3 mode results are slightly affected by the isotopic dilution. Phase relaxation mechanisms of these two motions of acetonitrile in the liquid state are proposed on the basis of these data, and a comparison is made with the results earlier published. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  5. Isotope effects in photochemical rearrangements

    International Nuclear Information System (INIS)

    Sommer, F.

    1983-01-01

    Taking anthracene resp. 9-deuteroanthracene as the initial substance, different substitution products have been prepared. The products originating by direct photolysis have been characterized and their structure has been determined. By comparing the measured kinetic isotope effect and the quantum yield of the nondeuterated and the monodeuterated fluorenes formed it could been demonstrated that the isotope effect mainly is due to the reaction rates and the influence of the deuterium substitution upon the radiationless desactivation against that is small. (HBR) [de

  6. Isotopic discrimination factors and nitrogen turnover rates in reared Atlantic bluefin tuna larvae (Thunnus thynnus: effects of maternal transmission

    Directory of Open Access Journals (Sweden)

    Amaya Uriarte

    2016-11-01

    Full Text Available The use of stable isotope analysis to study animal diets requires estimates of isotopic turnover rates (half time, t50 and discrimination factors (Δ for an accurate interpretation of trophic patterns. The stable isotopes of carbon and nitrogen were analysed for eggs and reared larvae of Thunnus thynnus, as well as for the different diets supplied during the experiment. The results showed high values of δ15N in eggs and larvae (n=646 until 4 DAH. After this time lapse, the stable isotope values declined progressively until 12 DAH, when notochord flexion began. The δ13C showed an inverse trend, suggesting that maternal inheritance of the stable isotopes is evident until pre-flexion stages. This study proposes a model for estimating maternal isotopic signatures of bluefin broodstock. After notochord flexion, larvae were fed with aquaculture-bred gilthead seabream, which resulted in a rapid increase of bluefin larvae δ15N values together with a rapid decrease in δ13C values. The estimated nitrogen half-time to reach the steady state from the diet was 2.5±0.3 days and the discrimination factor was 0.4±0.3(‰. These results represent the first data set that has allowed isotopic nitrogen turnover rates and discrimination factors of the larval stages of bluefin tuna to be estimated.

  7. Noncovalent Hydrogen Isotope Effects

    Science.gov (United States)

    Buchachenko, A. L.; Breslavskaya, N. N.

    2018-02-01

    Zero-point energies (ZPE) and isotope effects, induced by intermolecular, noncovalent vibrations, are computed and tested by experimental data. The ZPE differences of H- and D-complexes of water with hydrogen, methane, and water molecules are about 100-300 cal/mol; they result to isotope effects IE of 1.20-1.70. Semi-ionic bonds between metal ions and water ligands in M(H2O) 6 2+ complexes are much stronger; their ZPEs are about 12-14 kcal/mol per molecule and result to IE of 1.9-2.1 at 300 K. Protonated (deuterated) water and biwater exhibit the largest ZPE differences and isotope effects; the latter are 25-28 and 12-13 for water and biwater, respectively. Noncovalent IEs contribute markedly into the experimentally measured effects and explain many anomalous and even magic properties of the effects, such as the dependence of IE on the solvents and on the presence of the third substances, enormously large isotope effects at the mild conditions, the difference between IEs measured in the reactions of individual protiated and deuterated compounds and those measured in their mixture. Noncovalent IEs are not negligible and should be taken into account to make correct and substantiated conclusions on the reaction mechanisms. The kinetic equations are derived for the total isotope effects, which include noncovalent IEs as additive factors.

  8. Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects

    International Nuclear Information System (INIS)

    Engdahl, K.A.; Bivehed, H.; Ahlberg, P.; Saunders, W.H. Jr.

    1983-01-01

    Primary and secondary deuterium isotope effects have been measured by polarimetry, and primary isotope effects have been calculated for the classical bifunctional catalysis: 2-pyridinone-catalyzed mutarotation of 2,3,4,6-tetra-O-methyl-α-D-glucopyranose (α-TMG) in benzene. From the positively curved plot of the specific rate of epimerization vs. the mole fraction of 2 H in the ''pool'' of OH and NH hydrogens, the isotope effects k/sub HH//k/sub DD/ = 3.66 +/- 0.09, k/sub HH//k/sub DH/ = 1.5, and k/sub HH//k/sub HD/ = 2.4 have been calculated. A secondary isotope effect of 1.14 +/- 0.02 has been measured by using α-TMG and (1- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(l- 2 H)-α-TMG], the synthesis of which is described in detail, together with those for (N- 2 H)-2-pyridinone and (1-O- 2 H)-2,3,4,6-tetra-O-methyl-α-D-glucopyranose [(1-O- 2 H)-α-TMG]. The rate data obtained have also been analyzed by fractionation theory, yielding approximately equal fractionation factors (0.5). The interpretation of the results has been assisted by calculations of the primary deuterium isotope effects using the BEBOVIB IV program. Two models involving small and considerable coupling, respectively, of the transferring protons to heavy-atom motion have been considered. In the favored structure for the transition state of the rate-limiting step, two protons are in transit, and their motion is governed either by a potential with a barrier or by one without. Their motion is considerably coupled to the heavy-atom motion (i.e., the breakage of the ring C-O bond), and tunnel corrections to the isotope effects are found to be negligible

  9. Isotopic effect giant resonances

    International Nuclear Information System (INIS)

    Buenerd, M.; Lebrun, D.; Martin, P.; Perrin, G.; Saintignon, P. de; Chauvin, J.; Duhamel, G.

    1981-10-01

    The systematics of the excitation energy of the giant dipole, monopole, and quadrupole resonances are shown to exhibit an isotopic effect. For a given element, the excitation energy of the transition decreases faster with the increasing neutron number than the empirical laws fitting the overall data. This effect is discussed in terms of the available models

  10. Deuterium isotope effects on toluene metabolism. Product release as a rate-limiting step in cytochrome P-450 catalysis

    International Nuclear Information System (INIS)

    Ling, K.H.; Hanzlik, R.P.

    1989-01-01

    Liver microsomes from phenobarbital-induced rats oxidize toluene to a mixture of benzyl alcohol plus o-, m- and p-cresol (ca. 69:31). Stepwise deuteration of the methyl group causes stepwise decreases in the yield of benzyl alcohol relative to cresols (ca. 24:76 for toluene-d3). For benzyl alcohol formation from toluene-d3 DV = 1.92 and D(V/K) = 3.53. Surprisingly, however, stepwise deuteration induces stepwise increases in total oxidation, giving rise to an inverse isotope effect overall (DV = 0.67 for toluene-d3). Throughout the series (i.e. d0, d1, d2, d3) the ratios of cresol isomers remain constant. These results are interpreted in terms of product release for benzyl alcohol being slower than release of cresols (or their epoxide precursors), and slow enough to be partially rate-limiting in turnover. Thus metabolic switching to cresol formation causes a net acceleration of turnover

  11. Isotope effects on nuclear shielding

    International Nuclear Information System (INIS)

    Hansen, P.E.

    1983-01-01

    This review concentrates upon empirical trends and practical uses of mostly secondary isotope effects, both of the intrinsic and equilibrium types. The text and the tables are arranged in the following fashion. The most 'popular' isotope effect is treated first, deuterium isotope effects on 13 C nuclear shielding, followed by deuterium on 1 H nuclear shieldings, etc. Focus is thus on the isotopes producing the effect rather than on the nuclei suffering the effect. After a brief treatment of each type of isotope effect, general trends are dealt with. Basic trends of intrinsic isotope effects such as additivity, solvent effects, temperature effects, steric effects, substituent effects and hyperconjugation are discussed. Uses of isotope effects for assignment purposes, in stereochemical studies, in hydrogen bonding and in isotopic tracer studies are dealt with. Kinetic studies, especially of phosphates, are frequently performed by utilizing isotope effects. In addition, equilibrium isotope effects are treated in great detail as these are felt to be new and very important and may lead to new uses of isotope effects. Techniques used to obtain isotope effects are briefly surveyed at the end of the chapter. (author)

  12. Rate of oxygen isotope exchange between selenate and water.

    Science.gov (United States)

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

    The rate of oxygen isotope exchange between selenate and water was investigated at conditions of 10 to 80 °C and pH -0.6 to 4.4. Oxygen isotope exchange proceeds as a first-order reaction, and the exchange rate is strongly affected by reaction temperature and pH, with increased rates of isotope exchange at higher temperature and lower pH. Selenate speciation (HSeO(4)(-) vs SeO(4)(2-)) also has a significant effect on the rate of isotope exchange. The half-life for isotope exchange at example natural conditions (25 °C and pH 7) is estimated to be significantly in excess of 10(6) years. The very slow rate of oxygen isotope exchange between selenate and water under most environmental conditions demonstrates that selenate-δ(18)O signatures produced by biogeochemical processes will be preserved and hence that it will be possible to use the value of selenate-δ(18)O to investigate the biogeochemical behavior of selenate, in an analogous fashion to the use of sulfate-δ(18)O to study the biogeochemical behavior of sulfate.

  13. Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

    Science.gov (United States)

    Li, Jun; Guo, Hua

    2018-03-15

    Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

  14. Isotope effects on chemical equilibria

    International Nuclear Information System (INIS)

    Golding, P.D.

    1974-01-01

    The thermodynamic equilibrium constants of three deuterated substituted acetic acids are reported. The calculation of secondary isotope effects of the second kind for the three isotopic acid pairs has been accomplished by the appropriate comparison of thermodynamic equilibrium constants, and by the comparison of isotopic slopes. The effect of substituent variation on the isotope effects reported here disqualifies the simple inductive model as a legitimate description of secondary isotope effects of the second kind. The correlation of diminishing isotope effect per deuterium atom with increasing acidity is also invalidated by the present results. The syntheses of 9-thia-9,10-dihydrophenanthrene-9-oxide and thioxanthene-10-oxide are described. These compounds have been partially deuterated at their respective methylene positions. Spectral evidence indicates stereoselectivity of the methylene protons in the exchange reactions of both compounds. (author)

  15. The rate of second electron transfer to QB(-) in bacterial reaction center of impaired proton delivery shows hydrogen-isotope effect.

    Science.gov (United States)

    Maróti, Ágnes; Wraight, Colin A; Maróti, Péter

    2015-02-01

    The 2nd electron transfer in reaction center of photosynthetic bacterium Rhodobacter sphaeroides is a two step process in which protonation of QB(-) precedes interquinone electron transfer. The thermal activation and pH dependence of the overall rate constants of different RC variants were measured and compared in solvents of water (H2O) and heavy water (D2O). The electron transfer variants where the electron transfer is rate limiting (wild type and M17DN, L210DN and H173EQ mutants) do not show solvent isotope effect and the significant decrease of the rate constant of the second electron transfer in these mutants is due to lowering the operational pKa of QB(-)/QBH: 4.5 (native), 3.9 (L210DN), 3.7 (M17DN) and 3.1 (H173EQ) at pH7. On the other hand, the proton transfer variants where the proton transfer is rate limiting demonstrate solvent isotope effect of pH-independent moderate magnitude (2.11±0.26 (WT+Ni(2+)), 2.16±0.35 (WT+Cd(2+)) and 2.34±0.44 (L210DN/M17DN)) or pH-dependent large magnitude (5.7 at pH4 (L213DN)). Upon deuteration, the free energy and the enthalpy of activation increase in all proton transfer variants by about 1 kcal/mol and the entropy of activation becomes negligible in L210DN/M17DN mutant. The results are interpreted as manifestation of equilibrium and kinetic solvent isotope effects and the structural, energetic and kinetic possibility of alternate proton delivery pathways are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Nd isotopes and crustal growth rate

    International Nuclear Information System (INIS)

    Albarede, F.

    1988-01-01

    Sm/Nd isotopic constraints on crustal growth is discussed. In order to constrain Sm/Nd fractionation between continental crust and depleted mantle, an extensive data base of isotopic measurements (assumed to be adequately representative of continental crust) was compiled. The results imply that the evolution of depleted mantles was roughly linear, with no major discontinuities over the course of geologic time. This is different from other determinations of depleting mantle evolution, which show nonlinear behavior. The Sm/Nd evolution lines for continental crust and depleted mantle intersect between 3.8 to 4.0 Ga, which may indicate that the onset of continental growth was later than 4.5 Ga. A mathematical model is described, the results of which imply that time integrated crustal additions from the mantle are about 1.8 to 2.5 cu km/a, whereas crustal subtractions by sediment recycling are about 0.6 to 1.5 cu km/a. This results in a net time integrated crustal growth rate of about 1 cu km/a, which is similar to present day rates determined, for example, by Reymer and Schubert

  17. Isotope effects: definitions and consequences for pharmacologic studies

    International Nuclear Information System (INIS)

    Van Langenhove, A.

    1986-01-01

    The use of stable isotope-labeled compounds for pharmacologic studies requires careful consideration of the nature of the stable isotope label (2H, 13C, 15N, 18O) and its position of incorporation in the molecule. When deuterium is used, improper positioning can lead to significant primary isotope effects. Primary isotope effects occur when the breaking of the bond to the heavy isotope is the rate-limiting step in a reaction (or metabolic transformation). A reaction will proceed slower for the molecule with the heavy isotope label because of the mass difference between the light and the heavy isotope. In addition to these primary isotope effects, smaller but nevertheless important secondary isotope effects, physicochemical isotope effects, active hydrogen/deuterium exchange, or isotope effects associated with either the enzyme-catalyzed biotransformation or the mass spectrometric ionization and fragmentation can be operative. In mechanistic studies, isotope effects are used to their advantage; however, in pharmacokinetic studies, the occurrence of isotope effects can lead to grossly misleading biologic and analytic results: the metabolism of the drug will differ when in vivo isotope effects are operative, and isotope effects occurring during the analysis procedure will obscure the true metabolic profile of the drug

  18. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-01

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

  19. Rate of radiocarbon retention onto calcite by isotope exchange

    International Nuclear Information System (INIS)

    Lempinen, Janne; Lehto, Jukka

    2016-01-01

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

  20. Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

    Science.gov (United States)

    Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

    2017-11-30

    The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

  1. Protonation mechanism and location of rate-determining steps for the Ascaris suum nicotinamide adenine dinucleotide-malic enzyme reaction from isotope effects and pH studies

    International Nuclear Information System (INIS)

    Kiick, D.M.; Harris, B.G.; Cook, P.F.

    1986-01-01

    The pH dependence of the kinetic parameters and the primary deuterium isotope effects with nicotinamide adenine dinucleotide (NAD) and also thionicotinamide adenine dinucleotide (thio-NAD) as the nucleotide substrates were determined in order to obtain information about the chemical mechanism and location of rate-determining steps for the Ascaris suum NAD-malic enzyme reaction. The maximum velocity with thio-NAD as the nucleotide is pH-independent from pH 4.2 to 9.6, while with NAD, V decreases below a pK of 4.8. V/K for both nucleotides decreases below a pK of 5.6 and above a pK of 8.9. Both the tartronate pKi and V/Kmalate decrease below a pK of 4.8 and above a pK of 8.9. Oxalate is competitive vs. malate above pH 7 and noncompetitive below pH 7 with NAD as the nucleotide. The oxalate Kis increases from a constant value above a pK of 4.9 to another constant value above a pK of 6.7. The oxalate Kii also increases above a pK of 4.9, and this inhibition is enhanced by NADH. In the presence of thio-NAD the inhibition by oxalate is competitive vs. malate below pH 7. For thio-NAD, both DV and D(V/K) are pH-independent and equal to 1.7. With NAD as the nucleotide, DV decreases to 1.0 below a pK of 4.9, while D(V/KNAD) and D(V/Kmalate) are pH-independent. Above pH 7 the isotope effects on V and the V/K values for NAD and malate are equal to 1.45, the pH-independent value of DV above pH 7. Results indicate that substrates bind to only the correctly protonated form of the enzyme. Two enzyme groups are necessary for binding of substrates and catalysis. Both NAD and malate are released from the Michaelis complex at equal rates which are equal to the rate of NADH release from E-NADH above pH 7. Below pH 7 NADH release becomes more rate-determining as the pH decreases until at pH 4.0 it completely limits the overall rate of the reaction

  2. INTRAMOLECULAR ISOTOPE EFFECTS IN HYDROCARBON MASS SPECTRA

    Energy Technology Data Exchange (ETDEWEB)

    Stevenson, D. P.; Schachtschneider, J. H.

    1963-07-15

    Approximate calculations based on the quasi-equilibrium rate theory of the origin of mass spectra are shown to lead to an approximately correct magnitude for the intramolecular ( pi /sup -/) isotope effect on C--H bond dissociation probabilities of various deuterohydrocarbons. (auth)

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

    DEFF Research Database (Denmark)

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

    2010-01-01

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

  4. The Effect of Parasite Infection on Stable Isotope Turnover Rates of δ15N, δ13C and δ34S in Multiple Tissues of Eurasian Perch Perca fluviatilis.

    Directory of Open Access Journals (Sweden)

    Elizabeth Yohannes

    Full Text Available Stable isotope analysis of commercially and ecologically important fish can improve understanding of life-history and trophic ecology. However, accurate interpretation of stable isotope values requires knowledge of tissue-specific isotopic turnover that will help to describe differences in the isotopic composition of tissues and diet. We performed a diet-switch experiment using captive-reared parasite-free Eurasian perch (Perca fluviatilis and wild caught specimens of the same species, infected with the pike tapeworm Triaenophorus nodulosus living in host liver tissue. We hypothesize that metabolic processes related to infection status play a major role in isotopic turnover and examined the influence of parasite infection on isotopic turn-over rate of carbon (δ13C, nitrogen (δ15N and sulphur (δ34S in liver, blood and muscle. The δ15N and δ13C turnovers were fastest in liver tissues, followed by blood and muscle. In infected fish, liver and blood δ15N and δ13C turnover rates were similar. However, in infected fish, liver and blood δ13C turnover was faster than that of δ15N. Moreover, in infected subjects, liver δ15N and δ13C turnover rates were three to five times faster than in livers of uninfected subjects (isotopic half-life of ca.3-4 days compared to 16 and 10 days, respectively. Blood δ34S turnover rate were about twice faster in non-infected individuals implying that parasite infection could retard the turnover rate of δ34S and sulphur containing amino acids. Slower turnover rate of essential amino acid could probably decrease individual immune function. These indicate potential hidden costs of chronic and persistent infections that may have accumulated adverse effects and might eventually impair life-history fitness. For the first time, we were able to shift the isotope values of parasites encapsulated in the liver by changing the dietary source of the host. We also report variability in isotopic turnover rates between tissues

  5. Alpha-capture reaction rates for 22 Ne (α , n) via sub-Coulomb alpha-transfer and its effect on final abundances of s-process isotopes

    Science.gov (United States)

    Jayatissa, Heshani; Rogachev, Grigory; Koshchiy, Yevgeny; Goldberg, Vladilen; Hooker, Joshua; Hunt, Curtis; Magana, Cordero; Roeder, Brian; Saastamoinen, Antti; Spiridon, Alexandria; Upadhyayula, Sriteja; Trippella, Oscar

    2017-09-01

    The 22 Ne (α , n) reaction is a very important neutron source reaction for the slow neutron capture process (s-process) in asymptotic giant branch stars. These direct measurements are very difficult to carry out at the energy regimes of interest for astrophysics (Gamow energies) due to the extremely small reaction cross section. The large uncertainties introduced when extrapolating direct measurements at high energies down to the Gamow energies can be overcome by measuring the Asymptotic Normalization Coefficients (ANC) of the relevant states using α-transfer reactions at sub-Coulomb energies to reduce the optical model dependence. The study of the 22Ne(6Li,d) and 22Ne(7Li,t) reaction was carried out at the Cyclotron Institute at Texas A&M University. The α-ANC measurements for the near α-threshold resonances of 26Mg provide constraints for the 22Ne(α,n) reaction rate. The effect of this reaction rate on the final abundances of the s-process isotopes will be discussed.

  6. Isotope effect and isotope separation. A chemist's view

    International Nuclear Information System (INIS)

    Ishida, Takanobu

    2002-01-01

    What causes the isotope effects (IE)? This presentation will be centered around the equilibrium isotope effects due to the differences in the nuclear masses. The occurrence of the equilibrium constant, K, of isotope exchange reactions which differ from the values predicted by the classical theory of statistical mechanics, K cl , is explored. The non-classical K corresponds to the unit-stage separation factor, α, that is different from unity and forms a basis of an isotope separation process involving the chemical exchange reaction. Here, the word 'chemical exchange' includes not only the isotope exchange chemical reactions between two or more chemical species but also the isotope exchanges involving the equilibria between liquid and vapor phases and liquid-gas, liquid solution-gas, liquid-liquid, and solid-liquid phases. In Section I, origins of the isotope effect phenomena will be explored and, in the process, various quantities used in discussions of isotope effect that have often caused confusions will be unambiguously defined. This Section will also correlate equilibrium constant with separation factor. In Section II, various forms of temperature-dependence of IE and separation factor will be discussed. (author)

  7. Non-linear Isotope Effects

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht

    ’s stratosphere is nearly mass dependent, and only a small fraction of the observed anomalous oxygen-17 excess can be attributed to N2O photolysis. In contrast, stratospheric photolysis produces a significant inverse clumped isotope effect.(ii) Stratospheric OCS photolysis significantly enrich the remaining OCS...

  8. Effects of GC temperature and carrier gas flow rate on on-line oxygen isotope measurement as studied by on-column CO injection.

    Science.gov (United States)

    Chen, Zhi-Gang; Yin, Xi-Jie; Zhou, Youping

    2015-08-01

    Although deemed important to δ 18 O measurement by on-line high-temperature conversion techniques, how the GC conditions affect δ 18 O measurement is rarely examined adequately. We therefore directly injected different volumes of CO or CO-N 2 mix onto the GC column by a six-port valve and examined the CO yield, CO peak shape, CO-N 2 separation, and δ 18 O value under different GC temperatures and carrier gas flow rates. The results show the CO peak area decreases when the carrier gas flow rate increases. The GC temperature has no effect on peak area. The peak width increases with the increase of CO injection volume but decreases with the increase of GC temperature and carrier gas flow rate. The peak intensity increases with the increase of GC temperature and CO injection volume but decreases with the increase of carrier gas flow rate. The peak separation time between N 2 and CO decreases with an increase of GC temperature and carrier gas flow rate. δ 18 O value decreases with the increase of CO injection volume (when half m/z 28 intensity is rate. On average, the δ 18 O value of the injected CO is about 1‰ higher than that of identical reference CO. The δ 18 O distribution pattern of the injected CO is probably a combined result of ion source nonlinearity and preferential loss of C 16 O or oxygen isotopic exchange between zeolite and CO. For practical application, a lower carrier gas flow rate is therefore recommended as it has the combined advantages of higher CO yield, better N 2 -CO separation, lower He consumption, and insignificant effect on δ 18 O value, while a higher-than-60 °C GC temperature and a larger-than-100 µl CO volume is also recommended. When no N 2 peak is expected, a higher GC temperature is recommended, and vice versa. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  9. Use of isotope effects to elucidate enzyme mechanisms

    International Nuclear Information System (INIS)

    Cleland, W.W.

    1982-01-01

    The chemical bond breaking steps are normally not rate limiting for enzymatic reactions. However, comparison of deuterium and tritium isotope effects on the same reaction, especially when coupled with 13 C isotope effects for the same step measured with deuterated as well as unlabeled substrates, allows calculation of the intrinsic isotope effects on the bond breaking steps and thus a determination of the commitments to catalysis for the reactants. The variation in observed isotope effects as a function of reactant concentration can be used to determine kinetic mechanisms, while the pH variation of isotope effects can determine the stickiness of the reactants and which portions of the reactant mechanism are pH dependent. Finally the size of primary and secondary intrinsic isotope effects can be used to determine transition state structure

  10. Isotopic incorporation rates and discrimination factors in mantis shrimp crustaceans.

    Directory of Open Access Journals (Sweden)

    Maya S deVries

    Full Text Available Stable isotope analysis has provided insights into the trophic ecology of a wide diversity of animals. Knowledge about isotopic incorporation rates and isotopic discrimination between the consumer and its diet for different tissue types is essential for interpreting stable isotope data, but these parameters remain understudied in many animal taxa and particularly in aquatic invertebrates. We performed a 292-day diet shift experiment on 92 individuals of the predatory mantis shrimp, Neogonodactylus bredini, to quantify carbon and nitrogen incorporation rates and isotope discrimination factors in muscle and hemolymph tissues. Average isotopic discrimination factors between mantis shrimp muscle and the new diet were 3.0 ± 0.6 ‰ and 0.9 ± 0.3 ‰ for carbon and nitrogen, respectively, which is contrary to what is seen in many other animals (e.g. C and N discrimination is generally 0-1 ‰ and 3-4 ‰, respectively. Surprisingly, the average residence time of nitrogen in hemolymph (28.9 ± 8.3 days was over 8 times longer than that of carbon (3.4 ± 1.4 days. In muscle, the average residence times of carbon and nitrogen were of the same magnitude (89.3 ± 44.4 and 72.8 ± 18.8 days, respectively. We compared the mantis shrimps' incorporation rates, along with rates from four other invertebrate taxa from the literature, to those predicted by an allometric equation relating carbon incorporation rate to body mass that was developed for teleost fishes and sharks. The rate of carbon incorporation into muscle was consistent with rates predicted by this equation. Our findings provide new insight into isotopic discrimination factors and incorporation rates in invertebrates with the former showing a different trend than what is commonly observed in other animals.

  11. Using cosmogenic isotopes to measure basin-scale rates of erosion

    International Nuclear Information System (INIS)

    Bierman, P.R.; Steig, E.

    1992-01-01

    The authors present a new and different approach to interpreting the abundance of in situ-produced cosmogenic nuclides such as 36 Cl, 26 Al, and 10 Be. Unlike most existing models, which are appropriate for evaluating isotope concentrations on bedrock surfaces, this model can be used to interpret isotope concentration in fluvial sediment. Because sediment is a mixture of material derived from the entire drainage basin, measured isotope abundances can be used to estimate spatially-averaged rates of erosion and sediment transport. Their approach has the potential to provide geomorphologists with a relatively simple but powerful means by which to constrain rates of landscape evolution. The model considers the flux of cosmogenic isotopes into and out of various reservoirs. Implicit in model development are the assumptions that a geomorphic steady-state has been reached and that sampled sediment is spatially and temporally representative of all sediment leaving the basin. Each year, the impinging cosmic-ray flux produces a certain quantity of cosmogenic isotopes in the rock and soil of a drainage basin. For a basin in steady state, the outgoing isotope flux is also constant. They solve for the rate of mass loss as a function of isotope abundance in the sediment, the cosmic ray attenuation length, the isotope half life, and the effective isotope production rate. There are only a few published measurements of cosmogenic isotope abundance in sediment. They calculated model denudation rates for sediment samples from Zaire and central Texas. The denudation rates they calculated appear reasonable and are similar to those they have measured directly on granite landforms in Georgia and southeastern California and those calculated for the Appalachian Piedmont

  12. Experimental study of relationship between average isotopic fractionation factor and evaporation rate

    Directory of Open Access Journals (Sweden)

    Tao Wang

    2010-12-01

    Full Text Available Isotopic fractionation is the basis of tracing the water cycle using hydrogen and oxygen isotopes. Isotopic fractionation factors in water evaporating from free water bodies are mainly affected by temperature and relative humidity, and vary significantly with these atmospheric factors over the course of a day. The evaporation rate (E can reveal the effects of atmospheric factors. Therefore, there should be a certain functional relationship between isotopic fractionation factors and E. An average isotopic fractionation factor (α* was defined to describe isotopic differences between vapor and liquid phases in evaporation with time intervals of days. The relationship between α* and E based on the isotopic mass balance was investigated through an evaporation pan experiment with no inflow. The experimental results showed that the isotopic compositions of residual water were more enriched with time; α* was affected by air temperature, relative humidity, and other atmospheric factors, and had a strong functional relation with E. The values of α* can be easily calculated with the known values of E, the initial volume of water in the pan, and isotopic compositions of residual water.

  13. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  14. The effect of temperature, salinity and growth rate on the stable hydrogen isotopic composition of long chain alkenones produced by Emiliania huxleyi and Gephyrocapsa oceanica

    Directory of Open Access Journals (Sweden)

    S. Schouten

    2006-01-01

    Full Text Available Two haptophyte algae, Emiliania huxleyi and Gephyrocapsa oceanica, were cultured at different temperatures and salinities to investigate the impact of these factors on the hydrogen isotopic composition of long chain alkenones synthesized by these algae. Results showed that alkenones synthesized by G. oceanica were on average depleted in D by 30 compared to those of E. huxleyi when grown under similar temperature and salinity conditions. The fractionation factor, αalkenones-H2O, ranged from 0.760 to 0.815 for E. huxleyi and from 0.741 to 0.788 for G. oceanica. There was no significant correlation of αalkenones-H2O with temperature but a positive linear correlation was observed between αalkenones-H2O and salinity with ~3 change in fractionation per salinity unit and a negative correlation between αalkenones-H2O and growth rate. This suggests that both salinity and growth rate can have a substantial impact on the stable hydrogen isotopic composition of long chain alkenones in natural environments.

  15. Estimation of evapotranspiration rate in irrigated lands using stable isotopes

    Science.gov (United States)

    Umirzakov, Gulomjon; Windhorst, David; Forkutsa, Irina; Brauer, Lutz; Frede, Hans-Georg

    2013-04-01

    Agriculture in the Aral Sea basin is the main consumer of water resources and due to the current agricultural management practices inefficient water usage causes huge losses of freshwater resources. There is huge potential to save water resources in order to reach a more efficient water use in irrigated areas. Therefore, research is required to reveal the mechanisms of hydrological fluxes in irrigated areas. This paper focuses on estimation of evapotranspiration which is one of the crucial components in the water balance of irrigated lands. Our main objective is to estimate the rate of evapotranspiration on irrigated lands and partitioning of evaporation into transpiration using stable isotopes measurements. Experiments has done in 2 different soil types (sandy and sandy loam) irrigated areas in Ferghana Valley (Uzbekistan). Soil samples were collected during the vegetation period. The soil water from these samples was extracted via a cryogenic extraction method and analyzed for the isotopic ratio of the water isotopes (2H and 18O) based on a laser spectroscopy method (DLT 100, Los Gatos USA). Evapotranspiration rates were estimated with Isotope Mass Balance method. The results of evapotranspiration obtained using isotope mass balance method is compared with the results of Catchment Modeling Framework -1D model results which has done in the same area and the same time.

  16. Vadose Zone Infiltration Rates from Sr isotope Measurements

    Science.gov (United States)

    Maher, K.; Maher, K.; DePaolo, D. J.; DePaolo, D. J.; Conrad, M.

    2001-12-01

    Predicting infiltration rates and recharge through the vadose zone in arid regions is difficult and hence developing methods for the measurement of infiltration rates is important. We have been investigating the use of Sr isotope measurements for determining infiltration at the 200 Area plateau on the Hanford reservation in central Washington. In this context, infiltration affects the transport of contaminants to the water table as well as recharge of the groundwater system. Using Sr isotopes for this purpose requires drill core and water samples from the vadose zone, although leaches of the cores can substitute for water samples. Complementary information, including some constraints on regional recharge, can also be obtained using water samples from groundwater monitoring wells. The VZ method is based on the fact that the Sr isotope ratio of soil water just below the surface is often set by dissolution of aeolian material including carbonate, and this ratio is different from the average value in the deeper underlying vadose zone rock matrix. As water infiltrates, the Sr isotopic composition of the water changes toward the rock values as a result of Sr released from the rocks by weathering reactions. The rate of change with depth of the Sr isotope ratio of the vadose zone water is a function ultimately of q/R; the ratio of the infiltration flux (q) to the bulk rock weathering rate (R). Where it is possible to evaluate R, q can be estimated. As data accumulate it may be possible to improve the calibration of the method. At Hanford the vadose zone rock material is mostly unconsolidated sand, silt, and gravel of broadly granitic composition, which constitute the Hanford and Ringold formations. Annual precipitation is about 160 mm/yr. Drilling and coring of a ca. 70m hole to the water table in 1999 as part of the Hanford groundwater monitoring program, in a relatively undisturbed area of the site, allowed us to generate a unique Sr isotope data set. The Sr isotope

  17. Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

    International Nuclear Information System (INIS)

    Uda, Tatsuhiko

    1992-01-01

    Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

  18. Equilibrium deuterium isotope effect of surprising magnitude

    International Nuclear Information System (INIS)

    Goldstein, M.J.; Pressman, E.J.

    1981-01-01

    Seemingly large deuterium isotope effects are reported for the preference of deuterium for the α-chloro site to the bridgehead or to the vinyl site in samples of anti-7-chlorobicyclo[4.3.2]undecatetraene-d 1 . Studies of molecular models did not provide a basis for these large equilibrium deuterium isotope effects. The possibility is proposed that these isotope effects only appear to be large for want of comparison with isotope effects measured for molecules that might provide even greater contrasts in local force fields

  19. Isotope effect in gamma-radiolysis of absorbed ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Lyapina, T G; Kotov, A G [Nauchno-Issledovatel' skij Fiziko-Khimicheskij Inst., Moscow (USSR)

    1975-07-01

    The radiolysis of NH/sub 3/ of various isotopic compounds adsorbed on silica gel or zeolite at 77degK was studied. Experimental data were treated using the kinetic equation dR/dt=GI-kIR where R=radical concentration, G=radical yield, k=radical termination constant and I=radiation dose rate. Both the values of G and R for NH/sub 3/ adsorbed on silica gel are affected by the isotopic effect of /sup 15/N, but not on zeolite. The isotopic effect is explained by the influence of protonated acidity of the silica gel surface.

  20. Glutathione reductase: solvent equilibrium and kinetic isotope effects

    International Nuclear Information System (INIS)

    Wong, K.K.; Vanoni, M.A.; Blanchard, J.S.

    1988-01-01

    Glutathione reductase catalyzes the NADPH-dependent reduction of oxidized glutathione (GSSG). The kinetic mechanism is ping-pong, and we have investigated the rate-limiting nature of proton-transfer steps in the reactions catalyzed by the spinach, yeast, and human erythrocyte glutathione reductases using a combination of alternate substrate and solvent kinetic isotope effects. With NADPH or GSSG as the variable substrate, at a fixed, saturating concentration of the other substrate, solvent kinetic isotope effects were observed on V but not V/K. Plots of Vm vs mole fraction of D 2 O (proton inventories) were linear in both cases for the yeast, spinach, and human erythrocyte enzymes. When solvent kinetic isotope effect studies were performed with DTNB instead of GSSG as an alternate substrate, a solvent kinetic isotope effect of 1.0 was observed. Solvent kinetic isotope effect measurements were also performed on the asymmetric disulfides GSSNB and GSSNP by using human erythrocyte glutathione reductase. The Km values for GSSNB and GSSNP were 70 microM and 13 microM, respectively, and V values were 62 and 57% of the one calculated for GSSG, respectively. Both of these substrates yield solvent kinetic isotope effects greater than 1.0 on both V and V/K and linear proton inventories, indicating that a single proton-transfer step is still rate limiting. These data are discussed in relationship to the chemical mechanism of GSSG reduction and the identity of the proton-transfer step whose rate is sensitive to solvent isotopic composition. Finally, the solvent equilibrium isotope effect measured with yeast glutathione reductase is 4.98, which allows us to calculate a fractionation factor for the thiol moiety of GSH of 0.456

  1. Salars evaporation rates evaluation using isotope techniques, Bellavista Salar, Chile

    International Nuclear Information System (INIS)

    Grilli, A.; Ortiz, J.

    1989-01-01

    Long term evaporation rates are evaluated in different soil conditions at Bellavista Salar, using environmental isotope profiles (oxygen-18) of the unsaturated soil zone. The Barnes and Allison model was adapted to stratified soils under non-saturation conditions and for a non-isothermal permanent regime. To apply the proposed model, field data of the different variables were used and the evaporation rates were obtained adjunting the δ 18 O values generated by the model to those experimentally measured in the water extracted from the soil profile of the unsaturated soil zone. (author). 13 refs, 8 figs

  2. Predicting rates of isotopic turnover across the animal kingdom: a synthesis of existing data.

    Science.gov (United States)

    Thomas, Stephen M; Crowther, Thomas W

    2015-05-01

    The stable isotopes of carbon ((12)C, (13)C) and nitrogen ((14)N, (15)N) represent powerful tools in food web ecology, providing a wide range of dietary information in animal consumers. However, identifying the temporal window over which a consumer's isotopic signature reflects its diet requires an understanding of elemental incorporation, a process that varies from days to years across species and tissue types. Though theory predicts body size and temperature are likely to control incorporation rates, this has not been tested empirically across a morphologically and phylogenetically diverse range of taxa. Readily available estimates of this relationship would, however, aid in the design of stable isotope food web investigations and improve the interpretation of isotopic data collected from natural systems. Using literature-derived turnover estimates from animal species ranging in size from 1 mg to 2000 kg, we develop a predictive tool for stable isotope ecologists, allowing for estimation of incorporation rates in the structural tissues of entirely novel taxa. In keeping with metabolic scaling theory, we show that isotopic turnover rates of carbon and nitrogen in whole organisms and muscle tissue scale allometrically with body mass raised approximately to the power -0.19, an effect modulated by body temperature. This relationship did not, however, apply to incorporation rates in splanchnic tissues, which were instead dependent on the thermoregulation tactic employed by an organism, being considerably faster in endotherms than ectotherms. We believe the predictive turnover equations we provide can improve the design of experiments and interpretation of results obtained in future stable isotopic food web studies. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.

  3. Medium Effects in Reactions with Rare Isotopes

    International Nuclear Information System (INIS)

    Bertulani, C A; Karakoç, M

    2012-01-01

    We discuss medium effects in knockout reactions with rare isotopes of weakly-bound nuclei at intermediate energies. We show that the poorly known corrections may lead to sizable modifications of knockout cross sections and momentum dsitributions.

  4. Separation of rate processes for isotopic exchange between hydrogen and liquid water in packed columns 10

    International Nuclear Information System (INIS)

    Butler, J.P.; Hartog, J. den; Goodale, J.W.; Rolston, J.H.

    1977-01-01

    Wetproofed platinum catalysts in packed columns promote isotopic exchange between counter-current streams of hydrogen saturated with water vapour and liquid water. The net rate of deuterium transfer from isotopically enriched hydrogen has been measured and separated into two rate processes involving the transfer of deuterium from hydrogen to water vapour and from water vapour to liquid. These are compared with independent measurements of the two rate processes to test the two-step successive exchange model for trickle bed reactors. The separated transfer rates are independent of bed height and characterize the deuterium concentrations of each stream along the length of the bed. The dependences of the transfer rates upon hydrogen and liquid flow, hydrogen pressure, platinum loading and the effect of dilution of the hydrophobic catalyst with inert hydrophilic packing are reported. The results indicate a third process may be important in the transfer of deuterium between hydrogen and liquid water. (author)

  5. Calculation of turnover rates in stable-isotope studies

    International Nuclear Information System (INIS)

    Wootton, R.; Ford, G.C.; Cheng, K.N.; Halliday, D.

    1985-01-01

    In a comparison of glucose turnover measured with 2 H-glucose and with 13 C-glucose Tserng and Kalhan used five apparently different equations and obtained conflicting answers. There is, however, no difference in principle between the use of a stable isotope as a tracer and the use of a radioactive isotope, and the rate of appearance of tracee in a steady-state system (the turnover) can therefore be shown to be proportional to the equilibrium dilution of the infused tracer. Because the sensitivity of measurement of this dilution made using a gas chromatograph-mass spectrometer is lower than that made by radioactivity measurement, the contribution to the measured turnover rate due to the infusate cannot be neglected, as it usually is in radioisotope work. A convenient calibration curve to establish this dilution is the mole ratio of the pure infusate against the area ratio for the relevant ions. Tserng and Kalhan's apparently conflicting results for glucose-turnover using 13 C-glucose as the tracer can all be shown to amount to approximately 11.6 μmol min -1 kg -1 . This value is only slightly lower (0.05 2 H-glucose as the tracer and supports the use of 13 C-glucose as an alternative. (author)

  6. Bibliography on vapour pressure isotope effects

    International Nuclear Information System (INIS)

    Illy, H.; Jancso, G.

    1976-03-01

    The bibliography of research on vapour pressure isotope effects from 1919 to December 1975 is presented in chronological order. Within each year the references are listed alphabetically according to the name of the first author of each work. The bibliography is followed by a Compound Index containing the names o compounds, but the type of isotopic substituation is not shown. The Author Index includes all authors of the papers. (Sz.N.Z.)

  7. Effect of different rates of potassium fertilizer on nitrogen use efficiency and cotton yield using an 15N isotopic dilution technique

    International Nuclear Information System (INIS)

    Khalifa, Kh.; Al-Chamma'a, M.; Al-Ain, F.

    2005-03-01

    A field study was carried out during the 2003 growing season on a loamy to sandy clay loamy soil, located at the Lower Euphrate's Valley, 15 km southeast of Deir - Ezzor city to evaluate the effect of K fertilizer on nitrogen , potassium use efficiency and cotton yield. Three nitrogen ( N1 =120, N2 =180, and N3 = 240 kg N / ha ) and four potassium application rates ( K0 = 0 , K1 = 50, K2 = 100, K3 = 150 kg K2O / ha ) were employed. The cotton variety was Deir 22 sown on April 2003 at a spacing of 70 cm between rows and 20 cm between pits with 5 seeds per pit. The plants were thinned to 2 plants per pit 4 weeks after planting. Representative samples of aboveground portions of cotton plants were harvested from labeled subplots at 108 and 161 days after planting . Dry matter weight , N uptake, N fertilizer yield, N use efficiency, K use efficiency, seed cotton yield, earliness, leaf area, number of bolls / plant, and number of branches / plant were evaluated. The results showed that seed cotton yield increased with increasing K levels applied under each rate of N ( except N120 ). The highest seed cotton yield was obtained with the combined treatment N3K1 ( 6442 kg/ha ). This treatment gave also the optimum potassium use efficiency ( 42 % ). Nitrogen use efficiency (at 180 days of harvest ) increased with the increasing K application rate. Nitrogen use efficiency (NUE) was decreased with increasing N rates . Increasing K application rate ( KUE ) decreased potassium use efficiency. A maximum N use efficiency ( 98% ) was obtained for combined treatment N2 K3. Also the results indicated that dry matter weight and N uptake increased with increasing K rates applied. Nitrogen derived from fertilizer (Ndff ) was higher in combined treatments than the control treatments (K0 ). (Authors)

  8. Isotope effects of sulfur in chemical reactions

    International Nuclear Information System (INIS)

    Mikolajczuk, A.

    1999-01-01

    Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

  9. Kinetic isotope effects and aliphatic diazo-compounds

    International Nuclear Information System (INIS)

    Albery, W.J.; Conway, C.W.; Hall, J.A.

    1976-01-01

    Results are reported for the variation of the rate of decomposition of ethyl diazomalonate (EDM) and diazomalonate anions with pH and for the deuterium solvent isotope effect for EDM. The shape of the pH profile is explained by successive protonations of the anions. Ethyl diazoacetate is observed as an intermediate in the decomposition of EDM. The degree of proton transfer in the EDM transition state is deduced from the solvent isotope effect and the results together with those for other aliphatic diazo-compounds are discussed in terms of the Marcus theory. (author)

  10. Isotope effects in pericyclic reactions, ch. 2

    International Nuclear Information System (INIS)

    Dolbier, W.R. Jr.

    1975-01-01

    A distinction is made between primary and secondary isotope effects, the primary ones being based on the relative large vibrational frequencies and ensuing large zeroprint energies for C-H vibrations whereas the secondary effects are observed in systems where the vibrational modes of the isotopically labelled site are perturbed during transformation from reactant to product. Both effects are utilised in the elucidation of mechanism in pericyclic processes. The main processes dealt with in this chapter are cycloadditions of all types and sigmatropic rearrangements

  11. Secondary isotope effects on alpha-cleavage reactions

    International Nuclear Information System (INIS)

    Ingemann, S.; Hammerum, S.

    1980-01-01

    Kinetic deuterium isotope effects on mass spectral reactions have in several instances been utilized to provide structural information and to answer mechanistic questions. Typically, the influence of the deuterium label on the rate of one of a number of competing reactions has been studied. Secondary isotope effects have usually been assumed to be relatively insignificant in comparison with the observed kinetic effects, even though various workers have shown that secondary isotope effects may indeed exert a considerable influence on the rates of competing simple cleavages. Recent studies have provided quantitative data to show that the mere presence of deuterium atoms up to six bonds away may influence the rate of a simple cleavage reaction. In relation to an investigation of rearrangements accompanying simple cleavage reactions, a semi-quantitative measure was needed of the variation of the secondary isotope effect with the number of bonds between the deuterium label and the point of rupture. The influence has therefore been examined of the presence of remote deuterium atoms on a typical simple cleavage reaction, the α-cleavage of aliphatic amines. As a model compound, N-methyldipentylamine was chosen, systematically labelled with deuterium. (author)

  12. Metallicity-Dependent Isotopic Abundances and the Impact of Helium Rate Uncertainties in Massive Stars

    Science.gov (United States)

    West, Christopher

    2013-03-01

    model compared to the linear interpolation method, for the six s--only isotopes along the weak s--process path. As a second project, we study the sensitivity of presupernova evolution and supernova nucleosynthesis yields of massive stars to variations of the helium-burning reaction rates within the range of their uncertainties. The current solar abundances from Lodders (2010) are used for the initial stellar composition. We compute a grid of 12 initial stellar masses and 176 models per stellar mass to explore the effects of independently varying the 12C(alpha,gamma)16O and 3alpha reaction rates, denoted Ralpha,12 and R3alpha, respectively. The production factors of both the intermediate-mass elements (A=16--40) and the s--only isotopes along the weak s--process path ( 70Ge, 76Se, 80Kr, 82Kr, 86Sr, and 87Sr) were found to be in reasonable agreement with predictions for variations of R3alpha and Ralpha,12 of +/-25%; the s--only isotopes, however, tend to favor higher values of R3alpha than the intermediate-mass isotopes. The experimental uncertainty (one standard deviation) in R3alpha(Ralpha,12 ) is approximately +/-10%(+/-25%). The results show that a more accurate measurement of one of these rates would decrease the uncertainty in the other as inferred from the present calculations. We also observe sharp changes in production factors and standard deviations for small changes in the reaction rates, due to differences in the convection structure of the star. The compactness parameter was used to assess which models would likely explode as successful supernovae, and hence contribute explosive nucleosynthesis yields. We also provide the approximate remnant masses for each model and the carbon mass fractions at the end of core-helium burning as a key parameter for later evolution stages.

  13. On the Effect of Planetary Stable Isotope Compositions on Growth and Survival of Terrestrial Organisms.

    Directory of Open Access Journals (Sweden)

    Xueshu Xie

    Full Text Available Isotopic compositions of reactants affect the rates of chemical and biochemical reactions. Usually it is assumed that heavy stable isotope enrichment leads to progressively slower reactions. Yet the effect of stable isotopes may be nonlinear, as exemplified by the "isotopic resonance" phenomenon. Since the isotopic compositions of other planets of Solar system, including Mars and Venus, are markedly different from terrestrial (e.g., deuterium content is ≈5 and ≈100 times higher, respectively, it is far from certain that terrestrial life will thrive in these isotopic conditions. Here we found that Martian deuterium content negatively affected survival of shrimp in semi-closed biosphere on a year-long time scale. Moreover, the bacterium Escherichia coli grows slower at Martian isotopic compositions and even slower at Venus's compositions. Thus, the biological impact of varying stable isotope compositions needs to be taken into account when planning interplanetary missions.

  14. Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

    Science.gov (United States)

    Matsu'Ura, F.

    2009-12-01

    Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase

  15. High permeation rates in liposome systems explain rapid glyphosate biodegradation associated with strong isotope fractionation.

    Science.gov (United States)

    Ehrl, Benno; Mogusu, Emmanuel O; Kim, Kyoungtea; Hofstetter, Heike; Pedersen, Joel A; Elsner, Martin

    2018-05-23

    Bacterial uptake of charged organic pollutants such as the widely used herbicide glyphosate is typically attributed to active transporters, whereas passive membrane permeation as an uptake pathway is usually neglected. For 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomes, pH-dependent membrane permeation coefficients (Papp) of glyphosate, determined by nuclear magnetic resonance (NMR) spectroscopy, varied from Papp(pH 7.0) = 3.7 (+/-0.3) × 10-7 m∙s-1 to Papp(pH 4.1) = 4.2 (+/-0.1) × 10-6 m∙s-1. This surprisingly rapid membrane permeation depended on glyphosate speciation and was, at physiological pH, in the range of polar, non-charged molecules suggesting that passive membrane permeation is a potential uptake pathway during glyphosate biodegradation. To test this hypothesis, a Gram-negative glyphosate degrader, Ochrobactrum sp. FrEM, was isolated from glyphosate-treated soil and glyphosate permeation rates inferred from the liposome model were compared to bacterial degradation rates. Estimated maximum permeation rates were, indeed, two orders of magnitudes higher than glyphosate degradation rates. Moreover, biodegradation of millimolar glyphosate concentrations gave rise to pronounced carbon isotope fractionation with an apparent kinetic isotope effect of AKIEcarbon= 1.014 ± 0.003. This value is consistent with unmasked enzymatic isotope fractionation demonstrating that glyphosate biodegradation was little mass transfer-limited and glyphosate exchange across the cell membrane was rapid relative to enzymatic turnover.

  16. Rate of Isotope Exchange Reaction Between Tritiated Water in a Gas Phase and Water on the Surface of Piping Materials

    International Nuclear Information System (INIS)

    Nakashio, Nobuyuki; Yamaguchi, Junya; Kobayashi, Ryusuke; Nishikawa, Masabumi

    2001-01-01

    The system effect of tritium arises from the interaction of tritium in the gas phase with water on the surface of piping materials. It has been reported that the system effect can be quantified by applying the serial reactor model to the piping system and that adsorption and isotope exchange reactions play the main roles in the trapping of tritium. The isotope exchange reaction that occurs when the chemical form of tritium in the gas phase is in the molecular form, i.e., HT or T 2 , has been named isotope exchange reaction 1, and that which occurs when tritium in the gas phase is in water form, i.e., HTO or T 2 O, has been named isotope exchange reaction 2.The rate of isotope exchange reaction 2 is experimentally quantified, and the rate is observed to be about one-third of the rate of adsorption. The trapping and release behavior of tritium from the piping surface due to isotope exchange reaction 2 is also discussed. It is certified that swamping of water vapor to process gas is effective to release tritium from the surface contaminated with tritium

  17. Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

    Science.gov (United States)

    Fitzpatrick, Paul F.

    2014-01-01

    Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

  18. Modification of the isotope effect due to pair breaking

    International Nuclear Information System (INIS)

    Carbotte, J.P.; Greeson, M.; Perez-Gonzalez, A.

    1991-01-01

    We have calculated the effect of pair breaking on the isotope-effect coefficient (β) of a superconductor. We find that, as the pair-breaking scattering rate is increased, β also increases in absolute value. Values of β much larger than the canonical value of 1/2 can easily be achieved even in models where the electron-phonon interaction contributes only a very small amount to the value of the intrinsic critical temperature

  19. Effect of different rates of potassium fertilizer and soil moisture on nitrogen and potassium use efficiencies and tomato yield using an 15N isotopic dilution technique

    International Nuclear Information System (INIS)

    Khalifa, Kh.; Al-Ain, F.; Al-Chamma'a, M.

    2005-03-01

    A pot experiment was conducted to evaluate the response of tomato to 4 potassium rates (0, 90, 120, 150 kg K 2 O/ha), one rate of N (150 kg/ha) and two irrigation regimes 65 % and 85 % of field capacity (FC) on yield and the efficient use of N and K fertilizers. Results showed that dry matter yield was positively correlated with the rate of K fertilizer applied under the two irrigation regimes. However the increase in production of fruits and dry matter was higher at the 85% FC. The K-uptake in fruit and whole plant increased with increasing K application levels and was higher at the 85 % but the opposite was observed in shoots and roots. Potassium use efficiency increased with increasing K levels at the two irrigation regimes and the values were higher at the 85 %. The nitrogen use efficiency in shoots, roots , fruits and the whole plant increased with increasing K levels and was highest at the 85 % FC and 150 kg K 2 O/ ha fertilizer rate. (Authors)

  20. Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.; Kasprzyk, G.; Gumolka, L.; Staedter, W.

    1993-01-01

    The 13 C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphoric acids (PA) and by 85% H 3 PO 4 has been studied in the temperature interval of 60-150 deg C. The values of the 13 C (1) isotope effects in the decarbonylation of lactic acid in 100% H 3 PO 4 , in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C (1)- OH bond is broken in the rate-controlling step of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90-130 deg C the experimental 13 C fractionation factors determined in concentrated PA approach quite closely the 13 C fractionation corresponding to C (2)- C (1) bond scission. The 13 C (1) kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110-150 deg C coincide with the 13 C isotope effects calculated assuming that the frequency corresponding to the C (1) -OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H 3 PO 4 has been suggested. A possible secondary 18 O and a primary 18 O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too. (author) 21 refs.; 3 tabs

  1. H/D isotope effects in high temperature proton conductors

    DEFF Research Database (Denmark)

    Bonanos, Nikolaos; Huijser, A.; Poulsen, Finn Willy

    2015-01-01

    The atomic mass ratio of ca. 2 between deuterium and hydrogen is the highest for any pair of stable isotopes and results in significant and measurable H/D isotope effects in high temperature proton conductors containing these species. This paper discusses H/D isotope effects manifested in O-H/O-D...

  2. Isotope effect on confinement in DT plasmas

    International Nuclear Information System (INIS)

    Fukuyama, A.; Itoh, K.; Itoh, S.; Yagi, M.; Azumi, M.

    1994-03-01

    Isotope effect on the energy confinement time is discussed for the DT plasma. The transport theory which is based on the ballooning mode turbulence is applied. When the DT plasma is produced under the condition of β p >1, the energy confinement time of DT plasma (50% mixture) is expected to be about 1.2 times better than the D plasma with the same operation condition. (author)

  3. Hydrogen exchange rate of tyrosine hydroxyl groups in proteins as studied by the deuterium isotope effect on C(zeta) chemical shifts.

    Science.gov (United States)

    Takeda, Mitsuhiro; Jee, Jungoo; Ono, Akira Mei; Terauchi, Tsutomu; Kainosho, Masatsune

    2009-12-30

    We describe a new NMR method for monitoring the individual hydrogen exchange rates of the hydroxyl groups of tyrosine (Tyr) residues in proteins. The method utilizes (2S,3R)-[beta(2),epsilon(1,2)-(2)H(3);0,alpha,beta,zeta-(13)C(4);(15)N]-Tyr, zeta-SAIL Tyr, to detect and assign the (13)C(zeta) signals of Tyr rings efficiently, either by indirect (1)H-detection through 7-8 Hz (1)H(delta)-(13)C(zeta) spin couplings or by direct (13)C(zeta) observation. A comparison of the (13)C(zeta) chemical shifts of three Tyr residues of an 18.2 kDa protein, EPPIb, dissolved in H(2)O and D(2)O, revealed that all three (13)C(zeta) signals in D(2)O appeared at approximately 0.13 ppm ( approximately 20 Hz at 150.9 MHz) higher than those in H(2)O. In a H(2)O/D(2)O (1:1) mixture, however, one of the three signals for (13)C(zeta) appeared as a single peak at the averaged chemical shifts, and the other two appeared as double peaks at exactly the same chemical shifts in H(2)O and D(2)O, in 50 mM phosphate buffer (pH 6.6) at 40 degrees C. These three peaks were assigned to Tyr-36, Tyr-120, and Tyr-30, from the lower to higher chemical shifts, respectively. The results indicate that the hydroxyl proton of Tyr-120 exchanges faster than a few milliseconds, whereas those of Tyr-30 and Tyr-36 exchange more slowly. The exchange rate of the Tyr-30 hydroxyl proton, k(ex), under these conditions was determined by (13)C NMR exchange spectroscopy (EXSY) to be 9.2 +/- 1.1 s(-1). The Tyr-36 hydroxyl proton, however, exchanges too slowly to be determined by EXSY. These profound differences among the hydroxyl proton exchange rates are closely related to their relative solvent accessibility and the hydrogen bonds associated with the Tyr hydroxyl groups in proteins.

  4. Comparative evaluation of quantitative glomerular filtration rate measured by isotopic and nonisotopic methods

    International Nuclear Information System (INIS)

    Balachandran, S.; Toguri, A.G.; Petrusick, T.W.; Abbott, L.C.

    1981-01-01

    Good correlation of glomerular filtration rate (GFR) measured isotopically from plasma disappearance of Tc-99m-DTPA (Sn) was shown with inulin clearance, creatinine clearance, and graded radionuclide imaging. The isotopic GFR is a simple, urineless technique not requiring continuous infusion that enables one to perform simultaneous renal imaging with one radiotracer

  5. Characterization of a facility for the measurement of fission fragment transport effects: experimental determination of the fission rates for fissile and fissionable isotopes

    International Nuclear Information System (INIS)

    Benetti, P.; Raselli, G.L.; Tigliole, A. Borio di; Cagnazzo, M.; Cesana, A.; Mongelli, S.; Terrani, M.

    2002-01-01

    The transfer facility of the LENA laboratory allows the direct neutron irradiation of fissionable material in the D channel of the TRIGA reactor. A test measurement carried out with a ionization chamber and a 239 Pu sample shows the possibility to use this tool for the study of the transport effects of the fission fragment emerging from thin layers of fissile materials. (author)

  6. Magnetic field and magnetic isotope effects on photochemical reactions

    International Nuclear Information System (INIS)

    Wakasa, Masanobu

    1999-01-01

    By at present exact experiments and the theoretical analysis, it was clear that the magnetic field less than 2 T affected a radical pair reaction and biradical reaction. The radical pair life and the dissipative radical yield showed the magnetic field effects on chemical reactions. The radical pair mechanism and the triplet mechanism were known as the mechanism of magnetic field effects. The radical pair mechanism consists of four mechanisms such as the homogeneous hyperfine interaction (HFC), the delta-g mechanism, the relaxation mechanism and the level cross mechanism. In order to observe the magnetic effects of the radical pair mechanism, two conditions need, namely, the recombination rate of singlet radical pair > the dissipation rate and the spin exchange rate > the dissipation rate. A nanosecond laser photo-decomposition equipment can observe the magnetic field effects. The inversion phenomena of magnetic field effect, isolation of the relaxation mechanism and the delta-g mechanism, the magnetic field effect of heavy metal radical reaction, the magnetic field effect in homogeneous solvent, saturation of delta-g mechanism are explained. The succeeded examples of isotope concentration by the magnetic isotope effect are 17 O, 19 Si, 33 S, 73 Ge and 235 U. (S.Y.)

  7. Recent trends in accumulation rate, elemental and isotopic ...

    African Journals Online (AJOL)

    The isotope results show that the organic material deposited in the bay are generally derived from C4 type of plants and are not transported far from the river mouth. Also the results show that preservation of organic matter is high in open water probably due to high primary productivity owing to high concentration of nutrients ...

  8. Oxygen isotope exchange rate between dissolved sulfate and water at hydrothermal temperatures

    International Nuclear Information System (INIS)

    Chiba, H.; Sakai, H.

    1985-01-01

    Oxygen isotope exchange rate between dissolved sulfate and water was experimentally determined at 100, 200 and 300 deg C. The isotope exchange rate is strongly dependent on temperature and pH of the solution. Combining the temperature and pH dependence of the reaction rate, the exchange reaction was estimated to be first-order with respect to sulfate. The logarithm of apparent rate constant of exchange reaction at a given temperature is a function of the pH calculated at the experimental temperatures. From the pH dependence of the apparent rate constant, it was deduced that the isotope exchange reaction between dissolved sulfate and water proceeds through collision between H 2 SO 4 0 and H 2 O at low pH, and between HSO 4 - and H 2 O at intermediate pH. The isotope exchange rate obtained indicates that oxygen isotope geothermometry utilizing the studied isotope exchange is suitable for temperature estimation of geothermal reservoirs. The extrapolated half-life of this reaction to oceanic temperature is about 10 9 years, implying that exchange between oceanic sulfate and water cannot control the oxygen isotope ratio of oceanic sulfates. (author)

  9. Non - Adiabaticity and Novel Isotope Effect in the Doped Cuprates

    International Nuclear Information System (INIS)

    Kresin, V.; WOLF, S. A.

    1995-01-01

    This paper reports a novel isotope effect which is due to a strong non-adiabaticity that manifests itself in the dependence of the carrier concentration on the isotopic mass. The critical temperature in turn depends on the carrier concentration giving rise to a unique and non-phononic isotope shift. (author)

  10. Isotope and multiband effects in layered superconductors.

    Science.gov (United States)

    Bussmann-Holder, Annette; Keller, Hugo

    2012-06-13

    In this review we consider three classes of superconductors, namely cuprate superconductors, MgB(2) and the new Fe based superconductors. All of these three systems are layered materials and multiband compounds. Their pairing mechanisms are under discussion with the exception of MgB(2), which is widely accepted to be a 'conventional' electron-phonon interaction mediated superconductor, but extending the Bardeen-Cooper-Schrieffer (BCS) theory to account for multiband effects. Cuprates and Fe based superconductors have higher superconducting transition temperatures and more complex structures. Superconductivity is doping dependent in these material classes unlike in MgB(2) which, as a pure compound, has the highest values of T(c) and a rapid suppression of superconductivity with doping takes place. In all three material classes isotope effects have been observed, including exotic ones in the cuprates, and controversial ones in the Fe based materials. Before the area of high-temperature superconductivity, isotope effects on T(c) were the signature for phonon mediated superconductivity-even when deviations from the BCS value to smaller values were observed. Since the discovery of high T(c) materials this is no longer evident since competing mechanisms might exist and other mediating pairing interactions are discussed which are of purely electronic origin. In this work we will compare the three different material classes and especially discuss the experimentally observed isotope effects of all three systems and present a rather general analysis of them. Furthermore, we will concentrate on multiband signatures which are not generally accepted in cuprates even though they are manifest in various experiments, the evidence for those in MgB(2), and indications for them in the Fe based compounds. Mostly we will consider experimental data, but when possible also discuss theoretical models which are suited to explain the data.

  11. Rate of germanium-isotope production by background processes in the SAGE experiment

    International Nuclear Information System (INIS)

    Gavrin, V.N.; Gorbachev, V.V.; Ibragimova, T.V.; Cleveland, B.T.

    2002-01-01

    Data on a direct determination of systematic uncertainties caused by the background production of germanium isotopes in the radiochemical SAGE experiment measuring the solar-neutrino flux are analyzed. The result obtained for the rate of 68 Ge production is 6.5(1±1.0) times greater than the expected one; the rate of 69 Ge production does not exceed preliminary estimates. The above result for 68 Ge corresponds to the systematic uncertainty that is caused by the interaction of cosmic-ray muons and which is equal to 5.8% (4.5 SNU) at a solar-neutrino-capture rate of 77.0 SNU. An experiment is proposed that would test the effect of cosmic-ray muon influence on the SAGE systematic uncertainty and which would be performed at the location of the underground scintillation telescope facilities of the Baksan Neutrino Observatory (Institute for Nuclear Research, Russian Academy of Sciences)

  12. Some considerations of ''cold fusion'' including the calculation of fusion rates in molecules of hydrogen isotopes

    International Nuclear Information System (INIS)

    Cowley, S.C.; Kulsrud, R.M.

    1989-11-01

    We calculate the fusion reaction rates in molecules of hydrogen isotopes. The rates are calculated analytically (for the first time) as an asymptotic expansion in the ratio of the electron mass to the reduced mass of the nucleii. The fusion rates of the P-D, D-D, and D-T reactions are given for a variable electron mass by a simple analytic formula. However, we do not know any mechanism by which a sufficiently localized electron in solid can have an 'effective mass' large enough to explain the result of Fleischman and Pons (FP). This calculation indicates that P-D rates should exceed D-D rates for D-D fusion rates less than approximately 10 -23 per molecule per second. The D-D fusion rate is enhanced by a factor of 10 5 at 10,000 degree K if the excited vibrational states are populated with a Boltzmann distribution and the rotational excitations suppressed. The suggestion that experimental results could be explained by bombardment of cold deuterons by kilovolt deuterons is shown to be an unlikely from an energetic point of view. 12 refs., 3 figs., 1 tab

  13. Mechanistic studies on the bovine liver mitochondrial dihydroorotate dehydrogenase using kinetic deuterium isotope effects

    International Nuclear Information System (INIS)

    Hines, V.; Johnston, M.

    1989-01-01

    Dihydroorotates deuteriated at both C 5 and C 6 have been prepared and used to probe the mechanism of the bovine liver mitochondrial dihydroorotate dehydrogenase. Primary deuterium isotope effects on k cat are observed with both (6RS)-[5(S)- 2 H]- and (6RS)-[6- 2 H]dihydroorotates (3 and 6, respectively); these effects are maximal at low pH. At pH 6.6, D V = 3.4 for the C 5 -deuteriated dihydroorotate (3), and D V = 2.3 for the C 6 -deuteriated compound (6). The isotope effects approach unity at pH 8.8. Analysis of the pH dependence of the isotope effects on k cat reveals a shift in the rate-determining step of the enzyme mechanism as a function of pH. Dihydroorotate oxidation appears to require general base catalysis; this step is completely rate-determining at low pH and isotopically sensitive. Reduction of the cosubstrate, coenzyme Q 6 , is rate-limiting at high pH and is isotopically insensitive; this step appears to require general acid catalysis. The results of double isotope substitution studies and analysis for substrate isotope exchange with solvent point toward a concerted mechanism for oxidation of dihydroorotate. This finding serves to distinguish further the mammalian dehydrogenase from its parasitic cognate, which catalyzes a stepwise oxidation reaction

  14. Kinetic isotope effects and how to describe them

    Directory of Open Access Journals (Sweden)

    Konstantin Karandashev

    2017-11-01

    Full Text Available We review several methods for computing kinetic isotope effects in chemical reactions including semiclassical and quantum instanton theory. These methods describe both the quantization of vibrational modes as well as tunneling and are applied to the ⋅H + H2 and ⋅H + CH4 reactions. The absolute rate constants computed with the semiclassical instanton method both using on-the-fly electronic structure calculations and fitted potential-energy surfaces are also compared directly with exact quantum dynamics results. The error inherent in the instanton approximation is found to be relatively small and similar in magnitude to that introduced by using fitted surfaces. The kinetic isotope effect computed by the quantum instanton is even more accurate, and although it is computationally more expensive, the efficiency can be improved by path-integral acceleration techniques. We also test a simple approach for designing potential-energy surfaces for the example of proton transfer in malonaldehyde. The tunneling splittings are computed, and although they are found to deviate from experimental results, the ratio of the splitting to that of an isotopically substituted form is in much better agreement. We discuss the strengths and limitations of the potential-energy surface and based on our findings suggest ways in which it can be improved.

  15. Estimating blue whale skin isotopic incorporation rates and baleen growth rates: Implications for assessing diet and movement patterns in mysticetes

    Science.gov (United States)

    Busquets-Vass, Geraldine; Newsome, Seth D.; Calambokidis, John; Serra-Valente, Gabriela; Jacobsen, Jeff K.; Aguíñiga-García, Sergio; Gendron, Diane

    2017-01-01

    Stable isotope analysis in mysticete skin and baleen plates has been repeatedly used to assess diet and movement patterns. Accurate interpretation of isotope data depends on understanding isotopic incorporation rates for metabolically active tissues and growth rates for metabolically inert tissues. The aim of this research was to estimate isotopic incorporation rates in blue whale skin and baleen growth rates by using natural gradients in baseline isotope values between oceanic regions. Nitrogen (δ15N) and carbon (δ13C) isotope values of blue whale skin and potential prey were analyzed from three foraging zones (Gulf of California, California Current System, and Costa Rica Dome) in the northeast Pacific from 1996–2015. We also measured δ15N and δ13C values along the lengths of baleen plates collected from six blue whales stranded in the 1980s and 2000s. Skin was separated into three strata: basale, externum, and sloughed skin. A mean (±SD) skin isotopic incorporation rate of 163±91 days was estimated by fitting a generalized additive model of the seasonal trend in δ15N values of skin strata collected in the Gulf of California and the California Current System. A mean (±SD) baleen growth rate of 15.5±2.2 cm y-1 was estimated by using seasonal oscillations in δ15N values from three whales. These oscillations also showed that individual whales have a high fidelity to distinct foraging zones in the northeast Pacific across years. The absence of oscillations in δ15N values of baleen sub-samples from three male whales suggests these individuals remained within a specific zone for several years prior to death. δ13C values of both whale tissues (skin and baleen) and potential prey were not distinct among foraging zones. Our results highlight the importance of considering tissue isotopic incorporation and growth rates when studying migratory mysticetes and provide new insights into the individual movement strategies of blue whales. PMID:28562625

  16. Reaction rates and electrical resistivities of the hydrogen isotopes with, and their solubilities in, liquid lithium

    International Nuclear Information System (INIS)

    Pulham, R.J.; Adams, P.F.; Hubberstey, P.; Parry, G.; Thunder, A.E.

    1976-01-01

    The rate of reaction, k, of hydrogen and of deuterium with liquid lithium have been determined up to pressures of 20kNm -2 and at temperatures between 230 and 270 0 C. The reaction is first order with an apparent activation energy of 52.8 and 55.2 kJmol -1 for hydrogen and deuterium, respectively. The deuterium isotope effect, k/sub H/k/sub D/, decreases from 2.95 at 230 to 2.83 at 270 0 C. Tritium is predicted to react even more slowly than deuterium. The freezing point of lithium is depressed by 0.082 and 0.075 0 C, respectively, by dissolved hydride and deuteride giving eutectics at 0.016 mol percent H and 0.012 mol percent D in the metal-salt phase diagrams. The depression and eutectic concentration are expected to be less for tritium. The increase in the resistivity of liquid lithium caused by dissolved hydrogen isotopes is linear and relatively large, 5 x 10 -8 Ωm (mol percent H or D) -1 . The solubility of lithium hydride and deuteride was determined from the marked change in resistivity on saturation. The liquidus of the metal-salt phase diagram rises steeply from the eutectic point to meet the two-immiscible liquid region. Tritium is expected to be less soluble than deuterium. The partial molar enthalpies of solution are 44.2 and 55.0 kJmol -1 for hydrogen and deuterium, respectively. These values are used to calculate the solvation enthalpies of the isotope anions in the metal

  17. A model of the isotope effect of the oxide superconductor

    International Nuclear Information System (INIS)

    Zhang Liyuan.

    1989-03-01

    In this paper, a possible mechanism of producing negative correlation energy centers is proposed. Combining this electronic attractive potential with phonon mediated attractive potential between carriers the isotope effect exponent of La-Sr-Cu-O system is quantitatively explained. Generally, the isotope effect exponent is smaller than 1/2 in this mechanism. (author). 20 refs, 1 fig

  18. Secondary deuterium isotope effects in the hydrolysis of some acetals

    International Nuclear Information System (INIS)

    Paterson, R.V.

    Secondary α-deuterium kinetic isotope effects have been determined in the hydrolyses of some acetals. Benzaldehyde dimethyl acetal and 2-phenyl-1,3-dioxolan show isotope effects in agreement with an A1 mechanism. 2-Phenyl-4,4,5,5-tetramethyl-1,3-dioxolan, which has been shown to undergo hydrolysis by an A2 type mechanism, has an isotope effect in agreement with participation by water in the transition state. Hydrolysis of benzylidene norbornanediols, although complicated by isomerisation, has an isotope effect in agreement with an A2 mechanism. Kinetic isotope effects in acetals which have a neighbouring carboxyl group have also been determined. Hydrolysis of 2-carboxybenzaldehyde dimethyl acetal in aqueous and 82% w/w dioxan-water buffers has isotope effects in agreement with a large degree of carbonium ion character in the transition state. Anderson and Capon proposed nucleophilic participation in the hydrolysis of this acetal in 82% dioxan-water. The isotope effect determined in this study is not in agreement with this finding. Hydrolysis of 2-(2'-carboxyphenyl)-4,4,5,5-tetramethyl-1,3-dioxolan shows an isotope effect larger than the corresponding dioxolan without the carboxyl group in agreement with some carbonium ion character in the transition state. A new synthesis of a deuterated aldehyde is described which might be general for aldehydes which will not form benzoins readily. (author)

  19. Sodium isotopic exchange rate between crystalline zirconium phosphate and molten NaNO/sub 3/

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Y; Yamada, Y [Tohoku Univ., Sendai (Japan). Faculty of Engineering

    1975-12-01

    The isotopic exchange rate of sodium ion between crystalline zirconium phosphate and molten NaNO/sub 3/ has been measured at 312/sup 0/C and 362/sup 0/C by batch method. The equilibrium was reached within 20 minutes at either temperature, and the rate was very rapid as compared with that of sodium-potassium ion exchange.

  20. Environmental isotope balance of Lake Kinneret as a tool in evaporation rate estimation

    International Nuclear Information System (INIS)

    Lewis, S.

    1979-01-01

    The balance of environmental isotopes in Lake Kinneret has been used to obtain an independent estimate of the mean monthly evaporation rate. Direct calculation was precluded by the inadequacy of the isotope data in uniquely representing the system behaviour throughout the annual cycle. The approach adopted uses an automatic algorithm to seek an objective best fit of the isotope balance model to measured oxygen-18 data by optimizing the evaporation rate as a parameter. To this end, evaporation is described as a periodic function with two parameters. The sensitivity of the evaporation rate estimates to parameter uncertainty and data errors is stressed. Error analysis puts confidence limits on the estimates obtained. Projected improvements in data collection and analysis show that a significant reduction in uncertainty can be realized. Relative to energy balance estimates, currently obtainable data result in about 30% uncertainty. The most optimistic scenario would yield about 15% relative uncertainty. (author)

  1. Isotope effects on the optical spectra of semiconductors

    Science.gov (United States)

    Cardona, Manuel; Thewalt, M. L. W.

    2005-10-01

    Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

  2. recent trends in accumulation rate, elemental and isotopic ...

    African Journals Online (AJOL)

    Furthermore, the mean accumulation rates of organic carbon and nitrogen for the bay, range from 6.92 to 57.25 gC/m2/yr and 0.51 to 4.37 gN/m2/yr, respectively, and show that ... organic compounds (biomarkers) in ... Sampling and analysis.

  3. Great isotope effects in compounding of sodium isotopes by macrocyclic polyether

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1978-01-01

    Isotope effects appear in the compounding of the two sodium isotopes 24 Na + and 22 Na + with macrocyclic polyethers, whose value was determined for the 13 best known polyethers. A radiometric process was used for determining the different half life periods of the nuclides used. To separate the compound and non-compound types, these were distributed between water and chloroform. The isotope ratio in the chloroform phase was compared with the output isotope ratio and the separation facfor determined from this. When using crown ethers, there was enrichment of 24 Na + by a significant amount (large crown ether) up to 3.1 +- 0.4% for 18 crown 6. The remarkably high results can be correlated by Biegeleisen's theory with other chemical conditions. There is a report on the first results of transferring these conditions to the H + /T + system. (orig.) [de

  4. Calcium hydroxide isotope effect in calcium isotope enrichment by ion exchange

    International Nuclear Information System (INIS)

    Jepson, B.E.; Shockey, G.C.

    1984-01-01

    The enrichment of calcium isotopes has been observed in ion-exchange chromatography with an aqueous phase of calcium hydroxide and a solid phase of sulfonic acid resin. The band front was exceedingly sharp as a result of the acid-base reaction occuring at the front of the band. Single-stage separation coefficients were found to be epsilon( 44 Ca/ 40 Ca) = 11 x 10 -4 and epsilon( 48 Ca/ 40 Ca) = 18 x 10 -4 . The maximum column separation factors achieved were 1.05 for calcium-44 and 1.09 for calcium-48 with the heavy isotopes enriching in the fluid phase. The calcium isotope effect between fully hydrated aqueous calcium ions and undissociated aqueous calcium hydroxide was estimated. For the calcium-44/40 isotope pair the separation coefficient was 13 x 10 -4 . 20 references, 2 figures

  5. Isotope effect in the Knight shift of potassium

    International Nuclear Information System (INIS)

    Sahm, W.; Schwenk, A.

    1975-01-01

    The Knight shifts of the potassium isotopes 39 K and 41 K were determined with high accuracy: Ksup((39)) = 0.274 35(10)% and Ksup((41)) = 0.274 93(12)%. The relative isotope effect ΔK/K = -0.210 (20)% is in agreement with the hyperfine structure anomaly 39 Δ 41 . (orig.) [de

  6. Measurement of infiltration rates in urban sewer systems by use of oxygen isotopes.

    Science.gov (United States)

    De Bénédittis, J; Bertrand-Krajewski, J L

    2005-01-01

    The paper presents the principle of a method to measure infiltration rates in sewer systems based on the use of oxygen isotopes and its application in Lyon (France). In the urban area of Lyon, significant differences in delta 18O that can reach 3 per thousand are observed between the oxygen isotopic compositions of groundwater originating from Rhone, Saone and from their associated alluvial aquifers. Drinking water supplying Lyon results mainly from pumping in the Rhone alluvial aquifer. Therefore, in some areas, the difference of isotopic composition between wastewater resulting from the consumption of drinking water and local groundwater can be used to measure infiltration in sewer systems. The application in the catchment of Ecully shows that the infiltration flow rate presents strong fluctuations at an hourly scale: it varies between 15 and 40 m3/h. This variability could be explained by non-constant discharges of pumping and by variations of the water level in the sewer.

  7. Effects of must concentration techniques on wine isotopic parameters.

    Science.gov (United States)

    Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

    2006-12-27

    Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

  8. Symmetry effects in neutron scattering from isotopically enriched Se isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Lachkar, J.; Haouat, G.; McEllistrem, M. T.; Patin, Y.; Sigaud, J.; Cocu, F.

    1975-06-01

    Differential cross sections for neutron elastic and inelastic scattering from {sup 76}Se, {sup 78}Se, {sup 80}Se and {sup 82}Se, have been measured at 8-MeV incident neutron energy and from {sup 76}Se and {sup 82}Se at 6- and 10-MeV incident energies. The differences observed in the elastic scattering cross sections are interpretable as the effects of isospin term in the scattering potentials. A full analysis of the elastic scattering data are presented.

  9. Isotope effect on the zero point energy shift upon condensation

    International Nuclear Information System (INIS)

    Kornblum, Z.C.

    1977-01-01

    The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation have been derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, has been presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. Each intensity sum is expressed, in part, in terms of partial derivatives of the molecular dipole moment with respect to atomic cartesian coordinates. These derivatives are related to the isotope-independent effective charges of the atoms, which are theoretically calculated by means of a modified CNDO/2 computer program. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules

  10. Neutrino energy loss rates due to key iron isotopes for core-collapse physics

    International Nuclear Information System (INIS)

    Nabi, J.-U.

    2008-07-01

    Accurate estimates of neutrino energy loss rates are needed for the study of the late stages of the stellar evolution, in particular for the cooling of neutron stars and white dwarfs. The energy spectra of neutrinos and antineutrinos arriving at the Earth can also provide useful information on the primary neutrino fluxes as well as neutrino mixing scenario. Proton-neutron quasi-particle random phase approximation (pn-QRPA) theory has recently being used for a microscopic calculation of stellar weak interaction rates of fp-shell nuclide, particularly iron isotopes, with success. Here I present the calculation of neutrino and antineutrino energy loss rates due to key iron isotopes in stellar matter using the pn-QRPA theory. The rates are calculated on a fine grid of temperature-density scale suitable for core-collapse simulators. The calculated rates are compared against earlier calculations. The neutrino cooling rates due to even-even isotopes of iron, 54,56 Fe, are in good agreement with the rates calculated using the large-scale shell model. The pn-QRPA calculated neutrino energy loss rates due to 55 Fe are enhanced roughly around an order of magnitude compared to the large-scale shell model calculation during the oxygen and silicon shell burning stages of massive stars and favor a lower entropy for the cores of massive stars. (author)

  11. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  12. Theory of the isotope effect in superconducting compounds

    International Nuclear Information System (INIS)

    Culetto, F.J.; Rainer, D.

    1978-05-01

    We present a theoretical analysis of the isotope effect on the superconducting transition temperature. Our method is to calculate via formal perturbation theory the response of the transition temperature to small changes of the masses of the various constituents of the compound. We discuss the relation between the isotope effect and various more fundamental parameters in strong coupling superconductors. As illustrative examples, we consider the systems Pd-H(D) alloys and the binary Chevrel phase superconductor Mo 6 Se 8 , and show that analysis of the isotope effect can yield useful information concerning interaction mechanisms in these compounds. (orig.)

  13. Biosynthetic effects on the stable carbon isotopic compositions of agal lipids: Implications for deciphering the carbon isotopic biomarker record

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Schouten, S.; Klein Breteler, W.C.M.; Blokker, P.; Schogt, N.; Rijpstra, W.I.C.; Grice, K.; Baas, M.

    1998-01-01

    Thirteen species of algae covering an extensive range of classes were cultured and stable carbon isotopic compositions of their lipids were analysed in order to assess carbon isotopic fractionation effects during their biosynthesis. The fatty acids were found to have similar stable carbon isotopic

  14. Isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide and aqueous solutions

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi; Itami, Akira

    1989-01-01

    The isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide ion exchanger and aqueous solutions was radiochemically measured to obtain fundamental data which are useful for elucidating the ion-exchange kinetics of the material for the transition metal elements. The rate can be understood by considering that the cobalt ions were present in the exchanger as three kinds of species: (A 1 ) Free ions which can diffuse in the exchanger particles, (A 2 ) Weakly bound ions to the exchange sites which exchange rapidly with A 1 , and (B) Covalently fixed ions to the exchange sites which exchange very slowly with A 1 . At low fraction of B, the rate is controlled by the diffusion of A 1 with the effective diffusion coefficient, D eff , the values of which depend on the concentration ratios of A 2 to A 1 . When B predominates over the A species, the concentration ratios of B to A 1 affect greatly D eff . The values of D eff and their activation energy(20 kJ/mol) were also estimated

  15. Isotopically decoupled vibrational spectra and proton exchange rates for crystalline NH3 and ammonia hydrate

    Science.gov (United States)

    Thornton, Cynthia; Khatkale, M. S.; Devlin, J. Paul

    1981-12-01

    Codeposits of NH3 with ND3 or D2O have been prepared at liquid nitrogen temperatures in the absence of proton exchange. Vibrational data for the anhydrous cubic crystalline ammonia, containing isolated NH3 or ND3, confirm that, relative to water ice, intermolecular coupling in ammonia ice exerts a relatively minor influence on the infrared and Raman spectra. Nevertheless, sizeable decoupling shifts, particularly for ν1, have been observed and attributed to a combination of factors including correlation field and Fermi resonance effects. The Raman polarization data has also affirmed long standing assignments of ν1 and ν3 for ammonia ice. Warming of the ammonia thin films resulted in limited isotopic scrambling at 130 K, apparently possible only through the agency of trace concentrations of water. The vibrational coupling pattern for the resultant NHD2 and NH2D molecules suggest that proton (deuteron) migration away from the exchange centers is impossible at temperatures up to 150 K. By contrast, isotopic scrambling was rapid and complete at 140 K for amorphous ammonia hydrate films (˜35% NH3, ˜65% D2O) which were also prepared without exchange at ˜90 K. The proton (deuteron) exchange rate is much greater for the amorphous ammonia hydrate at 140 K than for pure water ice. Such exchange requires both ion-pair defect formation and proton mobility. Since the NH3 suppresses the H3O+ concentration via formation of NH+4, a suppression the likes of which has been shown to stop proton exchange in water ice, the evidence strongly suggests that NH4+ in ammonia, like H3O+ in water, is an effective proton transfer agent, probably acting through a tunneling mechanism (i.e., H3N+-HṡṡṡNH3→H3NṡṡṡH-N+H3 etc.) to render the proton mobile in the ammonia hydrate. This mobility combined with the greater NH4+ concentration, relative to the H3O+ concentration in H2O ice Ic, results in isotopic scrambling at the reduced temperature.

  16. Estimation of microbial respiration rates in groundwater by geochemical modeling constrained with stable isotopes

    International Nuclear Information System (INIS)

    Murphy, E.M.

    1998-01-01

    Changes in geochemistry and stable isotopes along a well-established groundwater flow path were used to estimate in situ microbial respiration rates in the Middendorf aquifer in the southeastern United States. Respiration rates were determined for individual terminal electron acceptors including O 2 , MnO 2 , Fe 3+ , and SO 4 2- . The extent of biotic reactions were constrained by the fractionation of stable isotopes of carbon and sulfur. Sulfur isotopes and the presence of sulfur-oxidizing microorganisms indicated that sulfate is produced through the oxidation of reduced sulfur species in the aquifer and not by the dissolution of gypsum, as previously reported. The respiration rates varied along the flow path as the groundwater transitioned between primarily oxic to anoxic conditions. Iron-reducing microorganisms were the largest contributors to the oxidation of organic matter along the portion of the groundwater flow path investigated in this study. The transition zone between oxic and anoxic groundwater contained a wide range of terminal electron acceptors and showed the greatest diversity and numbers of culturable microorganisms and the highest respiration rates. A comparison of respiration rates measured from core samples and pumped groundwater suggests that variability in respiration rates may often reflect the measurement scales, both in the sample volume and the time-frame over which the respiration measurement is averaged. Chemical heterogeneity may create a wide range of respiration rates when the scale of the observation is below the scale of the heterogeneity

  17. Isotopic alloying to tailor helium production rates in mixed spectrum reactors

    International Nuclear Information System (INIS)

    Mansur, L.K.; Rowcliffe, A.F.; Grossbeck, M.L.; Stoller, R.E.

    1985-01-01

    The purposes of this work are to increase the understanding of mechanisms by which helium affects microstructure and properties, to aid in the development of materials for fusion reactors, and to obtain data from fission reactors in regimes of direct interest for fusion reactor applications. Isotopic alloying is examined as a means of manipulating the ratio of helium transmutations to atom displacements in mixed spectrum reactors. The application explored is based on artificially altering the relative abundances of the stable isotopes of nickel to systematically vary the fraction of 58 Ni in nickel bearing alloys. The method of calculating helium production rates is described. Results of example calculations for proposed experiments in the High Flux Isotope Reactor are discussed

  18. Analysis of growth and tissue replacement rates by stable sulfur isotope turnover.

    Science.gov (United States)

    Arneson, L. S.; Macko, S. A.; Macavoy, S. E.

    2003-12-01

    Stable isotope analysis has become a powerful tool to study animal ecology. Analysis of stable isotope ratios of elements such as carbon, nitrogen, sulfur, hydrogen, oxygen and others have been used to trace migratory routes, reconstruct dietary sources and determine the physiological condition of individual animals. The isotopes most commonly used are carbon, due to differential carbon fractionation in C3 and C4 plants, and nitrogen, due to the approximately 3% enrichment in 15N per trophic level. Although all cells express sulfur-containing compounds, such as cysteine, methionine, and coenzyme A, the turnover rate of sulfur in tissues has not been examined in most studies, owing to the difficulty in determining the δ 34S signature. In this study, we have assessed the rate of sulfur isotopic turnover in mouse tissues following a diet change from terrestrial (7%) to marine (19%) source. Turnover models reflecting both growth rate and metabolic tissue replacement will be developed for blood, liver, fat and muscle tissues.

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

    International Nuclear Information System (INIS)

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

    1985-01-01

    The authors have measured the 13 C kinetic isotope effect at pH 4.0, 5.0, 6.0, and 6.5 and in D 2 O at pH 5.0 and the rate of D-H exchange of the alpha and beta protons of aspartic acid in D 2 O at pH 5.0 for the reaction catalyzed by the enzyme aspartate beta-decarboxylase from Alcaligenes faecalis. The 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 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

  20. Kinetic isotope effect in the thermolysis of methylenecyclobutane

    International Nuclear Information System (INIS)

    Chickos, J.S.

    1979-01-01

    The intramolecular kinetic isotope effect for the thermolysis of equilibrated methylenecyclobutane-d 2 was investigated at 515 0 C as a function of pressure. A high-pressure value of k/sub H/k/sub D/ (ethylene/ethylene-d 2 ) = 0.9 was obtained at 13 cm of N 2 pressure. This value decreased to 0.86 at 70 μm total pressure. No intermolecular kinetic isotope effect was measured for the formation of ethylene from labeled and unlabeled methylenecyclobutane. The pressure and temperature dependence of the intramolecular kinetic isotope effect was used as evidence in establishing the inverse nature of the effect. The isotope effect observed was explained in terms of competing equilibrium and kinetic isotope effects in which the equilibrium isotope effects dominate. It was concluded on the bases of these results that an acyclic intermediate is involved in the fragmentation of methylenecyclobutane to ethylene and allene. The results also support the notion that deuterium prefers to accumulate at the methylene group with the greatest p character in the carbon--hydrogen bond. 1 figure, 4 tables

  1. Absence of isotope effect of diffusion in a metallic glass

    International Nuclear Information System (INIS)

    Heesemann, A.; Raetzke, K.; Faupel, F.; Hoffmann, J.; Heinemann, K.

    1995-01-01

    The isotope effect E = d ln(D)/d ln (1/√m) of Co diffusion in structurally relaxed Co 86 Zr 14 and Co 81 Zr 19 glasses has been measured by means of a radiotracer technique. Within experimental accuracy no isotope effect was detected (E < 0.04). This suggests a highly cooperative diffusion mechanism. The connection between diffusion and collective low-frequency relaxations in glasses is discussed. (orig.)

  2. Isotopic exchange rate of sodium ions between hydrous metal oxides and aqueous solutions

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi

    1991-01-01

    To elucidate the kinetics of ion-exchange reaction on hydrous metal oxide, the isotopic exchange rates of sodium ions between hydrous metal oxides such as hydrous tin (IV), niobium (V), zirconium (IV) and titanium (IV) oxides, and aqueous solutions were measured radiochemically and compared with each other. The rate of reaction cannot be understood by an unified view since the rate controlling step differs with the kind of exchangers. The rate constants relevant to each exchanger such as diffusion constants and their activation energies were also determined. (author)

  3. Mass-independent isotope effects in chemical exchange reaction

    International Nuclear Information System (INIS)

    Nishizawa, Kazushige

    2000-01-01

    Isotope effects of some elements in chemical exchange reaction were investigated by use of liquid-liquid extraction, liquid membrane or chromatographic separation. Cyclic polyether was used for every method. All polyethers used in a series of the studies were made clear that they distinguished the isotopes not only by their nuclear masses but also by their nuclear sizes and shapes. Chromium isotopes, for example, were recognized to have enrichment factors being proportional to δ 2 > which is a parameter to show field shift or the nuclear size and shape of the isotope. It follows that the chromium isotopes are separated not by their masses but by their field shift effects. Nuclear spin also played a great role to separate odd mass number isotopes from even mass number isotopes in even atomic number elements. Contribution of the nuclear spin (I=3/2) of 53 Cr to total enrichment factor, ε 53/52 = -0.00028, for 53 Cr to 52 Cr was observed to be, ε spin = -0.0025. (author)

  4. H/D Isotope Effects in Hydrogen Bonded Systems

    Directory of Open Access Journals (Sweden)

    Aleksander Filarowski

    2013-04-01

    Full Text Available An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio nH/nD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δd (1H,2H on d (1H. This effect corresponds to the range of maximum on the correlation curve between dH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

  5. Isotope effect on the zero point energy shift upon condensation

    International Nuclear Information System (INIS)

    Kornblum, Z.C.; Ishida, T.

    1977-07-01

    The various isotope-dependent and independent atomic and molecular properties that pertain to the isotopic difference between the zero point energy (ZPE) shifts upon condensation were derived. The theoretical development of the change of the ZPE associated with the internal molecular vibrations, due to the condensation of the gaseous molecules, is presented on the basis of Wolfsberg's second-order perturbation treatment of the isotope-dependent London dispersion forces between liquid molecules. The isotope effect on the ZPE shift is related to the difference between the sums of the integrated intensities of the infrared absorption bands of the two gaseous isotopic molecules. The effective atomic charges are also calculated from available experimental infrared intensity data. The effects of isotopic substitutions of carbon-13 for carbon-12 and/or deuterium for protium, in ethylene, methane, and the fluorinated methanes, CH 3 F, CH 2 F 2 , CHF 3 , and CF 4 , on the ZPE shift upon condensation are calculated. These results compare well with the Bigeleisen B-factors, which are experimentally obtained from vapor pressure measurements of the isotopic species. Each of the following molecular properties will tend to increase the isotopic difference between the ZPE shifts upon condensation: (1) large number of highly polar bonds, (2) high molecular weight, (3) non-polar (preferably) or massive molecule, (4) non-hydrogenous molecule, and (5) closely packed liquid molecules. These properties will result in stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules. 36 tables, 9 figures

  6. 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?

    Science.gov (United States)

    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.

  7. Bibliography on vapor pressure isotope effects

    International Nuclear Information System (INIS)

    Jancso, G.

    1980-04-01

    The first Bibliography on Vapour Pressure Isotope and covered the literature of the period from 1919 through December 1975. The present Supplement reviews the literature from January 1976 through December 1979. The bibliography is arranged in chronological order; within each year the references are listed alphabetically according to the name of the first author of each work. (author)

  8. Carbon-13 kinetic isotope effects in the decarbonylations of lactic acid containing 13C at the natural abundance level

    International Nuclear Information System (INIS)

    Zielinski, M.; Czarnota, G.; Papiernik-Zielinska, H.

    1992-01-01

    The 13 C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20-80 deg C. The 13 C (1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40 deg C. Below this temperature the 13 C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found in the decarbonylation of lactic [1- 14 C] acid. The experimental values of k (12C) /k (13C) ratios of isotopic rate constants for 12 C and 13 C are close to, but slightly higher than theoretical 13 C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C (1) -OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H 2 O)/(H 2 SO 4 ) ratio caused the increase of the 13 C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5 deg C to 1.0536±0.0008 (at 80.6 deg C). A discussion of the abnormally high temperature dependence of 14 C and 13 C isotope fractionation in this reaction and the discussion of the problem of relative 14 C/ 13 C kinetic isotope effects is given. (author) 18 refs.; 2 tabs

  9. Isotopic effects on phonon anharmonicity in layered van der Waals crystals: Isotopically pure hexagonal boron nitride

    Science.gov (United States)

    Cuscó, Ramon; Artús, Luis; Edgar, James H.; Liu, Song; Cassabois, Guillaume; Gil, Bernard

    2018-04-01

    Hexagonal boron nitride (h -BN) is a layered crystal that is attracting a great deal of attention as a promising material for nanophotonic applications. The strong optical anisotropy of this crystal is key to exploit polaritonic modes for manipulating light-matter interactions in 2D materials. h -BN has also great potential for solid-state neutron detection and neutron imaging devices, given the exceptionally high thermal neutron capture cross section of the boron-10 isotope. A good knowledge of phonons in layered crystals is essential for harnessing long-lived phonon-polariton modes for nanophotonic applications and may prove valuable for developing solid-state 10BN neutron detectors with improved device architectures and higher detection efficiencies. Although phonons in graphene and isoelectronic materials with a similar hexagonal layer structure have been studied, the effect of isotopic substitution on the phonons of such lamellar compounds has not been addressed yet. Here we present a Raman scattering study of the in-plane high-energy Raman active mode on isotopically enriched single-crystal h -BN. Phonon frequency and lifetime are measured in the 80-600-K temperature range for 10B-enriched, 11B-enriched, and natural composition high quality crystals. Their temperature dependence is explained in the light of perturbation theory calculations of the phonon self-energy. The effects of crystal anisotropy, isotopic disorder, and anharmonic phonon-decay channels are investigated in detail. The isotopic-induced changes in the phonon density of states are shown to enhance three-phonon anharmonic decay channels in 10B-enriched crystals, opening the possibility of isotope tuning of the anharmonic phonon decay processes.

  10. Inverse isotope effect in iron-based superconductor

    International Nuclear Information System (INIS)

    Shirage, Parasharam M.; Kihou, Kunihiro; Miyazawa, Kiichi; Lee, Chul-Ho; Kito, Hijiri; Yoshida, Yoshiyuki; Eisaki, Hiroshi; Tanaka, Yasumoto; Iyo, Akira

    2010-01-01

    We have found that (Ba, K)Fe 2 As 2 superconductor (a transition temperature, T c ∼ 38 K) shows an inverse Iron isotope effect (α Fe = -0.18 ± 0.03, where T c ∼ M -αFe and M is the iron isotope mass), i.e. the sample containing the larger iron mass depicts higher T c . Systematic studies using three types of Fe-isotopes ( 54 Fe, natural Fe and 57 Fe) reveal a clear inverse shift on T c by measurements of temperature dependent magnetization and resistivity. The inverse isotope effect that is the first case in high-T c superconductors strongly suggests that superconducting mechanism of the iron-based system is not explained by conventional BCS theory mediated by phonons.

  11. Isotope effects in the non enzymic glycation of hemoglobin catalyzed by DPG

    International Nuclear Information System (INIS)

    Gil, Herminia; Uzcategui, Jorge

    1993-01-01

    The paradigmatic reaction of glucose with hemoglobin (Hb A o ) has been studied and is known to occur most rapidly at the N-terminal valine of the β-subunit. An initial, rapid imine formation is succeeded by slower Amadori rearrangement. Non enzymic glycation of Hb A o was studied in vitro in buffer Tris 10 mM in H 2 O and D 2 O, pH 7.3, pD 7.8 at 37 deg C at a fixed concentration of 2,3 diphosphoglycerate (DPG). The reaction exhibits identical rates in protium and deuterium oxides. When D-glucose-2-h is compared with D-glucose-2-d, the kinetic isotope effect for the DPG-dependent rate is 2.1 ± 0.3, while the DPG-independent rate constant shows no isotope effect (1.1 ± 0.1). The absence of a rate in isotopic water solvents shows that proton donation for solvent, lyons or DPG does not limit the rate. The substrate isotope effect of around 2 for the DPG kinetic term indicates that the proton abstraction step of the Amadori rearrangement by DPG is wholly or partially rate-limiting for this reaction. (author)

  12. Isotope effects in the non enzymic glycation of hemoglobin catalyzed by DPG

    Energy Technology Data Exchange (ETDEWEB)

    Gil, Herminia; Uzcategui, Jorge [Universidad de Los Andes, Merida (Venezuela). Dept. de Quimica

    1993-12-31

    The paradigmatic reaction of glucose with hemoglobin (Hb A{sub o}) has been studied and is known to occur most rapidly at the N-terminal valine of the {beta}-subunit. An initial, rapid imine formation is succeeded by slower Amadori rearrangement. Non enzymic glycation of Hb A{sub o} was studied in vitro in buffer Tris 10 mM in H{sub 2} O and D{sub 2} O, pH 7.3, pD 7.8 at 37 deg C at a fixed concentration of 2,3 diphosphoglycerate (DPG). The reaction exhibits identical rates in protium and deuterium oxides. When D-glucose-2-h is compared with D-glucose-2-d, the kinetic isotope effect for the DPG-dependent rate is 2.1 {+-} 0.3, while the DPG-independent rate constant shows no isotope effect (1.1 {+-} 0.1). The absence of a rate in isotopic water solvents shows that proton donation for solvent, lyons or DPG does not limit the rate. The substrate isotope effect of around 2 for the DPG kinetic term indicates that the proton abstraction step of the Amadori rearrangement by DPG is wholly or partially rate-limiting for this reaction. (author) 23 refs., 4 figs.

  13. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    Science.gov (United States)

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  14. FABGEN, a transient power-generation and isotope birth rate calculator

    International Nuclear Information System (INIS)

    Roland, H.C.

    1975-04-01

    A description is given of the FABGEN program, a fast-running program for calculating fuel element power-generation rates and selected fission product birth rates in a known neutron flux as functions of time. A first forward difference calculation is used, and the time step is one day. Provisions are made for including various fuel element lengths, variation of thermal flux with time, and use of different fertile isotopes. Five different fission products may be specified for birth-rate calculations. A daily summary may be output, or totals by days may be accumulated for final output. (U.S.)

  15. Vadose Zone Infiltration Rate at Hanford, Washington, Inferred from Sr Isotope Measurements

    International Nuclear Information System (INIS)

    Maher, Katharine; DePaolo, Donald J.; Conrad, Mark E.; Serne, R. Jeffrey

    2003-01-01

    Sr isotope ratios were measured in the pore water, acid extracts, and sediments of a 70-m vadose zone core to obtain estimates of the long-term infiltration flux for a site in the Hanford/DOE complex in eastern Washington State. The 87Sr/86Sr values of the pore waters decrease systematically with depth, from a high value of 0.721 near the surface toward the bulk sediment average value of 0.711. Estimates of the bulk weathering rate combined with Sr isotopic data were used to constrain the long-term (century to millenial scale) natural diffuse infiltration flux for the site given both steady state and nonsteady state conditions. The models suggest that the infiltration fluc for the site is 7+- 3 mm/yr. The method shows potential for providing long-term in situ estimates of infiltration rates for deep heterogeneous vadose zones

  16. Lithium isotope effect accompanying electrochemical intercalation of lithium into graphite

    CERN Document Server

    Yanase, S; Oi, T

    2003-01-01

    Lithium has been electrochemically intercalated from a 1:2 (v/v) mixed solution of ethylene carbonate (EC) and methylethyl carbonate (MEC) containing 1 M LiClO sub 4 into graphite, and the lithium isotope fractionation accompanying the intercalation was observed. The lighter isotope was preferentially fractionated into graphite. The single-stage lithium isotope separation factor ranged from 1.007 to 1.025 at 25 C and depended little on the mole ratio of lithium to carbon of the lithium-graphite intercalation compounds (Li-GIC) formed. The separation factor increased with the relative content of lithium. This dependence seems consistent with the existence of an equilibrium isotope effect between the solvated lithium ion in the EC/MEC electrolyte solution and the lithium in graphite, and with the formation of a solid electrolyte interfaces on graphite at the early stage of intercalation. (orig.)

  17. Clumped isotope effects during OH and Cl oxidation of methane

    DEFF Research Database (Denmark)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

    2017-01-01

    A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produ......A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...... reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane...

  18. Effectiveness of different pre-treatments in recovering pre-burial isotopic ratios of charred plants.

    Science.gov (United States)

    Brinkkemper, O; Braadbaart, F; van Os, B; van Hoesel, A; van Brussel, A A N; Fernandes, R

    2018-02-15

    Isotopic analysis of archaeological charred plant remains offers useful archaeological information. However, adequate sample pre-treatment protocols may be necessary to provide a contamination-free isotopic signal while limiting sample loss and achieving a high throughput. Under these constraints, research was undertaken to compare the performance of different pre-treatment protocols. Charred archaeological plant material was selected for isotopic analysis (δ 13 C and δ 15 N values) by isotope ratio mass spectrometry from a variety of plant species, time periods and soil conditions. Preservation conditions and the effectiveness of cleaning protocols were assessed through Fourier transform infrared spectroscopy and X-ray fluorescence (XRF) spectrometry. An acid-base-acid protocol, successfully employed in radiocarbon dating, was used to define a contamination-free isotopic reference. Acid-base-acid isotopic measurements were compared with those obtained from untreated material and an acid-only protocol. The isotopic signals of untreated material and the acid-only protocol typically did not differ more than 1‰ from those of the acid-base-acid reference. There were no significant isotopic offsets between acid-base-acid and acid-only or untreated samples. Sample losses in the acid-base-acid protocol were on average 50 ± 17% (maximum = 98.4%). Elemental XRF measurements showed promising results in the detection of more contaminated samples albeit with a high rate of false positives. For the large range of preservation conditions described in the study, untreated charred plant samples, water cleaned of sediments, provide reliable stable isotope ratios of carbon and nitrogen. The use of pre-treatments may be necessary under different preservation conditions or more conservative measurement uncertainties should be reported. Copyright © 2017 John Wiley & Sons, Ltd.

  19. Cl and C isotope analysis to assess the effectiveness of chlorinated ethene degradation by zero-valent iron: Evidence from dual element and product isotope values

    International Nuclear Information System (INIS)

    Audí-Miró, Carme; Cretnik, Stefan; Otero, Neus; Palau, Jordi; Shouakar-Stash, Orfan; Soler, Albert

    2013-01-01

    Highlights: ► TCE and cis-DCE Cl isotope fractionation was investigated for the first time with ZVI. ► A C–Cl bond is broken in the rate-limiting step during ethylene ZVI dechlorination. ► Dual C/Cl isotope plot is a promising tool to discriminate abiotic degradation. ► Product-related carbon isotopic fractionation gives evidence of abiotic degradation. ► Hydrogenolysis and β-dichloroelimination pathways occur simultaneously. - Abstract: This study investigated C and, for the first time, Cl isotope fractionation of trichloroethene (TCE) and cis-dichloroethene (cis-DCE) during reductive dechlorination by cast zero-valent iron (ZVI). Hydrogenolysis and β-dichloroelimination pathways occurred as parallel reactions, with ethene and ethane deriving from the β-dichloroelimination pathway. Carbon isotope fractionation of TCE and cis-DCE was consistent for different batches of Fe studied. Transformation of TCE and cis-DCE showed Cl isotopic enrichment factors (ε Cl ) of −2.6‰ ± 0.1‰ (TCE) and −6.2‰ ± 0.8‰ (cis-DCE), with Apparent Kinetic Isotope Effects (AKIE Cl ) for Cl of 1.008 ± 0.001 (TCE) and 1.013 ± 0.002 (cis-DCE). This indicates that a C–Cl bond breakage is rate-determining in TCE and cis-DCE transformation by ZVI. Two approaches were investigated to evaluate if isotope fractionation analysis can distinguish the effectiveness of transformation by ZVI as opposed to natural biodegradation. (i) Dual isotope plots. This study reports the first dual (C, Cl) element isotope plots for TCE and cis-DCE degradation by ZVI. The pattern for cis-DCE differs markedly from that reported for biodegradation of the same compound by KB-1, a commercially available Dehalococcoides-containing culture. The different trends suggest an expedient approach to distinguish abiotic and biotic transformation, but this needs to be confirmed in future studies. (ii) Product-related isotope fractionation. Carbon isotope ratios of the hydrogenolysis product cis

  20. Reconstruction of three centuries of annual accumulation rates based on the record of stable isotopes of water from Lomonosovfonna, Svalbard

    NARCIS (Netherlands)

    Pohjola, V.; Martma, T.; Meijer, H.A.J.; Moore, J.; Isaksson, E.; Vaikmae, R.; van de Wal, R.S.W.

    2002-01-01

    We use the upper 81 in of the record of stable isotopes of water from a 122 in long ice core from Lomonosovfonna, central Spitsbergen, Svalbard, to construct an ice-core chronology and the annual accumulation rates over the icefield. The isotope cycles are counted in the ice-core record using a

  1. Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

    Science.gov (United States)

    Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

    2017-12-01

    Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

  2. Pollution and Climate Effects on Tree-Ring Nitrogen Isotopes

    Science.gov (United States)

    Savard, M. M.; Bégin, C.; Marion, J.; Smirnoff, A.

    2009-04-01

    Georgian Bay reflect deposition of NOx emissions from cars and coal-power plants, with higher proportions from coal burning in Georgian Bay (Savard et al., 2009b). This interpretation is conceivable because recent monitoring indicates that coal-power plant NOx emissions play an important role in the annual N budget in Ontario, but they are negligible on the Quebec side. CONCLUSION Interpretations of long tree-ring N isotopic series in terms of effects generated by airborne N-species have been previously advocated. Here we further propose that the contrasted isotopic trends obtained for wood samples from two regions reflect different regional anthropogenic N deposition combined with variations of climatic conditions. This research suggests that nitrogen tree-ring series may record both regional climatic conditions and anthropogenic perturbations of the N cycle. REFERENCES Savard, M.M., Bégin,C., Marion, J., Aznar, J.-C., Smirnoff, A., 2009a. Changes of Air Quality in an urban region as inferred from tree-ring width and stable isotopes. Chapter 9 in "Relating Atmospheric Source Apportionment to Vegetation Effects: Establishing Cause Effect Relationships" (A. Legge ed.). Elsevier, Amsterdam; doi: 10.1016/S1474-8177(08)00209x. Savard, M.M., Bégin, C., Smirnoff, A., Marion, J., Rioux-Paquette, E., 2009b. Tree-ring nitrogen isotopes reflect climatic effects and anthropogenic NOx emissions. Env. Sci. Tech (doi: 10.1021/es802437k).

  3. Mass independent isotope effects and their observations in nature

    International Nuclear Information System (INIS)

    Thiemens, M.H.

    2002-01-01

    In 1983, Thiemens and Heidenreich reported the first chemically produced mass independent isotope effect. A significant feature of the fractionation was that it identically produced the isotopic relation observed in the calcium-aluminum inclusions in the Allende meteorite. This δ 17 O=δ 18 O composition had previously been thought to represent a nucleosynthetic component as no chemical process was capable of producing a mass independent isotopic composition. It now appears nearly certain that the meteoritic oxygen isotopic anomalies were produced by chemical, rather than nuclear, processes. Since oxygen is the major element in stony planets this represents a major event in the formation of the solar system. In a recent review (Thiemens, 1999), it has been shown that mass independent isotopic compositions are pervasive in the Earth's atmosphere. Molecules which have been demonstrated to possess mass independent isotopic compositions include: O 2 , O 3 , CO 2 , CO, and N 2 O. In each case, the specific nature of the mass independent isotopic composition has provided details of their atmospheric chemistry that could not have been obtained by any other measurement technique. Most recently, solid materials have been observed to possess mass independent isotopic composition. In this paper, these observations are briefly discussed. These solid reservoirs include: 1) carbonates and sulphates from Mars, 2) terrestrial aerosol sulphate, 3) sulphides and sulphates from the Earth, ranging in time from 3.8 to 2.2 billion years before present, 4) sulphates from the Namibian desert and 5) the Antartic Dry Valleys. The information obtained from these measurements is extraordinarily wide ranging, extending from understanding the history of Martian atmosphereregolith interaction to the evolution of the oxygen in the Earth's earliest atmosphere. As was the case for gas phase species, this information and insight could not have been obtained by any other measurement technique

  4. Transport hysteresis and hydrogen isotope effect on confinement

    Science.gov (United States)

    Itoh, S.-I.; Itoh, K.

    2018-03-01

    A Gedankenexperiment on hydrogen isotope effect is developed, using the transport model with transport hysteresis. The transport model with hysteresis is applied to case where the modulational electron cyclotron heating is imposed near the mid-radius of the toroidal plasmas. The perturbation propagates either outward or inward, being associated with the clockwise (CW) hysteresis or counter-clockwise (CCW) hysteresis, respectively. The hydrogen isotope effects on the CW and CCW hysteresis are investigated. The local component of turbulence-driven transport is assumed to be the gyro-Bohm diffusion. While the effect of hydrogen mass number is screened in the response of CW hysteresis, it is amplified in CCW hysteresis. This result motivates the experimental studies to compare CW and CCW cases in order to obtain further insight into the physics of hydrogen isotope effects.

  5. A calculation of the surface recombination rate constant for hydrogen isotopes on metals

    International Nuclear Information System (INIS)

    Baskes, M.J.

    1980-01-01

    The surface recombination rate constant for hydrogen isotopes on a metal has been calculated using a simple model whose parameters may be determined by direct experimental measurements. Using the experimental values for hydrogen diffusivity, solubility, and sticking coefficient at zero surface coverage a reasonable prediction of the surface recombination constant may be made. The calculated recombination constant is in excellent agreement with experiment for bcc iron. A heuristic argument is developed which, along with the rate constant calculation, shows that surface recombination is important in those metals in which hydrogen has an exothermic heat of solution. (orig.)

  6. Improved repetition rate mixed isotope CO{sub 2} TEA laser

    Energy Technology Data Exchange (ETDEWEB)

    Cohn, D. B., E-mail: dbctechnology@earthlink.net [DBC Technology Corp., 4221 Mesa St, Torrance, California 90505 (United States)

    2014-09-15

    A compact CO{sub 2} TEA laser has been developed for remote chemical detection that operates at a repetition rate of 250 Hz. It emits 700 mJ/pulse at 10.6 μm in a multimode beam with the {sup 12}C{sup 16}O{sub 2} isotope. With mixed {sup 12}C{sup 16}O{sub 2} plus {sup 13}C{sup 16}O{sub 2} isotopes it emits multiple lines in both isotope manifolds to improve detection of a broad range of chemicals. In particular, output pulse energies are 110 mJ/pulse at 9.77 μm, 250 mJ/pulse at 10 μm, and 550 mJ/pulse at 11.15 μm, useful for detection of the chemical agents Sarin, Tabun, and VX. Related work shows capability for long term sealed operation with a catalyst and an agile tuner at a wavelength shift rate of 200 Hz.

  7. Isotope and mixture effects on neoclassical transport in the pedestal

    Science.gov (United States)

    Pusztai, Istvan; Buller, Stefan; Omotani, John T.; Newton, Sarah L.

    2017-10-01

    The isotope mass scaling of the energy confinement time in tokamak plasmas differs from gyro-Bohm estimates, with implications for the extrapolation from current experiments to D-T reactors. Differences in mass scaling in L-mode and various H-mode regimes suggest that the isotope effect may originate from the pedestal. In the pedestal, sharp gradients render local diffusive estimates invalid, and global effects due to orbit-width scale profile variations have to be taken into account. We calculate neoclassical cross-field fluxes from a radially global drift-kinetic equation using the PERFECT code, to study isotope composition effects in density pedestals. The relative reduction to the peak heat flux due to global effects as a function of the density scale length is found to saturate at an isotope-dependent value that is larger for heavier ions. We also consider D-T and H-D mixtures with a focus on isotope separation. The ability to reproduce the mixture results via single-species simulations with artificial ``DT'' and ``HD'' species has been considered. These computationally convenient single ion simulations give a good estimate of the total ion heat flux in corresponding mixtures. Funding received from the International Career Grant of Vetenskapsradet (VR) (330-2014-6313) with Marie Sklodowska Curie Actions, Cofund, Project INCA 600398, and Framework Grant for Strategic Energy Research of VR (2014-5392).

  8. Anharmonic phonons and the isotope effect in superconductivity

    International Nuclear Information System (INIS)

    Crespi, V.H.; Cohen, M.L.; Penn, D.R.

    1991-01-01

    Anharmonic interionic potentials are examined in an Einstein model to study the unusual isotope-effect exponents for the high-T c oxides. The mass dependences of the electron-phonon coupling constant λ and the average phonon frequency √ left-angle ω 2 right-angle are computed from weighted sums over the oscillator levels. The isotope-effect exponent is depressed below 1/2 by either a double-well potential or a potential with positive quadratic and quartic parts. Numerical solutions of Schroedinger's equation for double-well potentials produce λ's in the range 1.5--4 for a material with a vanishing isotope-effect parameter α. However, low phonon frequencies limit T c to roughly 15 K. A negative quartic perturbation to a harmonic well can increase α above 1/2. In the extreme-strong-coupling limit, α is 1/2, regardless of anharmonicity

  9. Kinetic mechanism and isotope effects of Pseudomonas cepacia 3-hydroxybenzoate-t-hydroxylase

    International Nuclear Information System (INIS)

    Wang, L.H.; Yu, Y.; Hamzah, R.Y.; Tu, S.C.

    1986-01-01

    The kinetic mechanism of Pseudomonas cepacia 3-hydroxybenzoate-6-hydroxylase has been delineated. Double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a constant level of oxygen and several fixed concentrations of NADH yielded a set of converging lines. Similar reciprocal plots of velocity versus NADH concentration at a constant oxygen level and several fixed m-hydroxybenzoate concentrations also showed converging lines. In contrast, double reciprocal plots of initial rate versus NADH concentration at a fixed m-hydroxybenzoate level and several oxygen concentrations showed a series of parallel lines. Parallel lines were also obtained from double reciprocal plots of initial rate versus m-hydroxybenzoate concentration at a fixed NADH level and varying oxygen concentrations. These results suggest a sequential binding of m-hydroxybenzoate and NADH by the hydroxylase. The enzyme-bound FAD is reduced and NAD is released. The reduced enzyme subsequently reacts with oxygen leading to the formation of other products. This hydroxylase exhibited a primary isotope effect of /sup D/V = 3.5 for (4R)-[4- 2 H] NADH but no isotope effect was observed with (4S)-[4- 2 H]NADH. An isotope effect of /sup T/V/K = 5.0 was also observed using (4R)-[4- 3 H]NADH. This tritium isotope effect was apparently independent of m-hydroxybenzoate concentration

  10. Stable isotope methods: The effect of gut contents on isotopic ratios of zooplankton

    Science.gov (United States)

    Hill, J. M.; McQuaid, C. D.

    2011-05-01

    In the past decade there has been an increased awareness of the potential for methodological bias resulting from multiple pre-analytical procedures in foodweb interpretations based on stable isotope techniques. In the case of small organisms, this includes the effect of gut contents on whole body signatures. Although gut contents may not reflect actual assimilation, their carbon and nitrogen values will be isotopically lighter than after the same material has been assimilated. The potential skewing of isotopic ratios in whole organism samples is especially important for aquatic environments as many studies involve trophic relationships among small zooplankton. This is particularly important in pelagic waters, where herbivorous zooplankton comprise small taxa. Hence this study investigated the effect of gut contents on the δ13C and δ15N ratios of three size classes of zooplankton (1.0-2.0, 2.0-4.0 and >4.0 mm) collected using bongo net tows in the tropical waters of the south-west Indian Ocean. Animals were collected at night, when they were likely to be feeding, sieved into size classes and separated into genera. We focused on Euphausia spp which dominated zooplankton biomass. Three treatment types were processed: bulk animals, bulk animals without guts and tail muscle from each size class at 10 bongo stations. The δ15N ratios were influenced by zooplankton size class, presumably reflecting ontogenetic changes in diet. ANOVA post hoc results and correlations in δ15N signatures among treatments suggest that gut contents may not affect overall nitrogen signatures of Euphausia spp., but that δ13C signatures may be significantly altered by their presence. Carbon interpretations however, were complicated by potential effects of variation in chitin, lipids and metabolism among tissues and the possibility of opportunistic omnivory. Consequently we advocate gut evacuation before sacrifice in euphausiids if specific tissue dissection is impractical and recommend

  11. Shifts in rotifer life history in response to stable isotope enrichment: testing theories of isotope effects on organismal growth

    Science.gov (United States)

    2017-01-01

    In ecology, stable isotope labelling is commonly used for tracing material transfer in trophic interactions, nutrient budgets and biogeochemical processes. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism growth and metabolism. This assumption is, however, challenged by theoretical considerations and experimental studies on kinetic isotope effects in vivo. Here, I demonstrate profound changes in life histories of the rotifer Brachionus plicatilis fed 15N-enriched algae (0.4–5.0 at%); i.e. at the enrichment levels commonly used in ecological studies. These findings support theoretically predicted effects of heavy isotope enrichment on growth, metabolism and ageing in biological systems and underline the importance of accounting for such effects when using stable isotope labelling in experimental studies. PMID:28405367

  12. Low temperature isotope effects of hydrogen diffusion in metallic glasses

    International Nuclear Information System (INIS)

    Hofmann, A.; Kronmueller, H.

    1989-01-01

    Snoek-like relaxation peaks of Hydrogen and Deuterium in amorphous Fe 80 B 20 , Fe 40 Ni 40 P 14 B 6 and Fe 91 Zr 9 are detected. At low H, D concentrations the peaks are near 200 K and show small isotope effects of the average activation energies (anti Q H ≅ 0.6 eV, anti Q D - anti Q H ≤ 10 meV). For higher H, D-contents the peaks shift to lower temperatures around to 120 K and show distinct isotope effects in the activation energies (anti Q H ≅ 0.3 eV, anti Q D - anti Q H ≅ 30 meV) and in the amplitude of the low temperature tails of the relaxation peaks. This points to isotope mass dependent deviations from the Arrhenius law due to nonthermal tunneling processes. (orig.)

  13. Mathematical modeling of filling of gas centrifuge cascade for nickel isotope separation by various feed flow rate

    Science.gov (United States)

    Ushakov, Anton; Orlov, Alexey; Sovach, Victor P.

    2018-03-01

    This article presents the results of research filling of gas centrifuge cascade for separation of the multicomponent isotope mixture with process gas by various feed flow rate. It has been used mathematical model of the nonstationary hydraulic and separation processes occurring in the gas centrifuge cascade. The research object is definition of the regularity transient of nickel isotopes into cascade during filling of the cascade. It is shown that isotope concentrations into cascade stages after its filling depend on variable parameters and are not equal to its concentration on initial isotope mixture (or feed flow of cascade). This assumption is used earlier any researchers for modeling such nonstationary process as set of steady-state concentration of isotopes into cascade. Article shows physical laws of isotope distribution into cascade stage after its filling. It's shown that varying each parameters of cascade (feed flow rate, feed stage number or cascade stage number) it is possible to change isotope concentration on output cascade flows (light or heavy fraction) for reduction of duration of further process to set of steady-state concentration of isotopes into cascade.

  14. Attempt at estimating the rate of symbiotic fixation of nitrogen in the Lupine by natural isotopic tracing (/sup 15/N)

    Energy Technology Data Exchange (ETDEWEB)

    Amarger, Noelle [INRA Centre de Recherches de Dijon, 21 (France). Lab. de Microbiologie des Sols; Mariotti, Andre; Mariotti, Francoise [Paris-6 Univ., 75 (France)

    1977-06-06

    The rate of nitrogen fixation by a Rhizobium-Leguminous plant pair has been determined by natural isotopic tracing (/sup 15/N). After determining the isotopic fractionation coefficients between atmospheric nitrogen and plant nitrogen on the one hand (epsilon=-0.9) and nitrogen of the substrate and plant nitrogen on the other hand (epsilon=-1.1), the rate of nitrogen fixation by way of mixed nutrition cultures was calculated. The method is more accurate than standard methods.

  15. Mechanistic investigations of the hydrolysis of amides, oxoesters and thioesters via kinetic isotope effects and positional isotope exchange.

    Science.gov (United States)

    Robins, Lori I; Fogle, Emily J; Marlier, John F

    2015-11-01

    The hydrolysis of amides, oxoesters and thioesters is an important reaction in both organic chemistry and biochemistry. Kinetic isotope effects (KIEs) are one of the most important physical organic methods for determining the most likely transition state structure and rate-determining step of these reaction mechanisms. This method induces a very small change in reaction rates, which, in turn, results in a minimum disturbance of the natural mechanism. KIE studies were carried out on both the non-enzymatic and the enzyme-catalyzed reactions in an effort to compare both types of mechanisms. In these studies the amides and esters of formic acid were chosen because this molecular structure allowed development of methodology to determine heavy-atom solvent (nucleophile) KIEs. This type of isotope effect is difficult to measure, but is rich in mechanistic information. Results of these investigations point to transition states with varying degrees of tetrahedral character that fit a classical stepwise mechanism. This article is part of a special issue entitled: Enzyme Transition States from Theory and Experiment. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

    Science.gov (United States)

    Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

    2014-05-20

    Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

  17. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE dehalogenation was investigated. Selective biotransformation reactions (i of tetrachloroethene (PCE to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii of TCE to cis-1,2-dichloroethene (cis-DCE in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were −19.0‰ ± 0.9‰ (PCE and −12.2‰ ± 1.0‰ (TCE (95% confidence intervals. Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (−5.0‰ ± 0.1‰ and TCE (−3.6‰ ± 0.2‰. In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by −16.3‰ ± 1.4‰ (standard error than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of −2.4‰ ± 0.3‰ and the product chloride an isotope effect of −6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals. A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect. These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition. This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I or single electron transfer as reductive dehalogenation mechanisms.

  18. Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition

    International Nuclear Information System (INIS)

    Zielinski, M.; Zielinska, A.; Papiernik-Zielinska, H.; McKenzie, J.A.; Bernasconi, S.; Paul, H.

    1998-01-01

    Carbon-13 and oxygen-18 isotope effects in the decarboxylation of nicotinic acid of natural isotopic composition above and below its melting temperature have been studied and compared with the primary (PKIE) and secondary kinetic isotope effects (SKIE) of 13 C and 18 O, respectively, in the decarboxylation of other heterocyclic acids. The temperature dependence of the secondary oxygen-18 isotope effects is negative in the total 221-255 deg C temperature interval investigated initially. The 13 C KIE measured above melting point of N.A. (temperature interval 235-270 deg C) are located in the range 1.007-1.009. Below melting point of nicotinic acid the 13 C KIE are larger and reveal the negative temperature dependence ( 13 C KIE decreases with decreasing the reaction temperature from 1.013/at 230 deg C to 1.0114/at 221 deg C). A discussion of the above isotopic results is presented. (author)

  19. Evaluation of the isotope separation rate of deuterium exchange reaction between H2 and H2O with platinum catalyst

    International Nuclear Information System (INIS)

    Kitamoto, Asashi; Takashima, Yoichi; Shimizu, Masami.

    1983-01-01

    The high performance catalysts of hydrophobic carrier with fully dispersed platinum were used to measure the isotope separation performance of hydrogen by the chemical exchange method. The continuous injection of oxygen on the order of 10 3 ppm was effective in regenerating catalyst activity and in maintaining high performance for a long time. The separation performance in a trickle bed column should be evaluated by using two parameters, ksub(g) and ksub(l). These two parameters were unified to the overall transfer coefficient ksub(fg), which may be sufficient in the estimation of overall performance or the design of a separation plant by the chemical exchange method. When one wants to increase the transfer rate in a chemical exchange column, the improvement of ksub(l) rather than ksub(g) may be more effective in increasing the overall transfer rate (its coefficient is expressed by ksub(fg) in this paper). (author)

  20. Muon transfer rates in collisions of hydrogen isotope mesic atoms on 'bare' nuclei. Multichannel adiabatic approach

    International Nuclear Information System (INIS)

    Korobov, V.I.; Melezhik, V.S.; Ponomarev, L.I.

    1992-01-01

    A numerical scheme for solving the problem of slow collisions in the three-body adiabatic approach is applied for calculation of muon transfer rates in collisions of hydrogen isotope atoms on bare nuclei. It is demonstrated that the multichannel adiabatic approach allows one to reach high accuracy results (∼3%) estimating the cross sections of charge transfer processes which are the best ones up to date. The method is appliable in a wide range of energies (0.001-50 eV) which is of interest for analysis of muon catalysed fusion experiments. 20 refs.; 3 figs.; 5 tabs

  1. The germanium isotopes production rate in background process in SAGE experiment

    International Nuclear Information System (INIS)

    Gavrin, V.N.; Gorbachev, V.V.; Ibragimova, T.V.; Cleveland, B.T.

    2002-01-01

    The analysis of the direct determination of systematics connected with the germanium isotopes generation of in background processes in radiochemical SAGE experiments on measuring solar neutrinos is described. The found 68 Ge generation rate is 6.5 (1 ± 1.0) times higher than expected; the generation rate of 69 Ge does not exceed preliminary evaluations. The result on 68 Ge corresponds to the systematic of cosmic ray muons of 5.8% (4.5 SNU) for the measured capture rate of solar neutrino of 77.0 SNU. To check the cosmic-ray muon influence of the SAGE systematic one suggests the experiment in place of underground scintillation telescope of the Baksan neutrino observatory on the Institute for Nuclear Research of the RAS [ru

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

    Science.gov (United States)

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

    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

  3. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  4. Magic numbers and isotopic effect of ion clusters

    International Nuclear Information System (INIS)

    Wang Guanghou

    1989-04-01

    The magic numbers and isotopic effect as well as stable configurations in relation to the charge state of the clusters are discussed. Ionic (atomic) clusters are small atomic aggregates, a physical state between gas and solid states, and have many interesting properties, some of them are more or less similar to those in nuclei

  5. The Isotopologue Record of Repeat Vital Effect Offenders: Tracking (Dis)equilibrium Effects in Sea Urchins and Nannofossil Using Clumped Isotopes

    Science.gov (United States)

    John, C. M.; Davies, A.; Drury, A. J.

    2016-12-01

    . Rapid precipitation of calcite is however not considered as a likely mechanism as skeletal components with the largest growth rates show no clear clumped isotope vital effects.

  6. Cytochrome P-450 dependent ethanol oxidation. Kinetic isotope effects and absence of stereoselectivity

    International Nuclear Information System (INIS)

    Ekstroem, G.; Norsten, C.; Cronholm, T.; Ingelman-Sundberg, M.

    1987-01-01

    Deuterium isotope effects [/sup D/(V/K)] and stereoselectivity of ethanol oxidation in cytochrome P-450 containing systems and in the xanthine-xanthine oxidase system were compared with those of yeast alcohol dehydrogenase. The isotope effects were determined by using both a noncompetitive method, including incubation of unlabeled of [1,1- 2 H 2 ] ethanol at various concentrations, and a competitive method, where 1:1 mixtures of [1- 13 C]- and [ 2 H 6 ] ethanol or [2,2,2- 2 H 3 ]- and [1,1- 2 H 2 ] ethanol were incubated and the acetaldehyde formed was analyzed by gas chromatography/mass spectrometry. The /sup D/(V/K) isotope effects of the cytochrome P-450 dependent ethanol oxidation were about 4 with liver microsomes from imidazole-, phenobarbital- or acetone-treated rabbits or with microsomes from acetone- or ethanol-treated rats. Similar isotope effects were reached with reconstituted membranes containing the rabbit ethanol-inducible cytochrome P-450 (LMeb), whereas control rat microsomes and membranes containing rabbit phenobarbital-inducible P-450 LM 2 oxidized the alcohol with /sup D/(V/K) of about 2.8 and 1.8, respectively. Addition of Fe/sup III/EDTA either to microsomes from phenobarbital-treated rabbits or to membranes containing P-450 LMeb significantly lowered the isotope effect. Incubations of all cytochrome P-450 containing systems of the xanthine-xanthine oxidase systems with (1R)- and (1S)-[1- 2 H] ethanol, revealed, taking the isotope effects into account, that 44-66% of the ethanol oxidized had lost the 1-pro-R hydrogen. The data indicate that cytochrome P-450 dependent ethanol oxidation is not stereospecific and that cleavage of the C 1 -H bond appears to be a rate-determining step in the catalysis by the ethanol-inducible form of P-450. The contribution of hydroxyl radicals in ethanol oxidation by the various enzymic systems is discussed

  7. Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

    The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

  8. Evidence for H2/D2 isotope effects on Fischer-Tropsch synthesis over supported ruthenium catalysts

    International Nuclear Information System (INIS)

    Kellner, C.S.; Bell, A.T.

    1981-01-01

    The effects of using D 2 rather than H 2 during Fischer-Tropsch synthesis were investigated using alumina- and silica-supported Ru catalysts. For the alumina-supported catalysts, the rate of CD 4 formation was 1.4 to 1.6 times faster than the formation of CH 4 . A noticeable isotope effect was also observed for higher molecular weight products. The magnitude of the isotope effects observed using the silica-supported catalyst was much smaller than that found using the alumina-supported catalysts. The formation of olefins relative to paraffins was found to be higher when H 2 rather than D 2 was used, independent of the catalyst support. The observed isotope effects are explained in terms of a mechanism for CO hydrogenation and are shown to arise from a complex combination of the kinetic and equilibrium isotope effects associated with elementary processes occurring on the catalyst surface

  9. Isotope effects accompanying evaporation of water from leaky containers.

    Science.gov (United States)

    Rozanski, Kazimierz; Chmura, Lukasz

    2008-03-01

    Laboratory experiments aimed at quantifying isotope effects associated with partial evaporation of water from leaky containers have been performed under three different settings: (i) evaporation into dry atmosphere, performed in a dynamic mode, (ii) evaporation into dry atmosphere, performed in a static mode, and (iii) evaporation into free laboratory atmosphere. The results demonstrate that evaporative enrichment of water stored in leaky containers can be properly described in the framework of the Craig-Gordon evaporation model. The key parameter controlling the degree of isotope enrichment is the remaining fraction of water in the leaking containers. Other factors such as temperature, relative humidity, or extent of kinetic fractionation play only minor roles. Satisfactory agreement between observed and predicted isotope enrichments for both (18)O and (2)H in experiments for the case of evaporation into dry atmosphere could be obtained only when molecular diffusivity ratios of isotope water molecules as suggested recently by Cappa et al. [J. Geophys. Res., 108, 4525-4535, (2003).] were adopted. However, the observed and modelled isotope enrichments for (2)H and (18)O could be reconciled also for the ratios of molecular diffusivities obtained by Merlivat [J. Chem. Phys., 69, 2864-2871 (1978).], if non-negligible transport resistance in the viscous liquid sub-layer adjacent to the evaporating surface is considered. The evaporation experiments revealed that the loss of mass of water stored in leaky containers in the order of 1%, will lead to an increase of the heavy isotope content in this water by ca. 0.35 and 1.1 per thousand, for delta (18)O and delta (2)H, respectively.

  10. Growth Rates and Mechanisms of Magmatic Orbicule Formation: Insights from Calcium Isotopes

    Science.gov (United States)

    Antonelli, M. A.; Watkins, J. M.; DePaolo, D. J.

    2017-12-01

    Orbicular diorites and granites are rare plutonic rock textures that remain enigmatic despite a century of study. Orbicules consist of a rounded core (xenolith, xenocryst, or autolith) surrounded by a variable number of concentric rings defined by different modal mineralogies and textures. Recent work suggests that the alternating layers of mineral growth are a consequence of either changes in external conditions of the magma (e.g. temperature, magma composition due to mixing, changes in volatile abundances), or rapid growth of one mineral phase (e.g plagioclase) creating a depleted boundary layer that then promotes precipitation of an alternative mineral phase (e.g. pyroxene). This process can be repeated to produce multiple layers. The rates at which orbicules grow is also of interest and relates to the mechanisms. Studies of orbicular diorites from the northern Sierra Nevada suggest exceptionally high growth rates (McCarthy et al., 2016). Ca isotopes can offer a unique perspective on orbicule formation, as diffusive isotope fractionation should be substantial when growth rates are high, and they are also sensitive to the nature of the growth medium (silicate liquid or supercritical fluid phase). We present δ44Ca measurements and chemistry for a transect of a dioritic orbicule collected from Emerald Lake, California (Sierra Nevada), where the growth layers are defined by variations in plagioclase/pyroxene ratio, grain size, and texture. Ca concentration varies from 5-13 wt%, and d44Ca values oscillate between -0.5 to 0.0‰ relative to BSE, correlating with changes in mineralogy and texture. Zones of plagioclase comb texture are associated with negative δ44Ca excursions of -0.2 to -0.4‰, consistent with diffusive isotope fractionation during rapid mineral growth. Assuming a 10‰ difference in diffusivity for 44Ca vs. 40Ca in dioritic liquids (Watson et al., 2016), and using the models of Watson and Muller (2009) as a guide, these small fractionations

  11. Isotopic effects in the muon transfer from pmu and dmu to heavier atoms.

    Science.gov (United States)

    Dupays, Arnaud

    2004-07-23

    The results of accurate hyperspherical calculations of the muon-transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen, and neon are reported. Very good agreement with measured rates is obtained and, for the three systems, the isotopic effect is perfectly reproduced. The transfer rate is higher for deuterium in the cases of nitrogen and neon due to constructive interferences between two transfer paths. The lower transfer rate for deuterium in the case of oxygen results from a large resonant contribution. Copyright 2004 The American Physical Society

  12. Tritium conductivity and isotope effect in proton-conducting perovskites

    International Nuclear Information System (INIS)

    Mukundan, R.; Brosha, E.L.; Birdsell, S.A.; Costello, A.L.; Garzon, F.H.; Willms, R.S.

    1999-01-01

    The tritium ion conductivities of SrZr 0.9 Yb 0.1 O 2.95 and BaCe 0.9 Yb 0.1 O 2.95 have been measured by ac impedance analysis. The high tritium conductivity of these perovskites could potentially lead to their application as an electrochemical membrane for the recovery of tritium from tritiated gas streams. The conductivities of these perovskites, along with SrCe 0.95 Yb 0.05 O 2.975 , were also measured in hydrogen- and deuterium-containing atmospheres to illustrate the isotope effect. For the strontium zirconate and barium cerate samples, the impedance plot consists of two clearly resolved arcs, a bulk and a grain boundary arc, in the temperature range 50--350 C. However, for the strontium cerate sample, the clear resolution of the bulk conductivity was not possible and only the total conductivity was measurable. Thus, the isotope effect was clearly established only for the strontium zirconate and barium cerate samples. The decrease in bulk conductivity with increasing isotope mass was found to be a result of an increase in the activation energy for conduction accompanied by a decrease in the pre-exponential factor. Since the concentration of the mobile species (H+, D+, or T+) should remain relatively constant at T < 350 C, this increase in activation energy is directly attributable to the increased activation energy for the isotope mobility

  13. Modeling whole-tree carbon assimilation rate using observed transpiration rates and needle sugar carbon isotope ratios.

    Science.gov (United States)

    Hu, Jia; Moore, David J P; Riveros-Iregui, Diego A; Burns, Sean P; Monson, Russell K

    2010-03-01

    *Understanding controls over plant-atmosphere CO(2) exchange is important for quantifying carbon budgets across a range of spatial and temporal scales. In this study, we used a simple approach to estimate whole-tree CO(2) assimilation rate (A(Tree)) in a subalpine forest ecosystem. *We analysed the carbon isotope ratio (delta(13)C) of extracted needle sugars and combined it with the daytime leaf-to-air vapor pressure deficit to estimate tree water-use efficiency (WUE). The estimated WUE was then combined with observations of tree transpiration rate (E) using sap flow techniques to estimate A(Tree). Estimates of A(Tree) for the three dominant tree species in the forest were combined with species distribution and tree size to estimate and gross primary productivity (GPP) using an ecosystem process model. *A sensitivity analysis showed that estimates of A(Tree) were more sensitive to dynamics in E than delta(13)C. At the ecosystem scale, the abundance of lodgepole pine trees influenced seasonal dynamics in GPP considerably more than Engelmann spruce and subalpine fir because of its greater sensitivity of E to seasonal climate variation. *The results provide the framework for a nondestructive method for estimating whole-tree carbon assimilation rate and ecosystem GPP over daily-to weekly time scales.

  14. Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

    OpenAIRE

    Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

    1992-01-01

    The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuo...

  15. Implantation rate effects on microstructure

    International Nuclear Information System (INIS)

    Choyke, W.J.; Spitznagel, J.A.; Wood, S.; Doyle, N.J.

    1981-01-01

    We report a detailed TEM study of rate effects in a metal (304 SS) where we dope with an insoluble atom (He) and create the displacement damage with high energy Si. The rates of doping and the rates of producing lattice damage are independently varied during dual implantation. In addition to varying the doping rates of the He the magnitude of the displacement damage prior to He implantation is also varied (beam history). We find that the beam history has virtually no effect on maximum bubble size but it has a major effect on the average cavity diameter. A weak dependence of cavity number density on helium implantation rate is found. The total dislocation density is relatively independent of the doping rate and beam history at 550 and 700 0 C, whereas the loop fraction is sensitive to beam history at these temperatures. Acicular precipitate formation is weakly dependent on doping, doping rate and more strongly dependent on doping concentration and temperature. This form of solute segregation is very sensitive to beam history. (orig.)

  16. A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

    Science.gov (United States)

    Ghosh, S.; Odom, A. L.

    2007-12-01

    Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg

  17. Isotope effects in photo dissociation of ozone with visible light

    Science.gov (United States)

    Früchtl, Marion; Janssen, Christof; Röckmann, Thomas

    2014-05-01

    Ozone (O3) plays a key role for many chemical oxidation processes in the Earth's atmosphere. In these chemical reactions, ozone can transfer oxygen to other trace gases. This is particularly interesting, since O3 has a very peculiar isotope composition. Following the mass dependent fractionation equation δ17O = 0.52 * δ18O, most fractionation processes depend directly on mass. However, O3 shows an offset to the mass dependent fractionation line. Processes, which show such anomalies, are termed mass independent fractionations (MIF). A very well studied example for a chemical reaction that leads to mass independent fractionation is the O3 formation reaction. To what degree O3 destruction reactions need to be considered in order to understand the isotope composition of atmospheric O3 is still not fully understood and an open question within scientific community. We set up new experiments to investigate the isotope effect resulting from photo dissociation of O3 in the Chappuis band (R1). Initial O3 is produced by an electric discharge. After photolysis O3 is collected in a cold trap at the triple point temperature of nitrogen (63K). O3 is then converted to O2 in order to measure the oxygen isotopes of O3 using isotope ratio mass spectrometry. To isolate O3 photo dissociation (R1) from O3 decomposition (R2) and secondary O3 formation (R3), we use varying amounts of carbon monoxide (CO) as O atom quencher (R4). In this way we suppress the O + O3 reaction (R3) and determine the isotope fractionation in R1 and R2 separately. We present first results on the isotope effects in O3 photo dissociation with visible light in the presence of different bath gases. Results are interpreted based on chemical kinetics modeling. (R1) O3 + hυ → O (3P) + O2 (R2) O3 + O (3P) → 2 O2 (R3) O + O2 + M → O3 + M (R4) O (3P) + CO + M → CO2 + M

  18. Marginal-Fermi-liquid theory and the isotope effect

    International Nuclear Information System (INIS)

    Nicol, E.J.; Carbotte, J.P.

    1991-01-01

    In the marginal-Fermi-liquid model, the coupling between two electrons is via charge (attractive) and spin (repulsive) fluctuations, and so it does not exhibit an isotope effect. To include this effect, an additional phonon contribution must be introduced. Using the case of YBa 2 Cu 3 O 7 , for illustrative purposes, with a total isotope effect coefficient of β tot congruent 0.05 at a T c of 90 K, we find that the implied electron-phonon mass renormalization is very small for coupling to high-energy phonons but increases rapidly with decreasing phonon frequency or an increasing amount of spin fluctuations. Finally, we examine how β increases with decreasing T c when charge fluctuations are reduced or spin fluctuations augmented

  19. Level spectra, electromagnetic moments and transition rates and spectroscopic factors for odd rhodium isotopes in the Coriolis coupling model

    International Nuclear Information System (INIS)

    Bredbacka, A.; Brenner, M.; Malik, F.B.; Aabo Akademi, Turku

    1989-01-01

    Properties of low-lying positive- and negative-parity states of 97,99,101,103,105,107,109 Rh at low excitation energies have been analyzed in terms of a Coriolis coupling model. The model can account for the general trend of the level schemes for states of both parties. In particular, the 9/2, 7/2, and 5/2 triplet near the ground state, the occurrence of multiple 13/2 and at least one 15/2 and 19/2 state of positive parity are reasonably reproduced by the model. Similarly, 1/2 ground-state spin followed by a (3/2, 5/2) doublet, and one or more 13/2 and 17/2 states of negative parity are adequately understood in terms of the model. The calculated electromagnetic dipole and quadrupole moments and magnetic dipole and electric quadrupole transition rates are in broad agreement with the observed ones. This is achieved without the use of any effective charge. The general trend of observed spectroscopic factors for pick-up reactions is in agreement with the calculated ones. The results are presented as a function of deformation. Because of the sparsity of data on many of these isotopes, no attempt has been made to find the best fit for each isotope individually. Since the model can reasonably reproduce the general trend of level schemes, electromagnetic properties and spectroscopic factors, one may conclude that the Coriolis coupling model provides a good description of the nuclear properties of these isotopes. (orig.)

  20. Isotope effects in ion-exchange equilibria in aqueous and mixed solvent systems

    International Nuclear Information System (INIS)

    Gupta, A.R.

    1979-01-01

    Isotope effects in ion-exchange equilibria in aqueous and mixed solvents are analyzed in terms of the general features of ion-exchange equilibria and of isotope effects in chemical equilibria. The special role of solvent fractionation effects in ion-exchange equilibria in mixed solvents is pointed out. The various situations arising in isotope fractionation in ion exchange in mixed solvents due to solvent fractionation effects are theoretically discussed. The experimental data on lithium isotope effects in ion-exchange equilibria in mixed solvents are shown to conform to the above situations. The limitations of ion-exchange equilibria in mixed solvents for isotope fractionation are pointed out. 3 tables

  1. Kinetic tritium isotopic effects in the position 2 for 5'-hydroxy-L-tryptophane

    International Nuclear Information System (INIS)

    Boroda, E.; Kanska, M.

    2006-01-01

    Tryptophanase converts 5'-hydroxy-L-tryptophane to pyrogronic acid and ammonia, however there are known conditions for the reversed reaction. Mechanism of the processes are not known till now. Kinetic isotopic effect (KIE) permits finding the rate determining stage in the multistage process. In presented communication, 5'-hydroxy-[2- 3 H]-L-tryptophane was synthesized and the KIE in the room temperature determined for different reaction stages

  2. Absorption of carbon dioxide and isotope exchange rate of carbon in a reaction system between carbon dioxide and carbamic acid

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Kitamoto, Asashi

    1985-01-01

    The performance of isotope separation of carbon-13 by chemical exchange between carbon dioxide and carbamic acid was studied. The working fluid used in the study was a solution of DNBA, (C 4 H 9 ) 2 NH and n-octane mixture. Factors related to the isotope exchange rate were measured, such as the absorption rate of carbon dioxide into the solution of DNBA and n-octane, the isotope exchange rate and the separation factor in the reaction between CO 2 and carbamic acid. The absorption of CO 2 into the working fluid was the sum of chemical absorption by DNBA and physical absorption by n-octane. The absorption of carbon dioxide into the working fluid was negligible at temperatures over 90 0 C, but increased gradually at lower temperatures. Carbon dioxide was absorbed into DNBA by chemical absorption, and DNBA was converted to carbamic acid by the reaction. The reaction for synthesis and decomposition of carbamic acid was reversible. The separation factor in equilibrium reached a large value at lower temperatures. The isotope exchange rate between gas and liquid was proportional to the product of the concentration of carbamic acid and the concentration of CO 2 by physical absorption. The isotope separation of carbon by chemical exchange reaction is better operated under the conditions of lower temperature and higher pressure. (author)

  3. Cosmic-ray production rates of neon isotopes in meteorite minerals

    International Nuclear Information System (INIS)

    Bhandari, N.

    1988-01-01

    The rates of production of 21 Ne and 22 Ne in spallation reactions, both due to solar as well as galactic cosmic rays, in some major meteoritic minerals, e.g. olivines, feldspars and pyroxenes, are calculated using their energy spectra and excitation functions. The production profiles of 21 Ne and 22 Ne due to galactic cosmic rays, and the 22 Ne/ 21 Ne ratio depend upon the size of the meteoroid. The 22 Ne/ 21 Ne ratio is very sensitive to the abundance of sodium and consequently its depth profile is distinctly different in feldspars, the ratio increasing with depth rather than decreasing as in pyroxenes and olivines. In the near-surface regions, up to a depth of 2 cm, production due to solar flare protons dominates, giving rise to a steep gradient in isotopic production as well as in the 22 Ne/ 21 Ne ratio. Composite production profiles are given and compared with measurements in some meteorites. (author). 22 refs

  4. Assessment of sedimentation rate and hydrodynamics of Vembanad lagoon, Southern India, using isotope techniques

    International Nuclear Information System (INIS)

    Jacob, Noble; Joseph, T.B.; Hari Kumar, P.S.

    2012-01-01

    Wetlands are natural ecosystems that contribute to flood mitigation, fish and wildlife habitat protection and natural retention of pollutants and nutrients. Despite the importance, wetlands all over the world are undergoing severe degradation in the recent years, because of pollution and human interventions. Hydrology and water quality are the important factors controlling the ecological processes of wetlands and their understanding is essential for the wetlands restoration and management. Vembanad Lagoon, a major component of the Vembanad wetland system, is one of the largest coastal ecosystems in the southwestern part of India. Currently, it is facing numerous problems such as water quality deterioration due to ingression of saltwater, heavy metal contamination, weed infestation etc. and sedimentation due to large scale reclamation, intensive agriculture practices together with deforestation in its catchments. Hence, an isotope investigation was carried out to assess the sedimentation rate, pollution levels in sediments and hydrodynamics of Vembanad Lagoon

  5. Aerodynamic effects in isotope separation by gaseous diffusion

    International Nuclear Information System (INIS)

    Bert, L.A.; Prosperetti, A.; Fiocchi, R.

    1978-01-01

    The turbulent flow of an isotopic mixture in a porous-walled pipe is considered in the presence of suction through the wall. A simple model is formulated for the evaluation of aerodynamic effects on the separation efficiency. The predictions of the model are found to compare very favourably with experiment. In the limit of small suction velocities, results obtained by other investigators for diffusion in a turbulent steam are recovered. (author)

  6. Vapour pressure isotope effects in liquid hydrogen chloride

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, J.N.C.; Calado, J.C.G. (Instituto Superior Tecnico, Lisbon (Portugal)); Jancso, Gabor (Hungarian Academy of Sciences, Budapest (Hungary). Central Research Inst. for Physics)

    1992-08-10

    The difference between the vapour pressures of HCl and DCl has been measured over the temperature range 170-203 K by a differential manometric technique in a precision cryostat. In this range the vapour pressure of HCl is higher than that of DCl by 3.2% at 170 K, decreasing to 0.9% at 200 K. The reduced partition function ratios f[sub l]/f[sub g] derived from the vapour pressure data can be described by the equation ln(f[sub l]/f[sub g]) = (3914.57[+-]10)/T[sup 2] - (17.730[+-]0.055)/T. The experimentally observed H-D vapour pressure isotope effect, together with the values on the [sup 35]Cl-[sup 37]Cl isotope effect available in the literature, is interpreted in the light of the statistical theory of isotope effects in condensed systems by using spectroscopic data of the vapour and liquid phases. The results indicate that the rotation in liquid hydrogen chloride is hindered. Temperature-dependent force constants for the hindered translational and rotational motions were invoked in order to obtain better agreement between the model calculation and experiment. (author).

  7. Effect of Interband Interaction on Isotope Effect Coefficient of Mg B2 Superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Kumvongsa, C.; Burakorn, A.; Changkanarth, P.; Maneeratanakul, S.

    2005-10-01

    In this research, the exact formula of Tc s equation and the isotope effect coefficient of two-band s-wave superconductors in weak-coupling limit are derived by considering the influence of interband interaction .In each band ,our model consist of two paring interactions : the electron-phonon interaction and non-electron-phonon interaction . According to the numerical calculation, we find that the isotope effect coefficient of MgB 2 , α=3 . 0 with T c 40 K can be found in the weak coupling regime and interband interaction of electron-phonon show more effect on isotope effect coefficient than interband interaction of non-phonon-electron

  8. Isotopic modeling of the sub-cloud evaporation effect in precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Salamalikis, V., E-mail: vsalamalik@upatras.gr [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Argiriou, A.A. [Laboratory of Atmospheric Physics, Department of Physics, University of Patras, GR 26500 Patras (Greece); Dotsika, E. [Stable Isotope Unit, Institute of Nanoscience and Nanotechnology, National Center of Scientific Research ‘Demokritos’, Ag. Paraskevi Attikis, 15310 Athens (Greece)

    2016-02-15

    In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a ‘heat capacity’ model providing high correlation coefficients for both isotopes (R{sup 2} > 80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH = 95%) sub-cloud evaporation is negligible and the

  9. Isotopic modeling of the sub-cloud evaporation effect in precipitation

    International Nuclear Information System (INIS)

    Salamalikis, V.; Argiriou, A.A.; Dotsika, E.

    2016-01-01

    In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a ‘heat capacity’ model providing high correlation coefficients for both isotopes (R"2 > 80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH = 95%) sub-cloud evaporation is negligible and the

  10. Carbon-13 isotope effects on 199Hg nuclear shielding

    International Nuclear Information System (INIS)

    Sebald, Angelika; Wrackmeyer, Bernd

    1985-01-01

    Secondary 13 C/ 12 C isotope effects on 199 Hg nuclear shielding (Δdeltasup(i)( 199 Hg)) are of interest because of the unusual shift to high frequency which has been observed for a few alkyl mercury compounds. Continuing interest in the NMR parameters of mercury compounds prompted a search for the values Δdeltasup(i)( 199 Hg) in a greater variety of organomercurials. This should help to find out about the range of Δdeltasup(i)( 199 Hg) and to obtain a firmer basis for the discussion of the high-frequency shifts. The data and experimental conditions are given for chemical shifts delta 199 Hg, coupling constants sup(n)J( 199 Hg 13 C) and 13 C/ 12 C isotope shifts Δdeltasup(i)( 199 Hg) of fourteen 199 Hg organomercury compounds. The results are discussed. (author)

  11. Selected bibliography on deuterium isotope effects and heavy water

    International Nuclear Information System (INIS)

    Dave, S.M.; Donde, M.M.

    1983-01-01

    In recent years, there has been a great deal of interest in using deuterium and heavy water not only in nuclear industry but also in various fields of basic as well as applied research in physics, chemistry and biology. As a result, the literature is being enriched with a large number of research papers and technical reports published each year. Thus, to enable the scientists to have an easy reference to these works, an endeavour has been made in this selected bibliography, to enlist the publications related to these fields. Since the interest is concerned mainly with heavy water production processes, deuterium isotope effects etc., several aspects (e.g. nuclear) of deuterium have not been covered here. The material in this bibliography which cites 2388 references has been classified under six broad headings, viz. (1) Production of heavy water, (2) Study of deuterium isotope effects, (3) Analysis and Properties of heavy water, (4) Laser Separation of deuterium, (5) Isotopic exchange reactions, and (6) Miscellaneous. The sources of information used for this compilation are chemical abstracts, nuclear science abstracts, INIS Atomindex and also some scattered search through journals and reports available in the B.A.R.C. library. However, in spite of sincere attempts for a wide coverage, no claim is being made towards the exhaustiveness of this bibliography. (author)

  12. A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

    Science.gov (United States)

    Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

    2014-12-01

    Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

  13. Thorium isotopes as indicators of scavenging rates in the Venice lagoon

    International Nuclear Information System (INIS)

    Cochran, J. K.; Hirschberg, D.J.; Barnes, C.

    1995-01-01

    The naturally occurring thorium isotopes 228 Th and 234 Th, produced in sea water from decay of 228 Ra and 238 U, respectively, were used to estimate the rate of scavenging onto particle surfaces and the rate of removal of particles from the water column of the Venice Lagoon. Large water samples (1000-2000 L) were collected at three sites in the shallow ( 2 -impregnated cartridges to extract dissolved thorium. Activities of particulate 234 Th ranged from 510 to 1335 μBq L -1 and dissolved 234 Th was -1 . Relative to calculated 238 U activities in the lagoon, the 234 Th data yielded mean residence times as short as 2 h for the scavenging of dissolved 234 Th onto particles and 12 h for the removal of particulate 234 Th. Resuspension rates of 0.6 to 8 mg cm -2 day -1 were estimated from the data on dissolved and particulate 234 Th, these values being comparable to those determined by sediment traps (1.8-9.5 mg cm -2 day -1 ) at the same sites. These results suggest that Th and other similarly reactive trace metals are removed rapidly from the waters of the Venice Lagoon to the sediments. 23 refs., 4 tabs., 2 figs

  14. Dual temperature effects on oxygen isotopic ratio of shallow-water coral skeleton: Consequences on seasonal and interannual records

    Science.gov (United States)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

    Oxygen isotopic ratio from coral skeleton is regarded for a long time as promising climate archives at seasonal scale. Although in isotopic disequilibrium relative to seawater, it is supposed to obey to the isotope thermometer. Indeed, coral oxygen isotopic records are strongly temperature dependent, but d18O-temperature calibrations derived from different corals are highly variable. The isotope thermometer assumption does not take into account vital effects due to biogenic origin of the mineral. Corals are animals living in symbiosis with algae (zooxanthellae). Interactions between symbiont photosynthesis and coral skeleton carbonation have been abundantly observed but they remain poorly understood and the effects of photosynthesis on coral growth and skeleton oxygen ratio are ignored. Coral cultured under two light conditions enabled to relate metabolic parameters and oxygen isotopic variability with photosynthetic activity. By examining responses provided by each colony they revealed that photosynthesis significantly affected d18O, by an opposite sense compared with the sole temperature influence. Since temperature and light changes are associated during seasonal variations, this complicates the interpretation of seasonal record. Additionally, this complexity is amplified because photosynthetic activity is also directly impacted by temperature variability. Thus, the annual isotopic amplitude due to the "physical" temperature influence is partly compensated through photosynthesis. Similar opposite effect is also shown by extension rate of the cultured colonies. First, we will examine and quantify consequences of photosynthesis on growth rate and oxygen isotopic signature, from cultured corals. Second, we will consider the consequences of this vital effect on data series, at seasonal and interannual time scales.

  15. Comparing past accumulation rate reconstructions in East Antarctic ice cores using 10Be, water isotopes and CMIP5-PMIP3 models

    Directory of Open Access Journals (Sweden)

    A. Cauquoin

    2015-03-01

    Full Text Available Ice cores are exceptional archives which allow us to reconstruct a wealth of climatic parameters as well as past atmospheric composition over the last 800 kyr in Antarctica. Inferring the variations in past accumulation rate in polar regions is essential both for documenting past climate and for ice core chronology. On the East Antarctic Plateau, the accumulation rate is so small that annual layers cannot be identified and accumulation rate is mainly deduced from the water isotopic composition assuming constant temporal relationships between temperature, water isotopic composition and accumulation rate. Such an assumption leads to large uncertainties on the reconstructed past accumulation rate. Here, we use high-resolution beryllium-10 (10Be as an alternative tool for inferring past accumulation rate for the EPICA Dome C ice core, in East Antarctica. We present a high-resolution 10Be record covering a full climatic cycle over the period 269 to 355 ka from Marine Isotope Stage (MIS 9 to 10, including a period warmer than pre-industrial (MIS 9.3 optimum. After correcting 10Be for the estimated effect of the palaeomagnetic field, we deduce that the 10Be reconstruction is in reasonably good agreement with EDC3 values for the full cycle except for the period warmer than present. For the latter, the accumulation is up to 13% larger (4.46 cm ie yr−1 instead of 3.95. This result is in agreement with the studies suggesting an underestimation of the deuterium-based accumulation for the optimum of the Holocene (Parrenin et al. 2007a. Using the relationship between accumulation rate and surface temperature from the saturation vapour relationship, the 10Be-based accumulation rate reconstruction suggests that the temperature increase between the MIS 9.3 optimum and present day may be 2.4 K warmer than estimated by the water isotopes reconstruction. We compare these reconstructions to the available model results from CMIP5-PMIP3 for a glacial and an

  16. Early and long-term mantle processing rates derived from xenon isotopes

    Science.gov (United States)

    Mukhopadhyay, S.; Parai, R.; Tucker, J.; Middleton, J. L.; Langmuir, C. H.

    2015-12-01

    Noble gases, particularly xenon (Xe), in mantle-derived basalts provide a rich portrait of mantle degassing and surface-interior volatile exchange. The combination of extinct and extant radioactive species in the I-Pu-U-Xe systems shed light on the degassing history of the early Earth throughout accretion, as well as the long-term degassing of the Earth's interior in association with plate tectonics. The ubiquitous presence of shallow-level air contamination, however, frequently obscures the mantle Xe signal. In a majority of the samples, shallow air contamination dominates the Xe budget. For example, in the gas-rich popping rock 2ΠD43, 129Xe/130Xe ratios reach 7.7±0.23 in individual step-crushes, but the bulk composition of the sample is close to air (129Xe/130Xe of 6.7). Thus, the extent of variability in mantle source Xe composition is not well-constrained. Here, we present new MORB Xe data and explore constraints placed on mantle processing rates by the Xe data. Ten step-crushes were obtained on a depleted popping glass that was sealed in ultrapure N2 after dredge retrieval from between the Kane-Atlantis Fracture Zone of the Mid Atlantic Ridge in May 2012. 9 steps yielded 129Xe/130Xe of 7.50-7.67 and one yielded 7.3. The bulk 129Xe/130Xe of the sample is 7.6, nearly identical to the estimated mantle source value of 7.7 for the sample. Hence, the sample is virtually free of shallow-level air contamination. Because sealing the sample in N2upon dredge retrieval largely eliminated air contamination, for many samples, contamination must be added after sample retrieval from the ocean bottom. Our new high-precision Xe isotopic measurements in upper mantle-derived samples provide improved constraints on the Xe isotopic composition of the mantle source. We developed a forward model of mantle volatile evolution to identify solutions that satisfy our Xe isotopic data. We find that accretion timescales of ~10±5 Myr are consistent with I-Pu-Xe constraints, and the last

  17. No diurnal variation in rate or carbon isotope composition of soil respiration in a boreal forest

    International Nuclear Information System (INIS)

    Betson, N.R.; Gottlicher, S.G.; Hogberg, P.; Hall, M.; Wallin, G.; Richter, A.

    2007-01-01

    This study evaluated the diurnal variability in the rate and stable carbon isotope ratio ((delta) 13 C) of soil respiration in a northern boreal forest, measured with opaque chambers after the removal of understory vegetation. The experiment was conducted in June and August 2004 at the Picea abies L. Karst-dominated Flakaliden Research Forest in northern Sweden, using unfertilized girdled-tree plots and unfertilized non-girdled tree plots. Soil respiration and (delta) 13 C of soil-respired carbon dioxide (CO 2 ) were measured every 4 hours on 6 plots, with a total of 11 sampling times over each 48 hour period. The purpose was to clarify an earlier study regarding the origin of diurnal patterns of soil CO 2 flux. This study explored whether the diurnal patterns were the result of photosynthetic CO 2 uptake during the day by the understory or whether there were underlying trends in soil respiration driven by plant root allocation. The sampling campaigns undertaken in this study investigated whether diurnal variations in soil respiration rate and (delta) 13 C exist in this ecosystem when no understory vegetation is present. Shoot photosynthesis and environmental parameters were measured simultaneously. Despite significant variations in climatic conditions and shoot photosynthetic rates in non-girdled trees, no diurnal patterns in soil respiration rates and (delta) 13 C were noted in either treatment. The lack of detectable diurnal changes in both treatments indicates that modeling of daily boreal forest carbon balances based on single instantaneous measurements are unlikely to be misconstrued by substantial diurnal trends. However, it was suggested that spatial variable should be accounted for, given the large standard errors. The impact of tree girdling on soil respiration rates also emphasized the significance of canopy photosynthesis in driving soil processes. 37 refs., 2 figs

  18. Salt effects on isotope partitioning and their geochemical implications: An overview

    International Nuclear Information System (INIS)

    Horita, J.; Cole, D.R.; Fortier, S.M.

    1996-01-01

    Essential to the use of stable isotopes as natural tracers and geothermometers is the knowledge of equilibrium isotope partitioning between different phases and species, which is usually a function of temperature only. The one exception known to date is oxygen and hydrogen isotope fractionation between liquid water and other phases (steam, gases, minerals), which changes upon the addition of salts to water, i.e., the isotope salt salt effect. Our knowledge of this effect, the difference between activity and composition (a-X) of isotopic water molecules in salt solutions, is very limited and controversial, especially at elevated temperatures. For the last several years, we have been conducting a detailed, systematic experimental study at Oak Ridge National Laboratory to determine the isotope salt effects from room temperature to elevated temperatures (currently to 500 degree C). From this effort, a simple, coherent picture of the isotope salt effect is emerging, that differs markedly from the complex results reported in the literature. In this communication, we present an overview on the isotope salt effect, obtained chiefly from our study. Observed isotope salt effects in salt solutions are significant even at elevated temperatures. The importance and implications of the isotope salt effect for isotopic studies of brine-dominated systems are also discussed in general terms

  19. Isotope enrichment effect of gaseous mixtures in standing sound vibration

    International Nuclear Information System (INIS)

    Knesebeck, R.L.

    1984-01-01

    When standing acoustic waves are excited in a tube containing a mixture of two gases, a partial zonal fractioning of the components arises as consequence of mass transport by diffusion, driven by the thermal and pressure gradients which are associeted with the standing waves. This effect is present in each zone corresponding to a quarter wavelength, with the heavier component becoming enriched at the nodes fo the standing waves and deplected at the crests. The magnitude of the enrichment in one of the components of a binary gas mixture is given by Δω=ap 2 /lambda [b + (1-bω)] 2 . Where ω is the mass concentration of the component in the mixture, a and b are parameters which are related to molecular proprieties of the gases, p is the relative pressure amplitude of the standing wave and lambda is its wavelength. For a natural mixture of uranium hexafluorate, with 0.715% of the uranium isotope 340 an enrichment of about 2 x 10 -6 % in the concentration of this isotope is theorecticaly attainable per stage consisting of a quarter wavelenght, when a standing acoustical wave of relative pressure amplitude of 0,2 and wavelenght of 20 cm is used. Since standing acoustical waves are easely excited in gas columns, an isotope enrichment plant made of a cascade of tubes in which standing waves are excited, is presumably feasible with relatively low investment and operation costs. (Author) [pt

  20. Deuterium kinetic isotope effects in the 1,4-dimethylenecyclohexane boat cope rearrangement

    International Nuclear Information System (INIS)

    Gajewski, J.J.; Jimenez, J.L.

    1986-01-01

    In order to examine the extent of bond making in the boat-like 3,3-sigmatropic shift transition states, trans-2,3-dimethyl-1,4-dimethylenecyclohexane (T) and its exomethylene tetradeuteria derivative (TXD) were prepared. The 3,3-shift of TXD at 305 0 C results in interconversion of starting material, 5,5,6,6-tetradeuterio-trans-2,3-dimethyl-1,4-dimethylene-cyclohexane (TND), and 2,2,3,3-tetradeuterio-anti-1,4-diethylidenecyclohexane (AD). A kinetic analysis of the first-order rate equations for the three-component system in both protio and deuterio species by numerical integration of the data and simplex minimization of the rate constants with symmetry and the assumption of no equilibrium or kinetic isotope effect on the TND-AD reaction gives a bond making kinetic isotope effect of 1/1.04 (0.04). The equilibrium isotope effects observed are 1/1.16 (0.04) so that the extent of bond formation in this boat-like bicyclo[2.2.2]octyl transition state is roughly 25%, a value to be compared with ca. 67% in chair-like acyclic 3,3-shift transition states. This rules out significant intervention of a bicyclo[2.2.2]octane-1,4-diyl intermediate or transition state. 30 references, 6 figures, 4 tables

  1. Stable Isotopes Reveal Rapid Enamel Elongation (Amelogenesis) Rates for the Early Cretaceous Iguanodontian Dinosaur Lanzhousaurus magnidens.

    Science.gov (United States)

    Suarez, Celina A; You, Hai-Lu; Suarez, Marina B; Li, Da-Qing; Trieschmann, J B

    2017-11-10

    Lanzhousaurus magnidens, a large non-hadrosauriform iguanodontian dinosaur from the Lower Cretaceous Hekou Group of Gansu Province, China has the largest known herbivorous dinosaur teeth. Unlike its hadrosauriform relatives possessing tooth batteries of many small teeth, Lanzhousaurus utilized a small number (14) of very large teeth (~10 cm long) to create a large, continuous surface for mastication. Here we investigate the significance of Lanzhousaurus in the evolutionary history of iguanodontian-hadrosauriform transition by using a combination of stable isotope analysis and CT imagery. We infer that Lanzhousaurus had a rapid rate of tooth enamel elongation or amelogenesis at 0.24 mm/day with dental tissues common to other Iguanodontian dinosaurs. Among ornithopods, high rates of amelogenesis have been previously observed in hadrosaurids, where they have been associated with a sophisticated masticatory apparatus. These data suggest rapid amelogenesis evolved among non-hadrosauriform iguanodontians such as Lanzhousaurus, representing a crucial step that was exapted for the evolution of the hadrosaurian feeding mechanism.

  2. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    International Nuclear Information System (INIS)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya.

    1982-01-01

    The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C 2 and C 3 fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO 2 appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown. (author)

  3. Isotope Effects in the Reactions of Chloroform Isotopologues with Cl, OH and OD

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Nielsen, Claus J.

    2009-01-01

    The kinetic isotope effects in the reactions of CHCl3, CDCl3, and 13CHCl3 with Cl, OH, and OD radicals have been determined in relative rate experiments at 298 ( 1 K and atmospheric pressure monitored by long path FTIR spectroscopy. The spectra were analyzed using a nonlinear least-squares spectral.......002, kCHCl3+OD/kCDCl3+OD ) 3.95 ( 0.03, and kCHCl3+OD/k13CHCl3+OD ) 1.032 ( 0.004. Larger isotope effects in the OH reactions than in the Cl reactions are opposite to the trends for CH4 and CH3Cl reported in the literature. The origin of these differences was investigated using electronic structure...

  4. α and β deuterium isotope effects in the hydrolysis of naphthalene tetrahydro epoxides: rate-limiting hydrogen migration in the spontaneous hydrolysis of 6-methoxy-1,2,3,4-tetrahydronaphthalene oxide

    International Nuclear Information System (INIS)

    Gillilan, R.E.; Pohl, T.M.; Whalen, D.L.

    1982-01-01

    Data are reported that indicate that 6-methoxy-1,2,3-tetrahydronaphthalene oxide undergoes a spontaneous reaction to yield mostly 6-methyoxy-2-tetralone. Hydrogen-migration is reported to be the rate determining step in the reaction. Reaction mechanisms involving a one-step reaction with a concurrent C-O bond cleavage and hydrogen migration or reversible C-O bond cleavage followed by the rate-limiting hydrogen migration are proposed, but no clear distinction between the schemes is made

  5. Measurement of Hepatic Protein Fractional Synthetic Rate with Stable Isotope Labeling Technique in Thapsigargin Stressed HepG2 Cells

    Science.gov (United States)

    Song, Juquan; Zhang, Xiao-jun; Boehning, Darren; Brooks, Natasha C.; Herndon, David N.; Jeschke, Marc G.

    2012-01-01

    Severe burn-induced liver damage and dysfunction is associated with endoplasmic reticulum (ER) stress. ER stress has been shown to regulate global protein synthesis. In the current study, we induced ER stress in vitro and estimated the effect of ER stress on hepatic protein synthesis. The aim was two-fold: (1) to establish an in vitro model to isotopically measure hepatic protein synthesis and (2) to evaluate protein fractional synthetic rate (FSR) in response to ER stress. Human hepatocellular carcinoma cells (HepG2) were cultured in medium supplemented with stable isotopes 1,2-13C2-glycine and L-[ring-13C6]phenylalanine. ER stress was induced by exposing the cells to 100 nM of thapsigargin (TG). Cell content was collected from day 0 to 14. Alterations in cytosolic calcium were measured by calcium imaging and ER stress markers were confirmed by Western blotting. The precursor and product enrichments were detected by GC-MS analysis for FSR calculation. We found that the hepatic protein FSR were 0.97±0.02 and 0.99±0.05%/hr calculated from 1,2-13C2-glycine and L-[ring-13C6]phenylalanine, respectively. TG depleted ER calcium stores and induced ER stress by upregulating p-IRE-1 and Bip. FSR dramatically decreased to 0.68±0.03 and 0.60±0.06%/hr in the TG treatment group (pisotope tracer incorporation technique is a useful method for studying the effects of ER stress on hepatic protein synthesis. PMID:22298954

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-03-01

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

  7. A change in coral extension rates and stable isotopes after El Niño-induced coral bleaching and regional stress events

    Science.gov (United States)

    Hetzinger, S.; Pfeiffer, M.; Dullo, W.-Chr.; Zinke, J.; Garbe-Schönberg, D.

    2016-09-01

    Coral reefs are biologically diverse ecosystems threatened with effective collapse under rapid climate change, in particular by recent increases in ocean temperatures. Coral bleaching has occurred during major El Niño warming events, at times leading to the die-off of entire coral reefs. Here we present records of stable isotopic composition, Sr/Ca ratios and extension rate (1940-2004) in coral aragonite from a northern Venezuelan site, where reefs were strongly impacted by bleaching following the 1997-98 El Niño. We assess the impact of past warming events on coral extension rates and geochemical proxies. A marked decrease in coral (Pseudodiploria strigosa) extension rates coincides with a baseline shift to more negative values in oxygen and carbon isotopic composition after 1997-98, while a neighboring coral (Siderastrea siderea) recovered to pre-bleaching extension rates simultaneously. However, other stressors, besides high temperature, might also have influenced coral physiology and geochemistry. Coastal Venezuelan reefs were exposed to a series of extreme environmental fluctuations since the mid-1990s, i.e. upwelling, extreme rainfall and sediment input from landslides. This work provides important new data on the potential impacts of multiple regional stress events on coral isotopic compositions and raises questions about the long-term influence on coral-based paleoclimate reconstructions.

  8. Validity of the tritiated thymidine method for estimating bacterial growth rates: measurement of isotope dilution during DNA synthesis

    International Nuclear Information System (INIS)

    Pollard, P.C.; Moriarty, D.J.W.

    1984-01-01

    The rate of tritiated thymidine incorporation into DNA was used to estimate bacterial growth rates in aquatic environments. To be accurate, the calculation of growth rates has to include a factor for the dilution of isotope before incorporation. The validity of an isotope dilution analysis to determine this factor was verified in experiments reported here with cultures of a marine bacterium growing in a chemostat. Growth rates calculated from data on chemostat dilution rates and cell density agreed well with rates calculated by tritiated thymidine incorporation into DNA and isotope dilution analysis. With sufficiently high concentrations of exogenous thymidine, de novo synthesis of deoxythymidine monophosphate was inhibited, thereby preventing the endogenous dilution of isoope. The thymidine technique was also shown to be useful for measuring growth rates of mixed suspensions of bacteria growing anaerobically. Thymidine was incorporated into the DNA of a range of marine pseudomonads that were investigated. Three species did not take up thymidine. The common marine cyanobacterium Synechococcus species did not incorporate thymidine into DNA

  9. 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.

    Science.gov (United States)

    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.

  10. Monopole Effect on Isotopes in Sn and Pb Regions

    Directory of Open Access Journals (Sweden)

    M. KHITER

    2016-11-01

    Full Text Available Abstract. When going toward in description of neutron-rich nuclei, the monopole field plays a determining role in the properties of the quasiparticle states and their interactions. Detailed theoretical in shell model calculations of the characteristics of the neutron-rich isotopes in 132Sn and 208Pb regions are performed using the monopole hamiltonien effect. Some modification mentioned in literatures of effectives interactions are introduced for evaluated the effective single-particle energies. Their effect show a successful and consistent description of excitation energies spectra of these nuclei.Keywords:Nuclear Structure, Monopole Hamiltonian, Odd-Odd Nuclei,Three body Effects, Similarity, 21.60.Cs; 27.60. +j; 21.30.Fe

  11. Kinetics and mechanism of aquation and formation reactions of carbonato complexes. XII. Deuterium solvent isotope effect on the rate of acid-catalyzed decarboxylation of the carbonatobis (ethylenediamine) cobalt(III) complex ion. A mechanistic reappraisal

    International Nuclear Information System (INIS)

    Harris, G.M.; Hyde, K.E.

    1978-01-01

    A recent study of the acid-catalyzed decarboxylation of the carbonatotetrakis(pyridine)cobalt(III) complex ion showed there to be rate acceleration in D 2 O solvent, consistent with a proton-preequilibration mechanism. This observation directly contradicts the results of a similar study made some years ago of the analogous ion, carbonatobis(ethylenediamine)cobalt(III), for which there appeared to be deceleration in D 2 O solvent. A reinvestigation of the latter reaction over a much wider acidity range has now shown the earlier work to be in error. The previously proposed generalized mechanism for aquation of chelated carbonato complex ions of the form CoN 4 CO 3 + (N 4 identical with various tetramine ligand groupings of uni-, bi-, or quadridentate type) has thus been revised to include a proton equilibration step. An unexpected complication arises in the interpretation of the data for the bis(ethylenediamine) complex ion in the acidity range 0.1 + ] + ] term, overtakes and exceeds the true first-order rate constant for CO 2 release. The interesting implications of this unusual first-order successive reaction system are fully explored in the context of the present study

  12. Isotopic separation by ion chromatography

    International Nuclear Information System (INIS)

    Albert, M.G.; Barre, Y.; Neige, R.

    1994-01-01

    The isotopic exchange reaction and the isotopic separation factor are first recalled; the principles of ion chromatography applied to lithium isotope separation are then reviewed (displacement chromatography) and the process is modelled in the view of dimensioning and optimizing the industrial process; the various dimensioning parameters are the isotopic separation factor, the isotopic exchange kinetics and the material flow rate. Effects of the resin type and structure are presented. Dimensioning is also affected by physico-chemical and hydraulic parameters. Industrial implementation features are also discussed. 1 fig., 1 tab., 5 refs

  13. Daily cortisol production rate in man determined by stable isotope dilution/mass spectrometry

    International Nuclear Information System (INIS)

    Esteban, N.V.; Loughlin, T.; Yergey, A.L.; Zawadzki, J.K.; Booth, J.D.; Winterer, J.C.; Loriaux, D.L.

    1991-01-01

    Growth retardation as well as the development of Cushingoid features in adrenally insufficient patients treated with the currently accepted replacement dose of cortisol (33-41 mumol/day.m2; 12-15 mg/m2.day) prompted us to reevaluate the cortisol production rate (FPR) in normal subjects and patients with Cushing's syndrome, using a recently developed thermospray liquid chromatography-mass spectrometry method. The stable isotope [9,12,12-2H3]cortisol was infused continuously for 31 h at about 5% of the anticipated FPR. Blood samples were obtained at 20-min intervals for 24 h, spun, and pooled in 4-h groups. Tracer dilution in plasma was determined by liquid chromatography/mass spectrometry. The method was validated with controlled infusions in 6 patients with adrenal insufficiency. Results from 12 normal volunteers revealed a FPR of 27.3 +/- 7.5 mumol/day (9.9 +/- 2.7 mg/day) or 15.7 mumol/day.m2; 5.7 mg/m2. day. A previously unreported circadian variation in FPR was observed. Patients with Cushing's syndrome demonstrated unequivocal elevation of FPR and cortisol concentration correlated during each sample period in normal volunteers, indicating that cortisol secretion, rather than metabolism, is mainly responsible for changes in plasma cortisol. Our data suggest that the FPR in normal subjects may be lower than previously believed

  14. Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

    Science.gov (United States)

    Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

    2007-12-01

    and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

  15. Vinyl ether hydrolysis. VII. Isotope effects on catalysis by aqueous hydrofluoric acid

    International Nuclear Information System (INIS)

    Kresge, A.J.; Chen, H.J.; Chiang, Y.

    1977-01-01

    Comparison of rates of hydrolysis of three vinyl ethers catalyzed by HF in H 2 O and DF in D 2 O at 25 0 C gives primary isotope effects in the range k/sub H//k/sub D/ = 3.3 to 3.5. The unexpectedly small size of these effects may be attributed to strong, ω = 1325 to 1450 cm -1 , hydrogenic bending vibrations in the proton transfer transition states of these reactions along with the lack of compensatory bending vibrations in the diatomic proton donor

  16. Isotope effects in gas-phase chemical reactions and photodissociation processes: Overview

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

    The origins of isotope effects in equilibrium and non-equilibrium chemical processes are reviewed. In non-equilibrium processes, attention is given to isotope effects in simple bimolecular reactions, symmetry-related reactions, and photodissociation processes. Recent examples of isotope effects in these areas are reviewed. Some indication of other scientific areas for which measurements and/or calculations of isotope effects are used is also given. Examples presented focus on neutral molecule chemistry and in many cases complement examples considered in greater detail in the other chapters of this volume

  17. Soil erosion and sedimentation rates in a small eutrophic lake in southern Chile estimated by 210Pb isotope analysis

    International Nuclear Information System (INIS)

    Cisternas, M.; Urrutia, R.; Araneda, A.; Debels, P.; Rios, F.

    1999-01-01

    The purpose of this research is to study the effects of historical land use patterns on soil erosion within the San Pedro Lake watershed (Concepcion, VIII Region, Chile). To this end, a geochronological reconstruction of the last 50 years was accomplished by 210 Pb isotope and photo-interpretation analysis through the use of GIS. The erosion rate has varied from 0.40 t ha -1 y -1 in 1955 to 0.86 t ha -1 y -1 in 1994. The decrease in native forest was closely coupled with the increase in exotic forestry. The Total Change, meaning the land use change without considering each typology, shows a constant trend indicating a greater degree of anthropogenic intervention. As opposed to the expected, there is no relationship between land use typologies and erosion rates, however it is possible to recognise some degree of dependency between Total Change and erosion values. It is concluded that over the last 50 years the soil erosion processes in the San Pedro Lake watershed may have been more regulated more by land use changes than by land use typologies themselves. (author)

  18. Determining synthesis rates of individual proteins in zebrafish (Danio rerio) with low levels of a stable isotope labelled amino acid.

    Science.gov (United States)

    Geary, Bethany; Magee, Kieran; Cash, Phillip; Young, Iain S; Whitfield, Phillip D; Doherty, Mary K

    2016-05-01

    The zebrafish is a powerful model organism for the analysis of human cardiovascular development and disease. Understanding these processes at the protein level not only requires changes in protein concentration to be determined but also the rate at which these changes occur on a protein-by-protein basis. The ability to measure protein synthesis and degradation rates on a proteome-wide scale, using stable isotope labelling in conjunction with mass spectrometry is now a well-established experimental approach. With the advent of more selective and sensitive mass spectrometers, it is possible to accurately measure lower levels of stable isotope incorporation, even when sample is limited. In order to challenge the sensitivity of this approach, we successfully determined the synthesis rates of over 600 proteins from the cardiac muscle of the zebrafish using a diet where either 30% or 50% of the L-leucine was replaced with a stable isotope labelled analogue ([(2) H7 ]L-leucine]. It was possible to extract sufficient protein from individual zebrafish hearts to determine the incorporation rate of the label into hundreds of proteins simultaneously, with the two labelling regimens showing a good correlation of synthesis rates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Nitrogen Use Efficiency and Carbon Isotope Discrimination Study on NMR151 and NMR152 Mutant Lines Rice at Field Under Different Nitrogen Rates and Water Potentials

    International Nuclear Information System (INIS)

    Ahmad Nazrul Abdul Wahid; Shyful Azizi Abdul Rahman; Abdul Rahim Harun; Latiffah Nordin; Abdul Razak Ruslan; Hazlina Abdullah; Khairuddin Abdul Rahim

    2016-01-01

    This study was conducted to evaluate the nitrogen use efficiency and "1"3C isotope discrimination of rice mutant lines viz. NMR151 and NMR152. Both cultivars are developed under rice radiation mutagenesis programme for adaptability to aerobic conditions. In the present study, NMR151 and NMR152 were grown under conditions of varying water potentials and nitrogen levels in a field. Two water potentials and three nitrogen rates in a completely randomized design with three replications were carried out. The rice mutants were grown for 110 days under two water potentials, (i) Field capacity from 0 to 110 DAS [FC], and (ii) Field capacity from 0 to 40 DAS and 30 % dry of field capacity from 41 to 110 DAS [SS] and three nitrogen rates, (i) 0 kg N/ ha (0N), (ii) 60 kg N/ ha (60N), and (iii) 120 kg N/ ha (120N). "1"5N isotopic tracer technique was used in this study, whereby the "1"5N labeled urea fertilizer 5.20 % atom excess (a.e) was utilized as a tracer for nitrogen use efficiency (NUE) study. "1"5N isotope presence in the samples was determined using emission spectrometry and percentage of total nitrogen was determined by the Kjeldahl method. "1"5N a.e values of the samples were used in the determination of the NUE. The value of "1"3C isotope discrimination (Δ"1"3C) in the sample was determined using isotope ratio mass spectrometry (IRMS). The "1"3C isotope discrimination technique was used as a tool to identify drought resistance rice cultivars with improves water use efficiency. The growth and agronomy data, viz. plant height, number of tillers, grain yield, straw yield, and 1000 grain weight also were recorded. Results from this study showed nitrogen rates imparted significant effects on yield (grain and straw) plant height, number of tillers and 1000 grain weight. Water potentials had significant effects only on 1000 grain weight and Δ"1"3C. The NUE for both mutant lines rice showed no significant different between treatments. Both Rice mutant lines rice NMR151

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

    Science.gov (United States)

    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.

  1. Quantum tunneling observed without its characteristic large kinetic isotope effects.

    Science.gov (United States)

    Hama, Tetsuya; Ueta, Hirokazu; Kouchi, Akira; Watanabe, Naoki

    2015-06-16

    Classical transition-state theory is fundamental to describing chemical kinetics; however, quantum tunneling is also important in explaining the unexpectedly large reaction efficiencies observed in many chemical systems. Tunneling is often indicated by anomalously large kinetic isotope effects (KIEs), because a particle's ability to tunnel decreases significantly with its increasing mass. Here we experimentally demonstrate that cold hydrogen (H) and deuterium (D) atoms can add to solid benzene by tunneling; however, the observed H/D KIE was very small (1-1.5) despite the large intrinsic H/D KIE of tunneling (≳ 100). This strong reduction is due to the chemical kinetics being controlled not by tunneling but by the surface diffusion of the H/D atoms, a process not greatly affected by the isotope type. Because tunneling need not be accompanied by a large KIE in surface and interfacial chemical systems, it might be overlooked in other systems such as aerosols or enzymes. Our results suggest that surface tunneling reactions on interstellar dust may contribute to the deuteration of interstellar aromatic and aliphatic hydrocarbons, which could represent a major source of the deuterium enrichment observed in carbonaceous meteorites and interplanetary dust particles. These findings could improve our understanding of interstellar physicochemical processes, including those during the formation of the solar system.

  2. Charge exchange effect on laser isotope separation of atomic uranium

    International Nuclear Information System (INIS)

    Niki, Hideaki; Izawa, Yasukazu; Otani, Hiroyasu; Yamanaka, Chiyoe

    1982-01-01

    Uranium isotope separating experiment was performed using the two-step photoionization technique with dye laser and nitrogen laser by heating uranium metal with electron beam and producing atomic beam using generated vapour. The experimental results are described after explaining the two-step photoionization by laser, experimental apparatus, the selection of exciting wavelength and others. Enrichment factor depends largely on the spectrum purity of dye laser which is the exciting source. A large enrichment factor of 48.3 times was obtained for spectrum width 0.03A. To put the uranium isotope separation with laser into practice, the increase of uranium atomic density is considered to be necessary for improving the yield. Experimental investigation was first carried out on the charge exchange effect that seems most likely to affect the decrease of enrichment factor, and the charge exchange cross-section was determined. The charge exchange cross-section depends on the relative kinetic energy between ions and atoms. The experimental result showed that the cross-section was about 5 x 10 -13 cm 2 at 1 eV and 10 -13 cm 2 at 90 eV. These values are roughly ten times as great as those calculated in Lawrence Livermore Laboratory, and it is expected that they become the greatest factor for giving the upper limit of uranium atomic density in a process of practical application. (Wakatsuki, Y.)

  3. Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

    Science.gov (United States)

    Thiemens, Mark H

    2013-10-29

    Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    Deuterium isotope effects on 13C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on 13C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be nega...

  5. Ionic conductivity in aqueous solutions: deuterium isotope effect

    International Nuclear Information System (INIS)

    Samanta, Alok; Ghosh, Swapan K.

    1997-01-01

    A simple theoretical investigation of the calculation of ionic conductivity in aqueous solution is presented. The dipolar hard sphere model for the solvent which has been successful elsewhere has been employed here and it has been possible to reproduce the experimental results quite accurately for both water and heavy water using only two parameters. In a more detailed theoretical approach one should employ better models for water with proper account of its vibrations, liberations and also hydrogen bonding. It is also of interest to study the temperature effect and the concentration dependence of the conductivity. The time-dependent friction can also be calculated from the present formalism and be used for the study of isotope effect in proton transfer reactions or other aspects of chemical dynamics

  6. Kinetic isotope effect studies on milk xanthine oxidase and on chicken liver xanthine dehydrogenase

    International Nuclear Information System (INIS)

    D'Ardenne, S.C.; Edmondson, D.E.

    1990-01-01

    The effect of isotopic substitution of the 8-H of xanthine (with 2 H and 3 H) on the rate of oxidation by bovine xanthine oxidase and by chicken xanthine dehydrogenase has been measured. V/K isotope effects were determined from competition experiments. No difference in H/T (V/K) values was observed between xanthine oxidase and xanthine dehydrogenase. Xanthine dehydrogenase exhibited a larger T/D (V/K) value than that observed for xanthine oxidase. Observed H/T (V/K) values for either enzyme are less than those H/T (V/K) values calculated with D/T (V/K) data. These discrepancies are suggested to arise from the presence of a rate-limiting step(s) prior to the irreversible C-H bond cleavage step in the mechanistic pathways of both enzymes. These kinetic complexities preclude examination of whether tunneling contributes to the reaction coordinate for the H-transfer step in each enzyme. No observable exchange of tritium with solvent is observed during the anaerobic incubation of [8- 3 H]xanthine with either enzyme, which suggests the reverse commitment to catalysis (C r ) is essentially zero. With the assumption of adherence to reduced mass relationships, the intrinsic deuterium isotope effect ( D k) for xanthine oxidation is calculated. By the use of these values and steady-state kinetic data, the minimal rate for the hydrogen-transfer step is calculated to be ∼75-fold faster than k cat for xanthine oxidase and ∼10-fold faster than k cat for xanthine dehydrogenase. Values calculated for each enzyme were found to be identical within experimental uncertainty

  7. First-Principles Computed Rate Constant for the O + O2 Isotopic Exchange Reaction Now Matches Experiment.

    Science.gov (United States)

    Guillon, Grégoire; Honvault, Pascal; Kochanov, Roman; Tyuterev, Vladimir

    2018-04-19

    We show, by performing exact time-independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18 O + 32 O 2 , motivated by the understanding of a complex long-standing problem of isotopic ozone anomalies in the stratosphere and laboratory experiments, is explored in this context. The thermal rate constant for this key reaction is now in quantitative agreement with all experimental data available to date. A significant recent progress at the frontier of three research domains, advanced electronic structure calculations, ultrasensitive spectroscopy, and quantum scattering calculations, has therefore permitted a breakthrough in the theoretical modeling of this crucial collision process from first principles.

  8. The isotope altitude effect reflected in groundwater: a case study from Slovenia.

    Science.gov (United States)

    Mezga, Kim; Urbanc, Janko; Cerar, Sonja

    2014-01-01

    This paper presents the stable isotope data of oxygen (δ(18)O) and hydrogen (δ(2)H) in groundwater from 83 sampling locations in Slovenia and their interpretation. The isotopic composition of water was monitored over 3 years (2009-2011), and each location was sampled twice. New findings on the isotopic composition of sampled groundwater are presented, and the data are also compared to past studies regarding the isotopic composition of precipitation, surface water, and groundwater in Slovenia. This study comprises: (1) the general characteristics of the isotopic composition of oxygen and hydrogen in groundwater in Slovenia, (2) the spatial distribution of oxygen isotope composition (δ(18)O) and d-excess in groundwater, (3) the groundwater isotope altitude effect, (4) the correlation between groundwater d-excess and the recharge area altitude of the sampling location, (5) the relation between hydrogen and oxygen isotopes in groundwater in comparison to the global precipitation isotope data, (6) the groundwater isotope effect of distance from the sea, and (7) the estimated relation between the mean temperature of recharge area and δ(18)O in groundwater.

  9. Computational study of substrate isotope effect probes of transition state structure for acetylcholinesterase catalysis

    International Nuclear Information System (INIS)

    Sikorski, R.S.; Malany, S.; Seravalli, J.; Quinn, D.M.

    2002-01-01

    Secondary isotope effects for carbonyl addition reactions of methyl thioacetate, acetone and acetaldehyde have been calculated by ab initio quantum mechanical methods in an effect to interpret measured β-deuterium isotope effects on acetylcholinesterase-catalysed hydrolysis of acetylthiocholine. The calculated β-deuterium isotope effect for equilibrium addition of methanol to methyl thioacetate is D3 K eq = 0.965, and the corresponding effect for addition of methoxide ion to methyl thioacetate wherein three waters are hydrogen bonded to the carbonyl oxyanion is D3 K eq = 1.086. Neither of these calculated isotope effects is an inverse as the experimental β-deuterium isotope effect for acetylcholinesterase-catalysed hydrolysis of acetylthiocholine, D3 K eq = 0.90±0.03. Structural comparisons show that the water-solvated methoxide adduct of methyl thioacetate is more expanded than is the natural methanol addition adduct, and suggest that the degree of which the isotope effect is inverse (i.e. less than) is inversely correlated to the degree of expansion of the adduct. A similar correlation of α-deuterium and β-deuterium secondary isotope effects with the degree of expansion of the adducts is found for equilibrium additions of methanol and methoxide ion to acetylaldehyde. These computational results suggest that the markedly inverse β-deuterium isotope effect for the acetylcholinesterase reaction arises from enzymatic compression of the transition state. (author)

  10. Isotopic shifts in chemical exchange systems. 1. Large isotope effects in the complexation of Na+ isotopes by macrocyclic polyethers

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1981-01-01

    The complexation of 24 Na + and 22 Na + by 18 of the most widely used macrocyclic polyethers (crown ethers and monocyclic and bicyclic aminopolyethers) has been investigated in view of possible equilibrium isotope shifts. Solvated salts and polyether complexes were distributed differently into two phases and isotope ratios determined in both phases. Chloroform/water systems were shown to be particularly suitable to the investigations allowing favorable distribution for Na + and 13 of the 18 polyethers employed. With crown ethers 24 Na + enrichment varied from nonsignficant values (for large crown ethers) up to 3.1 +- 0.4% (18-crown-6). In the case of bicyclic aminopolyethers, ligands with cages of optimum size to accommodate Na + showed 24 Na + enrichment between O (nonsignificant) (2.2/sub B/2./sub B/) and 5.2 +- 1.8% (2.2.1). In contrast, for 2.2.2. and its derivatives, being too large for Na + , 22 Na + enrichment varying from O (nonsignificant) (2.2.2.p) up to 5.4 +- 0.5% (2.2.2.) has been observed. These values are remarkably high. They are explained by different bonding in solvate structure and polyether complex by using the theoretical approach of Bigeleisen

  11. Oxygen isotope effect on 55Mn nuclear magnetic shielding in permanganate

    International Nuclear Information System (INIS)

    Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.

    1976-01-01

    By Fourier transform NMR spectroscopy the 55 Mn resonance lines of the different permanganate species 55 Mn 16 Osub(4-n) 18 Osub(n) - (n=0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate. An isotope effect on the Larmor frequency of 55 Mn of (0.599 +- 0.015)ppm to lower frequency was found for the substition of an 16 O atom by an 18 O atom in the permanganate ion. An oxygen exchange rate in the permanganate-water system is given. (orig.) [de

  12. Isotope effect on superconductivity and Raman phonons of Pyrochlore Cd2Re2O7

    Science.gov (United States)

    Razavi, F. S.; Hajialamdari, M.; Reedyk, M.; Kremer, R. K.

    2018-06-01

    Cd2Re2O7 is the only α-Pyrochlore exhibiting superconductivity with a transition temperature (Tc) of ∼ 1 K. In this study, we present the effect of oxygen isotope (18O) as well as combined 18O and cadmium isotope (116Cd) substitution on the superconductivity and Raman scattering spectrum of Cd2Re2O7. The change of Tc and the energy gap Δ(T) are reported using various techniques including point contact spectroscopy. The shift in Raman phonon frequencies upon isotope substitution will be compared with measurement of the isotope effect on the superconducting transition temperature.

  13. Pre-steady state transients in the Drosophila alcohol dehydrogenase catalyzed reaction: isotope effects and stereospecificity

    International Nuclear Information System (INIS)

    Place, A.R.; Eccleston, J.F.

    1987-01-01

    The alcohol dehydrogenase (ADH) isolated from Drosophila is unique among alcohol metabolizing enzymes by not requiring metals for catalysis, by showing 4-pro-S (B-sided) hydride transfer stereospecificity, and by possessing a greater catalytic turnover rate for secondary alcohols than for primary alcohols. They have extended their studies on the kinetic mechanism for this enzyme by examining the pre-steady state transients of ternary complex interconversion using stopped-flow fluorescence methods. When enzyme and a 30-fold molar excess of NADH is mixed with excess acetadehyde, methyl ethyl ketone (MEK), or cyclohexanone a rapid (> 100 s -1 ) transient is observe before the steady-state. The rates are insensitive to isotope substitution. With the substrate MEK, the rate and amplitude suggests a single turnover of the enzyme. Similar pre-steady state transients are observed when enzyme and a 50-fold molar excess of NAD + is mixed with ethanol, 2-propanol, and cyclohexanol. The rates show a hyperbolic concentration dependence and a deuterium isotope effect. With d 6 -deuteroethanol the transient no longer occurs in the pre-steady state. When the optical isomers of secondary alcohols are used as substrates, transients are observed only in the R-(-) isomers for all chain lengths. With 2-S(+)-heptanol and 2-S(+)-octanol no transients occur

  14. Effects of Liraglutide on Heart Rate and Heart Rate Variability

    DEFF Research Database (Denmark)

    Kumarathurai, Preman; Anholm, Christian; Larsen, Bjørn Strøier

    2017-01-01

    OBJECTIVE: Reduced heart rate variability (HRV) and increased heart rate (HR) have been associated with cardiovascular mortality. Glucagon-like peptide 1 receptor agonists (GLP-1 RAs) increase HR, and studies have suggested that they may reduce HRV. We examined the effect of the GLP-1 RA...

  15. Kinetic α secondary deuterium isotope effects for O-ethyl S-phenyl benzaldehyde acetal hydrolysis

    International Nuclear Information System (INIS)

    Ferraz, J.P.; Cordes, E.H.

    1979-01-01

    The rate of hydrolysis of O-ethyl S-phenyl benzaldehyde acetal at 25 0 C in 20% dioxane--80% water is independent of pH over the range pH6-12; k/sub obsd/ = 1.9 x 10 -7 s -1 . Under more acidic conditions, the rate increases linearly with the activity of the hydrated proton; k 2 = 2.95 x 10 -2 M -1 s -1 . The kinetic α secondary deuterium isotope effect for acid-catalyzed hydrolysis of O-ethyl S-phenyl benzaldehyde acetal, measured at 25 0 C in 20% aqueous dioxane containing 0.05 M HCl, is k/sub H//k/sub D/ = 1.038 +- 0.008, a value consistent with a transition state in which the C--S bond is stretched rather little. In contrast, the corresponding isotope effect for the pH-independent hydrolysis of this substrate, measured at 42.5 0 C in 20% dioxane, is 1.13 +- 0.02, a value consistent with complete C--S bond cleavage in the transition state and rate-determining diffusion apart of the ion-pair formed as the initial intermediate, in accord with the suggestion of Jensen and Jencks. 1 figure, 4 tables

  16. Isotope Effect on the Thermal Conductivity of Graphene

    Directory of Open Access Journals (Sweden)

    Hengji Zhang

    2010-01-01

    Full Text Available The thermal conductivity (TC of isolated graphene with different concentrations of isotope (C13 is studied with equilibrium molecular dynamics method at 300 K. In the limit of pure C12 or C13 graphene, TC of graphene in zigzag and armchair directions are ~630 W/mK and ~1000W/mK, respectively. We find that the TC of graphene can be maximally reduced by ~80%, in both armchair and zigzag directions, when a random distribution of C12 and C13 is assumed at different doping concentrations. Therefore, our simulation results suggest an effective way to tune the TC of graphene without changing its atomic and electronic structure, thus yielding a promising application for nanoelectronics and thermoelectricity of graphene-based nano device.

  17. Mechanism of the flame ionization detector. II. Isotope effects and heteroatom effects

    DEFF Research Database (Denmark)

    Holm, Torkil

    1997-01-01

    The relative molar flame ionization detecton (FID) response (RMR) for a hydrocarbon does not change when deuterium is substituted for hydrogen. The exception is methane for which an inverse deuterium effect of 3..5% is observed for tetradeuteriomethane. [13C]Methane shows an inverse isotope effect...... of 2%. The reason for the small or non-existent isotope effects is that H/2H exchange takes place in the pre-combustion hydrogenolysis in the flame. This was shown by taking samples from the lower part of the flame by means of a fused silica capillary probe. By the same technique the hydrogenolytic...

  18. Hoof Growth Rates of the European Roe Deer (Capreolus capreolus for Dating the Hoof’s Isotopic Archive

    Directory of Open Access Journals (Sweden)

    Benjamin D. Hafner

    2017-11-01

    Full Text Available Hooves preserve the isotopic information laid down during their growth and may be used for reconstruction of animal feeding history. To assign certain positions along hooves to corresponding times, growth rates are required. Hoof growth rates are known for domestic animals; however, they cannot be obtained easily in wild animals. We estimated the hoof growth rate of the European roe deer (Capreolus capreolus L. by using the immediate drop in δ13C along the hoof as a tag that is assigned to the date of maize (Zea mays L. harvest. Keratin samples were taken each mm along 17 hooves and analyzed for their δ13C. A linear regression between (1 time differences of expected maize harvest to animal death and (2 distances between the points of the δ13C drop to the periople yielded the growth rate. Mean hoof growth rate was 0.122 mm/day (95% CI 0.014 mm/day and 0.365%/day (±0.026%/day of the hoof length and within the range of domestic animals. The method may be applied to determine growth rates of other incrementally growing tissues. Our estimated growth rate fosters dating isotopic information in hooves, facilitating research on feed resources and space use of roe deer.

  19. NMR spectroscopic determination of an equilibrium isotope effect on the hydration of cobalt(II)

    International Nuclear Information System (INIS)

    Evilia, R.F.; Saunders, M.

    1985-01-01

    A recently reported NMR method for the measurement of deuterium equilibrium isotope effects is applied to the hydration of the paramagnetic cobalt(II) ion. An isotope effect of about 1.3% is measured. A substantial difference between the intrinsic shift of H 2 O and D 2 O when coordinated to cobalt is also measured

  20. Electrochemical H-D isotope effect at metal-perovskite proton conductor interfaces

    DEFF Research Database (Denmark)

    Kek, D.; Bonanos, N.

    1999-01-01

    The H-D isotope effect on the electrode kinetics of a metal-proton conductor interface has been investigated. The current-voltage behaviour depends on the nature of the electrode (Ni, Ag), the atmosphere (H(2), D(2)), the partial pressures of the gases, and the temperature. The isotope effect was...

  1. A modified Gaussian integration method for thermal reaction rate calculation in U- and Pu-isotopes

    International Nuclear Information System (INIS)

    Bosevski, T.; Fredin, B.

    1966-01-01

    An advanced multi-group cell calculations a lot of data information is very often necessary, and hence the data administration will be elaborate, and the spectrum calculation will be time consuming. We think it is possible to reduce the necessary data information by using an effective reaction rate integration method well suited for U- and Pu-absorptions (author)

  2. Isotopic dilution methods to determine the gross transformation rates of nitrogen, phosphorus, and sulfur in soil: a review of the theory, methodologies, and limitations

    International Nuclear Information System (INIS)

    Di, H. J.; Cameron, K. C.; McLaren, R. G.

    2000-01-01

    The rates at which nutrients are released to, and removed from, the mineral nutrient pool are important in regulating the nutrient supply to plants. These nutrient transformation rates need to be taken into account when developing nutrient management strategies for economical and sustainable production. A method that is gaining popularity for determining the gross transformation rates of nutrients in the soil is the isotopic dilution technique. The technique involves labelling a soil mineral nutrient pool, e.g. NH 4 + , NO 3 - , PO 4 3- , or SO 4 2- , and monitoring the changes with time of the size of the labelled nutrient pool and the excess tracer abundance (atom %, if stable isotope tracer is used) or specific activity (if radioisotope is used) in the nutrient pool. Because of the complexity of the concepts and procedures involved, the method has sometimes been used incorrectly, and results misinterpreted. This paper discusses the isotopic dilution technique, including the theoretical background, the methodologies to determine the gross flux rates of nitrogen, phosphorus, and sulfur, and the limitations of the technique. The assumptions, conceptual models, experimental procedures, and compounding factors are discussed. Possible effects on the results by factors such as the uniformity of tracer distribution in the soil, changes in soil moisture content, substrate concentration, and aeration status, and duration of the experiment are also discussed. The influx and out-flux transformation rates derived from this technique are often contributed by several processes simultaneously, and thus cannot always be attributed to a particular nutrient transformation process. Despite the various constraints or possible compounding factors, the technique is a valuable tool that can provide important quantitative information on nutrient dynamics in the soil-plant system. Copyright (2000) CSIRO Publishing

  3. Effect of density of state on isotope effect exponent of two-band superconductors

    International Nuclear Information System (INIS)

    Udomsamuthirun, P.; Kumvongsa, C.; Burakorn, A.; Changkanarth, P.; Yoksan, S.

    2005-01-01

    The exact formula of T c 's equation and the isotope effect exponent of two-band s-wave superconductors in weak-coupling limit are derived by considering the influence of two kinds of density of state: constant and van Hove singularity. The paring interaction in each band consisted of two parts: the electron-phonon interaction and non-electron-phonon interaction are included in our model. We find that the interband interaction of electron-phonon show more effect on isotope exponent than the intraband interaction and the isotope effect exponent with constant density of state can fit to experimental data, MgB 2 and high-T c superconductor, better than van Hove singularity density of state

  4. Investigation of the enzymatic mechanism of yeast orotidine-5'-monophosphate decarboxylase using 13C kinetic isotope effects

    International Nuclear Information System (INIS)

    Smiley, J.A.; Bell, J.B.; Jones, M.E.; Paneth, P.; O'Leary, M.H.

    1991-01-01

    Orotidine-5'-monophosphate decarboxylase (ODCase) from Saccharomyces cerevisiae displays an observed 13 C kinetic isotope effect of 1.0247 ± 0.0008 at 25 C, pH 6.8. The observed isotope effect is sensitive to changes in the reaction medium, such as pH, temperature, or glycerol content. The value of 1.0494 ± 0.0006 measured at pH 4.0, 25 C, is not altered significantly by temperature or glycerol, and thus the intrinsic isotope effect for the reaction is apparently being observed under these conditions and decarboxylation is almost entirely rate-determining. These data require a catalytic mechanism with freely reversible binding and one in which a very limited contribution to the overall rate is made by chemical steps preceding decarboxylation; the zwitterion mechanism of Beak and Siegel, which involves only protonation of the pyrimidine ring, is such a mechanism. With use of an intrinsic isotope effect of 1.05, a partitioning factor of less than unity is calculated for ODCase at pH 6.0, 25 C. A quantitative kinetic analysis using this result excludes the possibility of an enzymatic mechanism involving covalent attachment of an enzyme nucleophile to C-5 of the pyrimidine ring. These data fit a kinetic model in which an enzyme proton necessary for catalysis is titrated at high pH, thus providing evidence for the catalytic mechanism of Beak and Siegal

  5. Possibilities and scope of the double isotope effect method in the elucidation of mechanisms of enzyme catalyzed reactions

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, H L; Medina, R [Technische Univ. Muenchen, Freising (Germany, F.R.). Lehrstuhl fuer Allgemeine Chemie und Biochemie

    1991-01-01

    Kinetic isotope effects on enzyme catalyzed reactions are indicative for the first irreversible in a sequence of individual steps. Hints on the relative velocities of other steps can only be obtained from the partitioning factor R and its dependence on external reaction conditions. In general, the experimental data needed are obtained from isotope abundance measurements in a defined position of the substrate or product as a function of turnover. This method does not reveal events dealing with neighbour atoms or preceding the main isotope sensitive step. In the method presented here, the analytical measurement is extended to the second atom involved in a bond fission of formation (Double Isotope Effect Method). It is shown that the additional results obtained support the identification of the main isotopically sensitive step and its relative contribution to the overall reaction rate, the identification of other kinetically significant steps and the differentiation between stepwise and concerted reaction mechanisms. The method and its advantages are demonstrated on reactions comprising C-N-bond splitting (urease and arginase reaction), C-C-bound fission (reactions catalyzed by pyruvate-dehydrogenase, pyruvate-formiate-lyase and lactate-oxidase), C-O-bound formation (ribulose-bisphosphate-oxygenase reaction), and N-O-bond fission (nitrate- and nitrite-reductase reactions). (orig.).

  6. Isotope effect and deuterium excess parameter revolution in ice and snow melt

    International Nuclear Information System (INIS)

    Yin Guan; Ni Shijun; Fan Xiao; Wu Hao

    2003-01-01

    The change of water isotope composition actually is a integrated reaction depending on the change of environment. The ice and snow melt of different seasons in high mountain can obviously influence the change of isotope composition and deuterium excess parameter of surface flow and shallow groundwater. To know the isotopic fractionation caused by this special natural background, explore its forming and evolvement, is unusually important for estimating, the relationship between the environment, climate and water resources in an area. Taking the example of isotope composition of surface flow and shallow groundwater in Daocheng, Sichuan, this paper mainly introduced the changing law of isotope composition and deuterium excess parameter of surface flow and hot-spring on conditions of ice and snow melt with different seasons in high mountain; emphatically discussed the isotope effect and deuterium excess parameter revolution in the process of ice and snow melting and its reason. (authors)

  7. Fusion rates for hydrogen isotopic molecules of relevance for ''cold fusion''

    International Nuclear Information System (INIS)

    Szalewicz, K.; Morgan, J.D. III; Monkhorst, H.J.

    1989-01-01

    In response to the recent announcements of evidence for room-temperature fusion in the electrolysis of D 2 O, we have analyzed how the fusion rate depends on the reduced mass of the fusing nuclei, the effective mass of a ''heavy'' electron, and the degree of vibrational excitation. Our results have been obtained both by accurately solving the Schroedinger equation for the hydrogen molecule and by using the WKB approximation. We find that in light of the reported d-d fusion rate, the excess heat in the experiment by Fleischmann, Pons, and Hawkins [J. Electroanal. Chem. 261, 301 (1989)] is difficult to explain in terms of conventional nuclear processes

  8. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

    Science.gov (United States)

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

    2016-04-01

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

  9. Effect of amino acids on the precipitation kinetics and Ca isotopic composition of gypsum

    Science.gov (United States)

    Harouaka, Khadouja; Kubicki, James D.; Fantle, Matthew S.

    2017-12-01

    Stirred gypsum (CaSO4 · 2H2O) precipitation experiments (initial Ωgypsum = 2.4 ± 0.14, duration ≈ 1.0-1.5 h) were conducted in the presence of the amino acids glycine (190 μM), L-alanine (190 μM), D- and L-arginine (45 μM), and L-tyrosine (200 μM) to investigate the effect of simple organic compounds on both the precipitation kinetics and Ca isotopic composition of gypsum. Relative to abiotic controls, glycine, tyrosine, and alanine inhibited precipitation rates by ∼22%, 27%, and 29%, respectively, while L- and D-arginine accelerated crystal growth by ∼8% and 48%, respectively. With the exception of tyrosine, amino acid induced inhibition resulted in fractionation factors (αs-f) associated with precipitation that were no more than 0.3‰ lower than amino acid-free controls. In contrast, the tyrosine and D- and L-arginine experiments had αs-f values associated with precipitation that were similar to the controls. Our experimental results indicate that Ca isotopic fractionation associated with gypsum precipitation is impacted by growth inhibition in the presence of amino acids. Specifically, we propose that the surface-specific binding of amino acids to gypsum can change the equilibrium fractionation factor of the bulk mineral. We investigate the hypothesis that amino acids can influence the growth of gypsum at specific crystal faces via adsorption and that different faces have distinct fractionation factors (αface-fluid). Accordingly, preferential sorption of amino acids at particular faces changes the relative, face-specific mass fluxes of Ca during growth, which influences the bulk isotopic composition of the mineral. Density functional theory (DFT) calculations suggest that the energetic favorability of glycine sorption onto gypsum crystal faces occurs in the order: (1 1 0) > (0 1 0) > (1 2 0) > (0 1 1), while glycine sorption onto the (-1 1 1) face was found to be energetically unfavorable. Face-specific fractionation factors constrained by

  10. Kinetics, isotope effects, and mechanism for the hydrogenation of carbon monoxide on supported nickel catalysts

    International Nuclear Information System (INIS)

    Mori, T.; Masuda, H.; Imai, H.; Miyamoto, A.; Baba, S.; Murakami, Y.

    1982-01-01

    Kinetics and hydrogen-deuterium isotope effects in the methanation of adsorbed CO molecules on a Ni/SiO 2 catalyst were precisely measured by using pulse surface reaction rate analysis (PSRA). When a CO pulse was injected into flowing hydrogen, it was immediately adsorbed on the catalyst and gradually hydrogenated to CH 4 and H 2 O. The amounts of CH 4 and H 2 O produced by the hydrogenation of the adsorbed CO were determined up to various times, and it was found that CH 4 and H 2 O were produced at the same rate. When O 2 instead of CO was injected, H 2 O was immediately produced. From these results, the rate-determining step of the reaction was found to be C-O bond dissociation of an adsorbed CO molecule or a partially hydrogenated CO species. By PSRA, the rate constant for the C-O bond dissocition process per adsorbed CO molecule (k/sub H/) was determined at various temperatures, and the Arrhenius parameters of the rate constant were obtained. The rate constant in flowing deuterium (k/sub D/) was also determined. it was found that k/sub D/ is considerably larger than k/sub H/, indicating an inverse isotope effect. The average value of k/sub H//k/sub D/ was 0.75. From these results, it was concluded that adsorbed CO is not directly dissociated to surface carbon and oxygen atoms but it is partially hydrogenated before C-O bond dissociation under the conditions of the PSRA experiment. 8 figures

  11. Silver diffusion and isotope effect in silver rubidium iodide

    International Nuclear Information System (INIS)

    Arzigian, J.S.

    1980-01-01

    The diffusion coefficient of silver in RbAg 4 I 5 was measured in both superionic phases using radiotracer Ag-110m and serial sectioning with a low temperature sectioning apparatus. The activation energies for diffusion in alpha-RbAg 4 I 5 and beta-RbAg 4 I 5 , respectively, are 0.11 +- 0.01 eV and 0.20 +- 0.04 eV. An isotope effect for diffusion was also measured in both superionic phases. Ag-105 and Ag-110m radioisotopes were used with gamma spectroscopy and energy discrimination. The effect is small, with no significant temperature variation, with the value at 333 0 K being 0.12 +- 0.01. The second-order phase transition at 208 0 K has a small effect, if any, on the magnitude of the effect. The data suggest that a highly cooperative transport mechanism is responsible for the unusually high values of both the conductivity and diffusion coefficient. Although it is not possible to deduce the particular mechanism involved, theories inolving ionic polarons, or cooperative motion, such as crowdions or solitons, seem consistent with the observed results

  12. Secondary isotope effects and tunneling in elimination reaction of quaternary ammonium salts

    International Nuclear Information System (INIS)

    Lin, S.

    1993-01-01

    In order to gain more experimental evidence of the tunneling effect on the non-transferred isotopically-substituted hydrogen in the rate determining step and to investigate in more detail concerning the variable nature of the E2 transition state, tritium tracer-labeled β- and/or α-phenyl substituted ethyltrimethylammonium ions in the elimination reaction and their 2,2-d 2 analogues were studied. The three different substrates are 2-(p-trifluoromethylphenyl)ethyltrimethylammonium bromide (I), 1-phenylethyltrimethylammonium bromide (II) and 1-phenyl- 2-p-chlorophenylethyltrimethylammonium bromide (III). The reactions were found to proceed via a concerted E2 process. The proton is more than one-half transferred to the base at the transition state, especially for case I and III. There is more C beta -H and less C alpha -N bond rupture at the transition state when an electron-withdrawing group is introduced on the β-phenyl ring, i.e., more carbonion character in the transition state. The secondary tritium isotope effects were measured and they were found larger than the maximum value. (1.17) for rehybridization. It was found that these values were strongly temperature dependent. They increase as the temperature goes down. The Arrenhius pre-exponential factors were below unity and the exponential factor to convert the isotope effect of D/T to H/T were much greater than predicted for zero-point energy effects alone (3.26). Tunneling turns to be the only plausible explanation. By reviewing this evidence, one may conclude that the contribution of tunneling is indeed a common occurrence in proton transfer processes. For elimination of compound I, the tunneling effect is greatest while it is less for the other two, which are about the same, but the nature of their transition states is quite different. The variable nature of the transition states for the three eliminations are discussed in terms of the More O'Ferral-Jencks diagram

  13. The dose-rate effect

    International Nuclear Information System (INIS)

    Steel, G.G.

    1989-01-01

    This paper presents calculations that illustrate two conclusions; for any particular cell type there will be a critical radius at which tumor control breaks down, and the radius at which this occurs is strongly dependent upon the low-dose-rate radiosensitivity of the cells

  14. Alpha heating and isotopic mass effects in JET plasmas with sawteeth

    Energy Technology Data Exchange (ETDEWEB)

    Budny, R. V. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States); Team, JET [EUROfusion Consortium, JET, Culham Science Centre, Abingdon, OX14 3DB, UK

    2016-02-09

    The alpha heating experiment in the Joint European Torus (JET) 1997 DTE1 campaign is re-examined. Several effects correlated with tritium content and thermal hydrogenic isotopic mass < A> weaken the conclusion that alpha heating was clearly observed. These effects delayed the occurrence of significant sawtooth crashes allowing the electron and ion temperatures T e and T i to achieve higher values. Under otherwise equal circumstances T e and T i were typically higher for discharges with higher < A >, and significant scaling of T i, T e, and total stored energy with < A > were observed. The higher T i led to increased ion–electron heating rates with magnitudes comparable to those computed for alpha electron heating. Rates of other heating/loss processes also had comparable magnitudes. Simulations of T e assuming the observed scaling of T i are qualitatively consistent with the measured profiles, without invoking alpha heating

  15. Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

    For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

  16. Investigation of hydrogen isotope exchange reaction rate in mixed gas (H2 and D2) at pressure up to 200 MPa using Raman spectroscopy

    International Nuclear Information System (INIS)

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

    2015-01-01

    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

  17. 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

    Energy Technology Data Exchange (ETDEWEB)

    Tikhonov, V.V.; Yukhimchuk, A.A.; Musyayev, R.K.; Gurkin, A.I. [Russian Federal Nuclear Center, All-Russian Research Institute of Experimental Physics, Sarov (Russian Federation)

    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.

  18. Isotopic effect on the quantum tunneling of the magnetization of molecular nanomagnets

    International Nuclear Information System (INIS)

    Sessoli, Roberta; Caneschi, Andrea; Gatteschi, Dante; Sorace, Lorenzo; Cornia, Andrea; Wernsdorfer, Wolfgang

    2001-01-01

    The molecular cluster [Fe 8 (tacn) 6 O 2 (OH) 12 ]Br 8 ·9H 2 O, Fe 8 , characterized by S=10, with biaxial magnetic anisotropy is an ideal system to investigate quantum effects in the dynamics of the magnetization. Resonant quantum tunneling gives rise to stepped hysteresis cycles and below 0.35 K pure quantum tunneling of the magnetization has been observed. The role of hyperfine fields in promoting the tunneling as a source of dynamic broadening of the states involved in the tunnel transition is investigated by preparing and characterizing two isotopically enriched samples using 57 Fe and 2 H. The relaxation rate in the tunneling regime is proportional to the hyperfine field generated by the nuclei. Also, the intrinsic linewidth of the tunneling resonance scales with the hyperfine field as confirmed by calculations of the super (or transfer) and direct hyperfine interactions. Preliminary results on a novel cluster of formula [Fe 4 (OCH 3 ) 6 (dpm) 6 ], Fe 4 , suited for a more dramatic isotope effect on the tunneling rate are also reported

  19. Isotopic effect on the quantum tunneling of the magnetization of molecular nanomagnets

    Energy Technology Data Exchange (ETDEWEB)

    Sessoli, Roberta E-mail: sessoli@chim1.unifi.it; Caneschi, Andrea; Gatteschi, Dante; Sorace, Lorenzo; Cornia, Andrea; Wernsdorfer, Wolfgang

    2001-05-01

    The molecular cluster [Fe{sub 8}(tacn){sub 6}O{sub 2}(OH){sub 12}]Br{sub 8}{center_dot}9H{sub 2}O, Fe{sub 8}, characterized by S=10, with biaxial magnetic anisotropy is an ideal system to investigate quantum effects in the dynamics of the magnetization. Resonant quantum tunneling gives rise to stepped hysteresis cycles and below 0.35 K pure quantum tunneling of the magnetization has been observed. The role of hyperfine fields in promoting the tunneling as a source of dynamic broadening of the states involved in the tunnel transition is investigated by preparing and characterizing two isotopically enriched samples using {sup 57}Fe and {sup 2}H. The relaxation rate in the tunneling regime is proportional to the hyperfine field generated by the nuclei. Also, the intrinsic linewidth of the tunneling resonance scales with the hyperfine field as confirmed by calculations of the super (or transfer) and direct hyperfine interactions. Preliminary results on a novel cluster of formula [Fe{sub 4}(OCH{sub 3}){sub 6}(dpm){sub 6}], Fe{sub 4}, suited for a more dramatic isotope effect on the tunneling rate are also reported.

  20. Effect of Calcium Oxide Microstructure on the Diffusion of Isotopes

    CERN Document Server

    Fernandes Ramos, João Pedro; Stora, T

    2012-01-01

    Calcium oxide (CaO) powder targets have been successfully used at CERN-ISOLDE to produce neutron deficient exotic argon and carbon isotopes under proton irradiation at high temperatures (>1000°C). These targets outperform the other related targets for the production of the same beams. However, they presented either slow release rates (yields) from the beginning or a rapid decrease over time. This problem was believed to come from the target microstructure degradation, justifying the material investigation. In order to do so, the synthesis, reactivity in ambient air and sintering kinetics of CaO were studied, through surface area determination by N2 adsorption, X-ray diffraction for crystalline phase identification and crystallite size determination, and scanning and transmission electron microscopy to investigate the microstructure. The synthesis studies revealed that a nanometric material is obtained from the decarbonation of CaCO3 in vacuum at temperatures higher than 550°C, which is very reactive in air....

  1. Determination of the variation of mercury isotope concentration based on spectral-phase effects

    International Nuclear Information System (INIS)

    Ganeev, A.A.; Man', D.D.; Turkin, Yu.I.

    1988-01-01

    A method of isotopic atomic-absorption analysis, based on spectral-phase effects in which there is no need to use several sources of radiation with pure isotopes of the analyte element, was developed. The method made it possible to simplify the analysis and to determine the variation of the concentration of mercury isotopes from one deposit to another with an accuracy several times higher that of traditional methods of spectral isotopic analysis. The method was tested on mercury 198 and mercury 202. The isotopic analyzer is diagramed and described. The mechanism of spectral-phase effects was determined by the difference in effective photon lifetimes, corresponding to different components of the hyperfine structure of the resonance line of mercury at 254 nm

  2. Effective Exchange Rate Classifications and Growth

    OpenAIRE

    Justin M. Dubas; Byung-Joo Lee; Nelson C. Mark

    2005-01-01

    We propose an econometric procedure for obtaining de facto exchange rate regime classifications which we apply to study the relationship between exchange rate regimes and economic growth. Our classification method models the de jure regimes as outcomes of a multinomial logit choice problem conditional on the volatility of a country's effective exchange rate, a bilateral exchange rate and international reserves. An `effective' de facto exchange rate regime classification is then obtained by as...

  3. Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

    Science.gov (United States)

    Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

    2014-01-01

    The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuous-flow technique using capillary GC/combustion IRMS. Quadriceps muscles were removed from four Sprague–Dawley rats after each was infused at a different rate with (1-13C)leucine for 6–8 h. Muscle leucine enrichment (at.% excess) measured by both methods differed by less than 4%, except at low (13C)leucine enrichments (IRMS was used to assess muscle (13C)leucine enrichment and fractional muscle protein synthesis rate in ten normal young men and women infused with (1,2-13C2)leucine for 12–14 h. This approach reduced the variability of the isotope abundance measure and gave estimates of muscle protein synthesis rate (0.050 ± 0.011% h−1 (mean ± SEM); range = 0.023–0.147% h−1) that agree with published values determined using the standard analytical approach. The measurement of (13C)leucine enrichment from skeletal muscle protein by capillary GC/combustion IRMS provides a simple, acceptable and practical alternative to preparative GC/ninhydrin IRMS. PMID:1420371

  4. Biological isotopy. Introduction to the isotopic effects and to their applications in biology

    International Nuclear Information System (INIS)

    Tcherkez, G.

    2010-01-01

    Since their discovery in the beginning of the 20. century, the study of stable isotopes has considerably developed. This domain, which remained limited in its applications until the 1990's, has become particularly important thereafter thanks to its practical applications and in particular to its economical impacts. Many techniques used in fraud control, in drugs use control, in selection of high-yield plants etc are based on isotopic abundance measurements. This reference book gives a synthesis of our actual knowledge on the use of stable isotopes and of isotope fractionation in biology. It presents the basic notions of isotopic biochemistry and explains the origin of the isotopic effects. The application principles of these effects to metabolism, to organisms physiology, to environmental biology etc are explained and detailed using examples and exercises. The first chapters present the basic knowledge which defines, from a mathematical point-of-view, the isotopic effects of chemical reactions or of physical processes taking place in biology. The measurements principle of natural isotopes abundance is then synthesised. Finally, all these notions are applied at different scales: enzymes, physiology, metabolism, environment, ecosystems and fraud crackdown. (J.S.)

  5. Isotope effect of impurity diffusion of cadmium in silver

    International Nuclear Information System (INIS)

    Rockosch, H.J.; Herzig, C.

    1984-01-01

    The isotope effect of impurity diffusion of cadmium in silver single crystals was measured with the radioisotopes 115 Cd/ 109 Cd by gamma spectrometry. As a mean value E = 0.37 at T = 1060 K was obtained. The correlation factor f /SUB Cd/ = 0.41 is in disagreement with previous results of other investigators due to their unfavourable experimental approach. The present value of f /SUB Cd/ , however, is consistent with those of In and Sn in Ag. A comparison with the corresponding correlation factors in the copper solvent reveals a distinct influence of lattice perturbations because of the different atomic volumes of the solvents. Since the size effect is neglected in the electrostatic diffusion model, the agreement with this model is only qualitative. The frequency ratios for vacancy jumps were calculated. The free binding enthalpy of the vacancy-impurity complex was estimated to be Δg /SUB Cd/ = -0.064 eV. This value is smaller than those for In and Sn in Ag and complies with the relative diffusivities of these impurities in Ag

  6. Use of stable and radioactive isotopes in the determination of the recharge rate in Djeffara aquifer system southern Tunisia

    International Nuclear Information System (INIS)

    Trabelisi, R.; Zouari, K.

    2012-12-01

    Southern Tunisia is characterized by the presence of several hydrogeological basins, which extend over Tunisian borders. The Djeffara aquifer is one of the most important aquifer systems n this area and contains several interconnected aquifer levels. Stable (δ 2 H, δ 18 O and δ 13 C) and radioactive isotopes (1 4C , 3 H ) have been used to evaluate recharge mechanisms and groundwater residence time in the Djeffara multi-aquifer. Thesis aquifer presents two compartments, the first one ( west of the Medenine fault system) is unconfined with a well defined isotope fingerprint, the second compartment is deeper and confined multi- tracer results show groundwater of different origins, and ages , and that tectonic features control ground water flows. The unconfined part was mostly recharged during the Holocene. The recharge rates of this aquifer, inferred by 1 4C ages, are variable and could reach 3.5 mm/year. However, stable isotope composition and 1 4 'C content of the confined groundwater indicates carrier recharge during late pelistocene cold periods. (Author)

  7. Effect of interband interaction on isotope effect exponent of MgB2 ...

    Indian Academy of Sciences (India)

    The interband interaction of the electron–phonon interaction shows more effect on the isotope exponent than on the non-phonon interaction. Acknowledgement. The authors would like to thank Thailand Research Fund for financial support and the University of the Thai Chamber of Commerce for partial financial support and.

  8. Isotope effects in lithium hydride and lithium deuteride crystals by molecular dynamics simulations.

    Science.gov (United States)

    Dammak, Hichem; Antoshchenkova, Ekaterina; Hayoun, Marc; Finocchi, Fabio

    2012-10-31

    Molecular dynamics (MD) simulations have been carried out to study isotope effects in lithium hydride and lithium deuteride crystals. Quantum effects on nuclear motion have been included through a quantum thermal bath (QTB). The interatomic forces were described either within the density functional theory (DFT) in the generalized gradient approximation (GGA) or by the phenomenological approach using the shell model. For both models, the isotopic shift in the lattice parameter can be successfully predicted by QTB-MD simulations. The slope of the experimental isotopic shift in pressure is satisfactorily reproduced by QTB-MD within DFT-GGA, in contrast to both density functional perturbation theory and QTB-MD with the shell model. We have analyzed the reasons for these discrepancies through the vibrational densities of states and the isotopic shifts in bulk modulus. The results illustrate the importance of anharmonic contributions to vibrations and to the isotopic pressure shift between LiH and LiD.

  9. Thermal Conductivity of Nanotubes: Effects of Chirality and Isotope Impurity

    OpenAIRE

    Gang, Zhang; Li, Baowen

    2005-01-01

    We study the dependence of thermal conductivity of single walled nanotubes (SWNT) on chirality and isotope impurity by nonequilibrium molecular dynamics method with accurate potentials. It is found that, contrary to electronic conductivity, the thermal conductivity is insensitive to the chirality. The isotope impurity, however, can reduce the thermal conductivity up to 60% and change the temperature dependence behavior. We also study the dependence of thermal conductivity on tube length for t...

  10. Kinetic isotope effects in the OH and Cl reactions of the clumped methane species 13CH3D

    DEFF Research Database (Denmark)

    Joelsson, Magnus

    . As is proven in the current research project, the clumped isotopes are removed by oxidation mechanisms at a slower rate. The residual methane pool is therefore enriched in clumped isotopes compared to the methane from the sources. In order to construct a top-down budget of methane, the clumped kinetic effect...... of the sinkmechanisms must be taken into account. The clumped kinetic effect in atmospheric oxidation of methane has been studied experimentally and theoretically in the three current papers: In Paper I the effect of oxidation by the chlorine radical at roomtemperature (25 ±C) was studied, in Paper II the effect...... of oxidation by the hydroxyl radical over a range of temperatures (5 ±C–40 ±C) was studied, and in Paper III the effect of both the chlorine and the hydroxyl radical at room temperature was studied. All the experiments were conducted in the smog chamber of the Department of Chemistry, University of Copenhagen...

  11. Hydrogen isotope effect through Pd in hydrogen transport pipe

    International Nuclear Information System (INIS)

    Tamaki, Masayoshi

    1992-01-01

    This investigation concerns hydrogen system with hydrogen transport pipes for transportation, purification, isotope separation and storage of hydrogen and its isotopes. A principle of the hydrogen transport pipe (heat pipe having hydrogen transport function) was proposed. It is comprised of the heat pipe and palladium alloy tubes as inlet, outlet, and the separation membrane of hydrogen. The operation was as follows: (1) gas was introduced into the heat pipe through the membrane in the evaporator; (2) the introduced gas was transported toward the condenser by the vapor flow; (3) the transported gas was swept and compressed to the end of the condenser by the vapor pressure; and (4) the compressed gas was exhausted from the heat pipe through the membrane in the condenser. The characteristics of the hydrogen transport pipe were examined for various working conditions. Basic performance concerning transportation, evacuation and compression was experimentally verified. Isotopic dihydrogen gases (H 2 and D 2 ) were used as feed gas for examining the intrinsic performance of the isotope separation by the hydrogen transport pipe. A simulated experiment for hydrogen isotope separation was carried out using a hydrogen-helium gas mixture. The hydrogen transport pipe has a potential for isotope separation and purification of hydrogen, deuterium and tritium in fusion reactor technology. (author)

  12. Matrix effects in laser ablation molecular isotopic spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Staci, E-mail: staci.brown@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Ford, Alan, E-mail: alan.ford@alakaidefense.com [Alakai Defense Systems, 197 Replacement Ave, Suite 102, Fort Leonard Wood, MO 65473 (United States); Akpovo, Charlemagne C., E-mail: charlemagne.akpovo@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Martinez, Jorge, E-mail: jmartinez@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States); Johnson, Lewis, E-mail: lewis@cepast.famu.edu [Department of Physics, Florida A and M University, 2077 E. Paul Dirac Drive, Tallahassee, FL 32310 (United States)

    2014-11-01

    Recently, it has been shown that laser-induced breakdown spectroscopy (LIBS) can be used for the detection of isotopes of elements via isotopic shifts in diatomic species in a technique known as laser ablation molecular isotopic spectrometry (LAMIS). While LAMIS works quite well for isotopic analysis of pure compounds under optimal conditions, it is desirable for it to be applicable for a variety of compounds and matrices. However, the LIBS plasma emission associated with LAMIS depends on several parameters, including the applied electric field of the laser pulse, the physical properties of the material being investigated, and the presence of additional elements other than the element of interest. In this paper, we address some of the pitfalls arising from these dependencies when using LAMIS for the determination of the relative isotopic abundance of boron-containing materials with varying chemical matrices. - Highlights: • LAMIS usually determines isotopic composition of boron compounds within 3 percent. • LaBO{sub 3} and some boron-containing mixtures yield inaccurate LAMIS results. • Higher laser energy reduces variability but does not remedy poor LAMIS outcomes.

  13. Behavior of uranium and thorium isotopes in soils of the Boreon area, Mercantour Massif (S.E. France). Leaching and weathering rate modeling

    International Nuclear Information System (INIS)

    Rezzoug, S.; Michel, H.; Barci-Funel, G.; Barci, V.; Fernex, F.

    2009-01-01

    Four cores were collected in weathered rocks and soils in the Boreon forest area (1765 m, Mercantour Massif, France). The samples were analyzed for the isotopes 230 Th, 232 Th, 234 U and 238 U. The activity and isotopic ratio profiles suggest that uranium was mobilized (leaching and precipitation) during the weathering process, as well as thorium but in a much less proportion. A model was drawn up to evaluate the U leaching rate and the time that some levels of the weathered rocks have been subjected to weathering. It utilizes LATHAM and SCHWARCZ's two equations,15 expressed as 234 U/ 238 U and 230 Th/ 238 U activity ratios, which assume that the alpha recoil effect allows easier leaching for 234 U than 238 U and no Th mobility. But this last assumption does not correspond to the observations made in the Boreon area, since it appears that in some soil deeper layers 230 Th and 228 Th are in radioactive deficit relatively to their parents. As there are four unknown quantities (the time, the leaching rates of 238 U, 234 U, 230 Th), the problem to be solved requires two more equations; these can be obtained utilizing the U activity ratio in water, and taking into account the 232 Th behavior. In some sites the 238 U leaching rate is high in deeper soil levels (near the fresh rocks); this would correspond to a loss of half the U amount in less than 24 000 years. (author)

  14. Investigations on the heterogenous catalytic hydrogenation using isotope effect and gamma- and neutron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Kudlacek, R; Cabicar, J [Ceske Vysoke Uceni Technicke, Prague (Czechoslovakia). Katedra Jaderne Chemie

    1976-01-01

    The kinetic and solvent isotope effects during the maleic acid heterogeneous catalytic hydrogenation and deuteration in light and heavy water have been studied. Also the effect of the gamma and neutron irradiation on the Ni-ZnO catalysts (with various ratios of components) on the reaction kinetics and mechanism has been measured, as well as the effect of pH on the adsorption behaviour of maleic acid and the temperature dependence of the reaction rate. Existence of different adsorption centers for hydrogen and maleic acid could be deduced from these experiments. A reaction mechanism based on the two-dimensional diffusion of components in the surface is proposed. The catalyst is formed from Ni and ZnO-microspheres. Hydrogen is bound to nickel and maleic acid is adsorbed on the ZnO-microspheres. The reaction takes place on the boundary layers of these microspheres.

  15. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear...... least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC(34)S relative to OC(32)S was found to be 0.9783 ± 0.0062 ((34)e = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory......; at 300 K, the isotopic fractionation was found to be (34)e = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)e in OCS photolysis and OH oxidation are not larger than 10‰, indicating that...

  16. The Effect of Phytase on the Oxygen Isotope Composition of Phosphate

    Science.gov (United States)

    von Sperber, C.; Tamburini, F.; Bernasconi, S. M.; Frossard, E.

    2013-12-01

    Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi) (1-2). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. The enzymatic hydrolysis leads, via a nucleophilic attack, to the incorporation of one oxygen atom from the water into the newly formed Pi molecule. During the incorporation, an isotopic fractionation occurs, which might be used to identify the origin of Pi in the environment (3-6). While the effect of phosphomonoesterases and phosphodiesterases on the oxygen isotope composition of phosphate has been examined, there are, so far, no studies dealing with the effect of phytases (4-6). Phytases catalyze the hydrolysis of myo-inositol-hexakis-phosphate (IP6), which is an important component of organic P in many ecosystems (7). Enzymatic assays with phytase from wheat germ and Aspergillus niger were prepared under sterile and temperature controlled conditions in order to determine the effect of phytases on the oxygen isotope composition of phosphate, which has been liberated from IP6 via enzymatic hydrolysis. Assays with phytase from wheat germ lead to a turnover of the substrate close to 100%, while assays with phytase from Aspergillus niger lead to a turnover of the substrate close to 80%. In the case of the assays with phytase from wheat germ, our results indicate that one sixth of the total 24 oxygen which are associated to the phosphates in IP6 are exchanged with oxygen from water. From this we conclude that the incorporation of one oxygen atom from water occurs only at four phosphate molecules of IP6, while two phosphate molecules do not experience an incorporation of oxygen. This suggests that during the enzymatic hydrolysis, four P-O bonds and two C-O bonds are broken. Provided that, the isotopic fractionation can be calculated with an isotopic mass balance resulting in -8.4‰ (×3.6 SD). This is a value very similar to those reported

  17. Investigation of the feeding effect on the 13C/12C isotope ratio of the hormones in bovine urine using gas chromatography/combustion isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Balizs, Gabor; Jainz, Annett; Horvatovich, Peter

    2005-01-01

    The effect of the feeding on the 13C/12C isotope ratio of four endogenous steroid hormones testosterone (T), epi-testosterone (epi-T), dehydroepiandrosterone (DHEA) and etiocholanolone (ETIO) in bovine urine was investigated. An analytical method to determine the accurate isotope ratio was developed

  18. Intramolecular kinetic isotope effect in gas-phase proton-transfer reactions

    International Nuclear Information System (INIS)

    Wellman, K.M.; Victoriano, M.E.; Isolani, P.C.; Riveros, J.M.

    1979-01-01

    The k/sub H//k/sub D/ isotope effects were determined by ICR for the reaction of substituted toluenes with several alkoxides. The results showed a definite trend for k/sub H//k/sub D/ starting as a normal isotope effect for appreciably exothermic reaction (> 3 kcal mol -1 ) and proceeding smoothly toward an inverse isotope effect as the reaction approached thermoneutrality or becomes endothermic. These observations were explained by a reaction which involved a double minima potential with a central energy barrier

  19. Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Maggi, F.M.; Riley, W.J.

    2009-06-01

    The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

  20. Effect Of Substrates On The Fractionation Of Hydrogen Isotopes During Lipid-Biosynthesis By Haloarcula marismortui

    Science.gov (United States)

    Dirghangi, S. S.; Pagani, M.

    2010-12-01

    Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our

  1. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    Science.gov (United States)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  2. Gamma ray heating rates due to chromium isotopes in stellar core during late stages of high mass stars (>10M⊙

    Directory of Open Access Journals (Sweden)

    Nabi Jameel-Un

    2017-01-01

    Full Text Available Gamma ray heating rates are thought to play a crucial role during the pre-supernova stage of high mass stars. Gamma ray heating rates, due to β±-decay and electron (positron capture on chromium isotopes, are calculated using proton-neutron quasiparticle random phase approximation theory. The electron capture significantly affects the lepton fraction (Ye and accelerates the core contraction. The gamma rays emitted as a result of weak processes heat the core and tend to hinder the cooling and contraction due to electron capture and neutrino emission. The emitted gamma rays tend to produce enormous entropy and set the convection to play its role at this stage. The gamma heating rates, on 50-60Cr, are calculated for the density range 10 < ρ (g.cm-3 < 1011 and temperature range 107 < T (K < 3.0×1010.

  3. Amide proton exchange rates of a bound pepsin inhibitor determined by isotope-edited proton NMR experiments

    International Nuclear Information System (INIS)

    Fesik, S.W.; Luly, J.R.; Stein, H.H.; BaMaung, N.

    1987-01-01

    From a series of isotope-edited proton NMR spectra, amide proton exchange rates were measured at 20 C, 30 C, and 40 0 C for a tightly bound 15 N-labeled tripeptide inhibitor of porcine pepsin (IC50 = 1.7 X 10(-) M). Markedly different NH exchange rates were observed for the three amide protons of the bound inhibitor. The P1 NH exchanged much more slowly than the P2 NH and P3 NH. These results are discussed in terms of the relative solvent accessibility in the active site and the role of the NH protons of the inhibitor for hydrogen bonding to the enzyme. In this study a useful approach is demonstrated for obtaining NH exchange rates on ligands bound to biomacromolecules, the knowledge of which could be of potential utility in the design of therapeutically useful nonpeptide enzyme inhibitors from peptide leads

  4. Isotope effect in the photochemical decomposition of CO{sub 2} (ice) by Lyman-{alpha} radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Chunqing; Yates, John T. Jr. [Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904 (United States)

    2013-04-21

    The photochemical decomposition of CO{sub 2}(ice) at 75 K by Lyman-{alpha} radiation (10.2 eV) has been studied using transmission infrared spectroscopy. An isotope effect in the decomposition of the CO{sub 2} molecule in the ice has been discovered, favoring {sup 12}CO{sub 2} photodecomposition over {sup 13}CO{sub 2} by about 10%. The effect is caused by electronic energy transfer from the excited CO{sub 2} molecule to the ice matrix, which favors quenching of the heavier electronically-excited {sup 13}CO{sub 2} molecule over {sup 12}CO{sub 2}. The effect is similar to the Menzel-Gomer-Redhead isotope effect in desorption from adsorbed molecules on surfaces when electronically excited. An enhancement of the rate of formation of lattice-trapped CO and CO{sub 3} species is observed for the photolysis of the {sup 12}CO{sub 2} molecule compared to the {sup 13}CO{sub 2} molecule in the ice. Only 0.5% of the primary photoexcitation results in O-CO bond dissociation to produce trapped-CO and trapped-CO{sub 3} product molecules and the majority of the electronically-excited CO{sub 2} molecules return to the ground state. Here either vibrational relaxation occurs (majority process) or desorption of CO{sub 2} occurs (minority process) from highly vibrationally-excited CO{sub 2} molecules in the ice. The observation of the {sup 12}C/{sup 13}C isotope effect in the Lyman-{alpha} induced photodecomposition of CO{sub 2} (ice) suggests that over astronomical time scales the isotope enrichment effect may distort historical information derived from isotope ratios in space wherever photochemistry can occur.

  5. Estimation of soil respiration rates and soil gas isotopic composition for the different land use of Ultisols from Calhoun CZO.

    Science.gov (United States)

    Cherkinsky, A.; Brecheisen, Z.; Richter, D. D., Jr.; Sheng, H.

    2017-12-01

    CO2 flux from soil is significant in most ecosystems and can account for more than 2/3 of total ecosystem respiration. In many cases CO2 fluxes from soil are estimated using eddy covariance techniques or the classical chamber method with measures of bulk concentrations and isotope composition of CO2. Whereas most of these studies estimate flux from the soil surface, we analyzed its concentration and isotope composition directly in soil profiles down to 8.5m depth. This experiment was conducted in Sumter National Forest in summer of 2016. The samples were collected from 3 different land use history sites: a) reference hardwood stands, mainly of oak and hickory that are taken to be never cultivated; b) cultivated plots, which were also used growing cotton prior to the 1950's but for the last 50 years for growing corn, wheat, legume, sorghum, and sunflowers; c) pine stands, which had been used for growing cotton from beginning of the 19th century and then was abandoned in 1920s and planted with loblolly pine. We have analyzed 3 replicates of each land use. There were measured in the field CO2 and O2 concentration and collected gas samples were analyzed for Δ14C, δ13C and δ18O. CO2 concentration in all types of land use has a maximum about 3m depth, approximately the same depth as the minimum of O2 concentration. Isotope analyses revealed that carbon isotopic composition tend to become lighter with the depth for all three types of land use: in cultivated site it changes from -18%o at 0.5m to -21%o at 5m; in pine site from -22%o to -25%o and in hardwood from-21.5 -24.5%o correspondently, the O2 isotopic composition does not change significantly. Based on analysis of Δ14C the turnover rate of CO2 is getting slower as depth increases. At the first 50 cm the exchange rate is the fastest on cultivated site, likely due to annual tilling, and concentration of 14C is actually equal to atmospheric. However, the turnover rate of Δ14C in soil CO2 slows down significantly as

  6. Determination of the δ13C (per mille) isotopic rate of the Brazilian beer pilsen type

    International Nuclear Information System (INIS)

    Rossete, Alexssandra L.R.M.; Bendassolli, Jose Albertino; Lopes, Fabio; Martinelli, Luiz Antonio

    2002-01-01

    Beer has been consumed in Brazil since the XIX century. However, at that time, this beverage was imported from England, and the first Brazilian breweries just appeared at the end of the XX century. Basically, beer is made from: malt of barley, Humulus lupulus, water and yeast. In this work, twenty brands of national beer (Pilsen type), and also two different cereals, barley, a C3 metabolism plant, corn, a C4 plant, were analysed to determine their isotope composition δ 13 C (per mille) utilizing a mass spectrometer Delta Plus Finigam and Anca S.L. An aliquot of each sample was transferred using a capillary of glass to a tin capsule contends a small amount of sorbitol. The isotope compositions, δ 13 C, of barley and corn samples determined were -27.2 and -11.5 per mille, respectively. These results were used to calculate the equation of mixture model. Considering the beer samples, the δ 13 C ranged from -18.3 to -23.1 per mille; this result means that the percentage of C3 plant is from 43.3 to 73.9 per mille. In this manner, it is possible to concluded that all beer samples has malted cereals (C4 plant), as far as the low values of C3 plants were presented in these samples as shown through the equation of mixtures model. (author)

  7. Carbon isotope effects in carbohydrates and amino acids of photosynthesizing organisms

    Energy Technology Data Exchange (ETDEWEB)

    Ivlev, A.A.; Kaloshin, A.G.; Koroleva, M.Ya. (Ministerstvo Geologii SSR, Moscow)

    1982-02-10

    The analysis of the carbon isotope distribution in carbohydrates and amino acids of some photosynthesizing organisms revealed the close relationship between distribution and the pathways of biosynthesis of the molecules. This relationship is explained on the basis of the previously proposed mechanism of carbon isotope fractionation in a cell, in which the chief part is played by kinetic isotope effects in the pyruvate decarboxylation reaction progressively increased in the conjugated processes of gluconeogenesis. Isotope differences of C/sub 2/ and C/sub 3/ fragments arising in decarboxylation of pyruvate, as well as isotope differences of biogenic acceptor and environmental CO/sub 2/ appearing in assimilation are the main reasons of the observed intramolecular isotopic heterogeneity of biomolecules. The heterogeneity is preserved in metabolites owing to an incomplete mixing of carbon atoms in biochemical reactions. The probable existence of two pools of carbohydrates in photosynthesizing organisms different in isotopic composition is predicted. Two types of intramolecular isotope distribution in amino acids are shown.

  8. Prediction of isotope effects for anticipated intermediate structures in the course of bacterial denitrification

    International Nuclear Information System (INIS)

    Morgenstern, M.A.; Schowen, R.L.

    1989-01-01

    Vibrational-analysis methods have been used to estimate the equilibrium 14 N/ 15 N isotope effects to be expected for conversion of nitrite anion to thirteen possible intermediate-state and product-state structures [HONO, NO + , NO, NO - , FeNO, ON * NO 2 , O * NNO 2 , O 2 NNO 2 , ONO * N, O * NON, ONNO, * NNO, N * NO] in the reduction of nitrite ion to nitrous oxide denitrifying bacteria. The results, taken in combination with previous experimental isotope-effect and tracer studies of the Pseudomonas stutzeri and related systems, are consistent with a suggestion that a second nitrite anion enters the enzyme-catalytic cycle at the stage of a nitrosyl-ion intermediate but re-emerges after entry of the reducing electrons; the product nitrous oxide is then formed by disproportionation of enzymically generated hyponitrous acid. The calculations are consistent with contributions, under different experimental conditions, of several different transition states to limiting the rate of the enzymic reaction. These transition states (and the corresponding experimental conditions) are the transition states for N-O fission in the generation of a mononitrogen electrophilic species from nitrite anion (high reductant, high nitrite concentrations), for attack of nitrite on this electrophile (high reductant, low nitrite concentrations) and for electron transfer to a dinitrogen-trioxide-like species (low reductant concentration). (orig.)

  9. Effect of the magnetic isotope of magnesium, 25Mg, on post-radiation recovery of Saccharomyces cerevisiae

    International Nuclear Information System (INIS)

    Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.; Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.; Grodzinskij, D.M.; Evstyukhina, T.A.; Kol'tover, V.K.; Korolev, V.G.; Kutlakhmedov, Yu.A.

    2011-01-01

    Among three stable magnesium isotopes, 24 Mg, 25 Mg, and 26 Mg with natural abundance 79, 10, and 11%, only 25 Mg has the nuclear spin (I=5/2) and, therefore, the nuclear magnetic moment. Two other isotopes are spinless (I=0) and, hence, have no magnetic moment. We have revealed that magnetic isotope 25 Mg, by comparison to nonmagnetic isotope 24 Mg, essentially stimulates the recovery process in the yeast cells, Saccharomyces cerevisiae, after UV irradiation. Thus, we have first documented the magnetic isotope effect in radiation biology. This finding opens up the way to the development of novel radio-protectors based on the stable magnetic isotopes.

  10. Mechanism and activation for allosteric adenosine 5'-monophosphate nucleosidase. Kinetic alpha-deuterium isotope effects for the enzyme-catalyzed hydrolysis of adenosine 5'-monophosphate and nicotinamide mononucleotide

    International Nuclear Information System (INIS)

    Skoog, M.T.

    1986-01-01

    The kinetic alpha-deuterium isotope effect on Vmax/Km for hydrolysis of NMN catalyzed by AMP nucleosidase at saturating concentrations of the allosteric activator MgATP2- is kH/kD = 1.155 +/- 0.012. This value is close to that reported previously for the nonenzymatic hydrolysis of nucleosides of related structure, suggesting that the full intrinsic isotope effect for enzymatic NMN hydrolysis is expressed under these conditions; that is, bond-changing reactions are largely or completely rate-determining and the transition state has marked oxocarbonium ion character. The kinetic alpha-deuterium isotope effect for this reaction is unchanged when deuterium oxide replaces water as solvent, corroborating this conclusion. Furthermore, this isotope effect is independent of pH over the range 6.95-9.25, for which values of Vmax/Km change by a factor of 90, suggesting that the isotope-sensitive and pH-sensitive steps for AMP-nucleosidase-catalyzed NMN hydrolysis are the same. Values of kH/kD for AMP nucleosidase-catalyzed hydrolysis of NMN decrease with decreasing saturation of enzyme with MgATP2- and reach unity when the enzyme is less than half-saturated with this activator. This requires that the rate-determining step changes from cleavage of the covalent C-N bond to one which is isotope-independent. In contrast to the case for NMN hydrolysis, AMP nucleosidase-catalyzed hydrolysis of AMP at saturating concentrations of MgATP2- shows a kinetic alpha-deuterium isotope effect of unity. Thus, covalent bond-changing reactions are largely or completely rate-determining for hydrolysis of a poor substrate, NMN, but make little or no contribution to rate-determining step for hydrolysis of a good substrate, AMP, by maximally activated enzyme. This behavior has several precedents

  11. Studies of isotopic effects in the excited electronic states of molecular systems

    International Nuclear Information System (INIS)

    1982-01-01

    Rare gas halogen (RGH) lasers serve as convenient tools for a range of photophysical processes which exhibit isotope effects. This document summarizes progress in the production of molecular systems in their electronic excited states with the aid of RGH lasers, and the various isotopic effects one can study under these conditions. We conclude that the basic physical mechanisms involved in the isotopically sensitive characteristics of excited molecular electronic states are sufficiently selective to be useful in both the detection and separation of many atomic materials

  12. D/H isotope effects in π-complexes of deuterated hexamethylbenzenes with the nitrosonium cation

    International Nuclear Information System (INIS)

    Borodkin, G.I.; Elanov, I.R.; Shakirov, M.M.; Shubin, V.G.

    1993-01-01

    The isotope effects of deuterium, manifested in the 13 C NMR spectra of complexes of deuterated hexamethylbenzenes C 6 (CD 3 ) n ·(CH 3 ) 6-n with the nitrosonium cation, have been studied. The small values observed for the isotopic perturbation are evidence of π-bonding of the NO + group to the hexamethylbenzene molecule. The applicability of an additive scheme of calculation of isotope effects for the ring carbon atoms of the complexes, based on the increment of replacement of the CH 3 group by CD 3 in hexamethylbenzene, has been demonstrated

  13. Secondary partitioning isotope effects on solvolytic ion pair intermediates

    International Nuclear Information System (INIS)

    Abbey, K.J.

    1976-01-01

    The thermal decomposition of N-benzhydryl N-nitrosobenzamide (BNB) has been shown to produce an ion pair which either forms ester or reacts with the solvent. In ethanol, the fraction of ester produced, R, was much smaller than R values obtained from solvolysis or from the diphenyldiazomethane (DDM)-benzoic acid reaction, which was suggested to yield the same ion pair as solvolysis. This difference led to the conclusion that the ionic species for the nitrosamide decomposition is a nitrogen-separated ion pair. This study was initiated on the assumption that BNB led to solvolytic ion pairs, but that both the intimate and solvent-separated ion pairs were produced directly from the nitrosamide. The use of α-tritiated BNB for the study of partitioning isotope effects (PIE's) in this system led to activity ratios much lower than expected from other reported work. Results of studies of ''special'' salt effect were not consistent for all situations, but the results do suggest that the assumption that BNB leads to solvolytic ion pairs is probably valid. The investigation of the more stable p-methoxybenzhydryl benzoate system proved to be highly productive. The ester fraction produced, R, responded dramatically to the addition of common-ion as well as ''special'' salts. The functional relationship of R on salt concentration could be explained in terms of Winstein's solvolytic scheme where the intimate ion pair, the solvent-separated ion pair, and the dissociated ion were important. Tritium-labelled compounds were used for PIE studies on 3 different compounds, and three different methods of reaction are proposed

  14. Gamma dose rate effect on JFET transistors

    International Nuclear Information System (INIS)

    Assaf, J.

    2011-04-01

    The effect of Gamma dose rate on JFET transistors is presented. The irradiation was accomplished at the following available dose rates: 1, 2.38, 5, 10 , 17 and 19 kGy/h at a constant dose of 600 kGy. A non proportional relationship between the noise and dose rate in the medium range (between 2.38 and 5 kGy/h) was observed. While in the low and high ranges, the noise was proportional to the dose rate as the case of the dose effect. This may be explained as follows: the obtained result is considered as the yield of a competition between many reactions and events which are dependent on the dose rate. At a given values of that events parameters, a proportional or a non proportional dose rate effects are generated. No dependence effects between the dose rate and thermal annealing recovery after irradiation was observed . (author)

  15. A study of hydrogen isotopes fuel control by wall effect in magnetic fusion devices

    Energy Technology Data Exchange (ETDEWEB)

    Motevalli, S.M., E-mail: motavali@umz.ac.ir; Safari, M.

    2016-11-15

    Highlights: • A particle balance model for the main plasma and wall inventory in magnetic fusion device has been represented. • The dependence of incident particles energy on the wall has been considered in 10–300 eV for the sputtering yield and recycling coefficient. • The effect of fueling methods on plasma density behavior has been studied. - Abstract: Determination of plasma density behavior in magnetic confinement system needs to study the plasma materials interaction in the facing components such as first wall, limiter and divertor. Recycling of hydrogen isotope is an effective parameter in plasma density rate and plasma fueling. Recycling coefficient over the long pulse operation, gets to the unity, so it has a significant effect on steady state in magnetic fusion devices. Typically, sputtered carbon atoms from the plasma facing components form hydrocarbons and they redeposit on the wall. In this case little rate of hydrogen loss occurs. In present work a zero dimensional particle equilibrium model has been represented to determine particles density rate in main plasma and wall inventory under recycling effect and codeposition of hydrogen in case of continues and discontinues fueling methods and effective parameters on the main plasma decay has been studied.

  16. Heavy-atom isotope effects on binding of reactants to lactate dehydrogenase and pyruvate kinase

    International Nuclear Information System (INIS)

    Gawlita, E.

    1993-04-01

    18 O and 13 C kinetic isotope effects have been measured on the reaction of pyruvate kinase with phospho-enol-pyruvate and ADP using a remote label technique. The magnitude of both investigated isotope effects showed a dependence on the concentration of ADP. However, while the carbon effect was simply 'washed out' to unity at high ATP concentration, the oxygen effect becomes inverse and reached 0.9928 at the highest used concentration of ADP. Such a result testifies that the assumption of the negligible effect of isotopic substitution on enzyme-substrate associations remains correct only for carbon effects. An equilibrium 18 O isotope effect on association of oxalate with lactate dehydrogenase in the presence of NADHP has been evaluated by both experimental and theoretical means. Experimental methods, which involved equilibrium dialysis and gas chromatographic/mass spectrometric measurement of isotopic ration, yielded an inverse value of 0.9840. Semiempirical methods involved vibrational analysis of oxalate in two different environments. The comparison of calculated values with the experimentally determined isotope effect indicated that the AM 1 Hamiltonian proved superior to its PM 3 counterpart in this modelling. 160 refs, 8 figs, 18 tabs

  17. Limits on the expression of enzyme-mediated solvent isotope effects

    International Nuclear Information System (INIS)

    Northrop, D.B.

    1981-01-01

    Steady-state analysis of primary solvent isotope effects on enzyme-catalyzed reactions, mediated by solvent-shielded di- or triprotic groups on the enzyme, yields equations describing the upper limit of intramolecular isotopic discrimation. For diprotic groups [P/sub H]/[P/sub D/] = 3k/sub H//k/sub D/ + 3), and for triprotic groups [P/sub H/]/[P/sub D/] = [7(k/sub H//k/sub D/ 2 = 10k/sub H/k/sub D/ + 1]/[(k/sub H//k/sub D/) 2 + 10k/sub H//k/sub D/ + 7]. Given a normal intrinsic isotope effect of k/sub H//k/sub D/ = 7, maximal isotopic discrimation in 50:50 H 2 O:D 2 O is therefore 2.2 and 3.3, respectively, versus 1.0 for a monoprotic group. Intermediate values of isotope discrimination may be interpreted with respect to distinguishing enzyme-mediated catalytic mechanisms from those of direct transfer between solvent and substrate, and to identifying mediating groups, by comparisons of isotopic discrimination at high and low concentrations of substrates and by reference to intrinsic and intermolecular isotope effects

  18. Solvent-dependent deuterium isotope effects in the 15N NMR spectra of an ammonium ion

    International Nuclear Information System (INIS)

    Wielogorska, E.; Jackowski, K.

    2000-01-01

    Deuterium isotope effects on 15 N NMR chemical shifts and spin-spin coupling constants have been investigated for the 15 N enriched ammonium chloride (conc. 15 NH 4 + ion has been observed in water, methanol, ethanol and dimethylsulfoxide, while the 15 ND 4 + has been monitored in the analogous deuterated liquids. It is shown that the isotope effect in nitrogen chemical shifts ( 1 Δ 15 N( 2/1 H)), significantly different in various solvents, changes from -1.392 ppm in dimethylsulfoxide to -0.071 ppm in ethanol. The 1 J(N,H) and 1 J(N,D) coupling constants have been measured for acidic solutions under conditions of slow proton (or deuterium) exchange. The reduced coupling constants have been estimated to present isotope effects in the spin-spin coupling constants. The latter isotope effects are fairly small. (author)

  19. Isotope effects in the equilibrium and non-equilibrium vaporization of tritiated water and ice

    International Nuclear Information System (INIS)

    Baumgaertner, F.; Kim, M.-A.

    1990-01-01

    The vaporization isotope effect of the HTO/H 2 O system has been measured at various temperatures and pressures under equilibrium as well as non-equilibrium conditions. The isotope effect values measured in equilibrium sublimation or distillation are in good agreement with the theoretical values based on the harmonic oscillator model. In non-equilibrium vaporization at low temperatures ( 0 C), the isotope effect decreases rapidly with decreasing system pressure and becomes negligible when the system pressure is lowered more than one tenth of the equilibrium vapor pressure. At higher temperatures, the isotope effect decreases very slowly with decreasing system pressure. Discussion is extended for the application of the present results to the study of biological enrichment of tritium. (author)

  20. In-situ buildup of cosmogenic isotopes at the earth`s surface: measurement of erosion rates and exposure times

    Energy Technology Data Exchange (ETDEWEB)

    Fifield, L K; Allan, G L; Stone, J O.H.; Evans, J M; Cresswell, R G; Ophel, T R [Australian National Univ., Canberra, ACT (Australia)

    1994-12-31

    Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes {sup 10}Be (t{sub 1/2} = 1.5Ma), {sup 26}Al (0.7Ma) and {sup 36}Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on {sup 36}Cl. The accumulation of cosmogenic {sup 36}Cl in calcite (CaCO{sub 3}) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of {sup 36}Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of {sup 36}Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of {sup 36}Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs.

  1. In-situ buildup of cosmogenic isotopes at the earth's surface: measurement of erosion rates and exposure times

    International Nuclear Information System (INIS)

    Fifield, L.K.; Allan, G.L.; Stone, J.O.H.; Evans, J.M.; Cresswell, R.G.; Ophel, T.R.

    1993-01-01

    Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes 10 Be (t 1/2 = 1.5Ma), 26 Al (0.7Ma) and 36 Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on 36 Cl. The accumulation of cosmogenic 36 Cl in calcite (CaCO 3 ) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of 36 Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of 36 Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of 36 Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs

  2. In-situ buildup of cosmogenic isotopes at the earth`s surface: measurement of erosion rates and exposure times

    Energy Technology Data Exchange (ETDEWEB)

    Fifield, L.K.; Allan, G.L.; Stone, J.O.H.; Evans, J.M.; Cresswell, R.G.; Ophel, T.R. [Australian National Univ., Canberra, ACT (Australia)

    1993-12-31

    Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes {sup 10}Be (t{sub 1/2} = 1.5Ma), {sup 26}Al (0.7Ma) and {sup 36}Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on {sup 36}Cl. The accumulation of cosmogenic {sup 36}Cl in calcite (CaCO{sub 3}) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of {sup 36}Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of {sup 36}Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of {sup 36}Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs.

  3. Evaluating origins and water seepage rates at the subdam A of the Dong Mo reservoir using environmental isotope technique

    International Nuclear Information System (INIS)

    Bui Dac Dung; Trinh Van Giap; Dang Anh Minh; Nguyen Van Hoan

    2008-01-01

    Environmental isotope techniques have been world-widely used for investigating origins and the rates of the seepage - leakage water at reservoir dams. We have conducted a research on the use of environmental isotope techniques for evaluating the origin of the seepage water and the seepage rate at the sub dam A of the Dong Mo reservoir. The main works were collecting water samples, analyzing for 18 O/ 16 O, 2 H(D)/ 1 H ratios, analyzing for 3 H(T) and chemical contents. Findings of the project showed that: a) Waters at the piezometers on the top and the 1st roof are not originated from lake water; b) Waters at the piezometers on 1st and 2nd levels, as well as seepage waters at the dam toe are mixed of lake and ground waters, and the old river bed could be the channel for ground water upcoming from beneath the dam body; c) The transit times of water from the lake to the observation points are from 3 to 4 months, and the seepage velocity is of about 1.1x10 -3 cm/s; d) The findings from tritium analyses show that all waters around the Dong Mo area are recent waters recharged regularly by meteoric water. (author)

  4. Influences of gas stream conditions on efficiency of tritiated moisture collection with P2O5-desiccant and isotope effect

    International Nuclear Information System (INIS)

    Kotoh, Kenji; Miura, Katsuya; Kashio, Yousuke; Nishikawa, Masabumi

    1991-01-01

    A method was proposed previously for collection and measurement of tritiated moisture in gas stream using P 2 O 5 -desiccant. Influences of the gas humidity, the gas flow rate and the distance between gas nozzle and P 2 O 5 -desiccant layer surface on the moisture collection efficiency have been examined through experiments, and the isotope effect on the collection has been investigated. The collection efficiency is the ratio of collected to supplied moisture, and the moisture supplying rate is in proportion to the humidity and flow rate of feed gas. The experiments show that; the collection efficiency dose not depend on the gas humidity, but is affected by the gas flow rate and by the nozzle-layer distance. The effects of the flow rate and the nozzle position are related to the mass transfer distance from the bulk of gas stream to the desiccant layer surface in the collection cell. The moisture collecting rate is promoted by the approach of the gas stream to the layer surface. An expression of effective separation factor has been derived to explain the isotope effect on the moisture collection. Experimental data distribution of the separation factor have been reasonably simulated by the analysis. (author)

  5. Isotopic effect of the mean lifetimes of the NeAr2+ doubly charged rare-gas dimer

    International Nuclear Information System (INIS)

    Ben-Itzhak, I.; Bouhnik, J.P.; Chen, Z.; Gertner, I.; Heinemann, C.; Koch, W.; Lin, C.D.; Rosner, B.

    1995-01-01

    It has been suggested recently by Chen et al. [Phys. Rev. A 49, 3472 (1994)] that the measured long-lived NeAr 2+ formed in fast NeAr + + Ar charge-stripping collisions is mostly in its v=12 vibrational state bound to the electronic ground state, and that this molecular ion decays by tunneling through the potential barrier. Such a decay rate is expected to depend strongly on the reduced mass of the molecular ion leading to large isotopic effects. We have measured the mean lifetimes of the 20 Ne 40 Ar 2+ and 22 Ne 40 Ar 2+ isotopes in order to see this isotopic effect. Surprisingly, the mean lifetimes of both isotopes are similar to each other. Thus, it is suggested that the observed NeAr 2+ molecular ions do not decay via a tunneling mechanism, which would indicate that they reside in the metastable electronic ground state. Rather, electronic transitions from bound or metastable excited states into other repulsive states are the origin for the experimentally observed decay. Qualitative estimates for the shapes and ordering of these states in the electronic spectrum of NeAr 2+ are given

  6. Measurement of apolipoprotein E and amyloid β clearance rates in the mouse brain using bolus stable isotope labeling

    Science.gov (United States)

    2012-01-01

    Background Abnormal proteostasis due to alterations in protein turnover has been postulated to play a central role in several neurodegenerative diseases. Therefore, the development of techniques to quantify protein turnover in the brain is critical for understanding the pathogenic mechanisms of these diseases. We have developed a bolus stable isotope-labeling kinetics (SILK) technique coupled with multiple reaction monitoring mass spectrometry to measure the clearance of proteins in the mouse brain. Results Cohorts of mice were pulse labeled with 13 C6-leucine and the brains were isolated after pre-determined time points. The extent of label incorporation was measured over time using mass spectrometry to measure the ratio of labeled to unlabeled apolipoprotein E (apoE) and amyloid β (Aβ). The fractional clearance rate (FCR) was then calculated by analyzing the time course of disappearance for the labeled protein species. To validate the technique, apoE clearance was measured in mice that overexpress the low-density lipoprotein receptor (LDLR). The FCR in these mice was 2.7-fold faster than wild-type mice. To demonstrate the potential of this technique for understanding the pathogenesis of neurodegenerative disease, we applied our SILK technique to determine the effect of ATP binding cassette A1 (ABCA1) on both apoE and Aβ clearance. ABCA1 had previously been shown to regulate both the amount of apoE in the brain, along with the extent of Aβ deposition, and represents a potential molecular target for lowering brain amyloid levels in Alzheimer's disease patients. The FCR of apoE was increased by 1.9- and 1.5-fold in mice that either lacked or overexpressed ABCA1, respectively. However, ABCA1 had no effect on the FCR of Aβ, suggesting that ABCA1 does not regulate Aβ metabolism in the brain. Conclusions Our SILK strategy represents a straightforward, cost-effective, and efficient method to measure the clearance of proteins in the mouse brain. We expect that

  7. Isotope effects associated with the anaerobic oxidation of sulfide by the purple photosynthetic bacterium, Chromatium vinosum

    International Nuclear Information System (INIS)

    Fry, B.; Gest, H.; Hayes, J.M.

    1984-01-01

    Small inverse isotope effects of 1-3 per thousand were consistently observed for the oxidation of sulfide to elemental sulfur during anaerobic photometabolism by Chromatium vinosum. The inverse fractionation can be accounted for by an equilibrium isotope effect between H 2 S and HS - , and may indicate that C. vinosum (and other photosynthetic bacteria) utilizes H 2 S rather than HS - as the substrate during sulfide oxidation. (Auth.)

  8. Kinetic isotope effect in dehydration of ionic solids. II. The kinetics of dehydration of calcium oxalate monohydrate

    International Nuclear Information System (INIS)

    Manche, E.P.; Carroll, B.

    1977-01-01

    The kinetics of the isothermal dehydration of the protonated and deuterated monohydrate of calcium oxalate has been investigated at 120, 150, and 170 0 C. The rate of dehydration for these salts was found to be k/sub H//k/sub D/ = 1.025 +- 0.012. This result rules out the enormous kinetic isotope effect as given in the literature. An isotope effect of a few percent is not ruled out; this magnitude is in keeping with that found by Heinzinger in other dehydration processes. An estimated difference of about 150 cal/mol between the heat of desorption for H 2 O and D 2 O should have led to a ratio, k/sub h//k/sub D/ = 1.20. The smaller observed ratio has been explained on the basis of a compensation effect and may be considered an example of the Barclay--Butler correlation

  9. Macroscopic rate equation modeling of trapping/detrapping of hydrogen isotopes in tungsten materials

    Energy Technology Data Exchange (ETDEWEB)

    Hodille, E.A., E-mail: etienne.hodille@cea.fr [CEA, IRFM, F-13108 Saint Paul lez Durance (France); Bonnin, X. [LSPM-CNRS, Université Paris 13, Sorbonne Paris Cité, F-93430 Villetaneuse (France); Bisson, R.; Angot, T. [Aix-Marseille Université, PIIM, CNRS, UMR 7345, 13397 Marseille (France); Becquart, C.S. [Université Lille I, UMET, UMR 8207, 59655 Villeneuve d’Ascq cédex France (France); Layet, J.M. [Aix-Marseille Université, PIIM, CNRS, UMR 7345, 13397 Marseille (France); Grisolia, C. [CEA, IRFM, F-13108 Saint Paul lez Durance (France)

    2015-12-15

    Relevant parameters for trapping of Hydrogen Isotopes (HIs) in polycrystalline tungsten are determined with the MHIMS code (Migration of Hydrogen Isotopes in MaterialS) which is used to reproduce Thermal Desorption Spectrometry experiments. Three types of traps are found: two intrinsic traps (detrapping energy of 0.87 eV and 1.00 eV) and one extrinsic trap created by ion irradiation (detrapping energy of 1.50 eV). Then MHIMS is used to simulate HIs retention at different fluences and different implantation temperatures. Simulation results agree well with experimental data. It is shown that at 300 K the retention is limited by diffusion in the bulk. For implantation temperatures above 500 K, the retention is limited by trap creation processes. Above 600 K, the retention drops by two orders of magnitude as compared to the retention at 300 K. With the determined detrapping energies, HIs outgassing at room temperature is predicted. After ions implantation at 300 K, 45% of the initial retention is lost to vacuum in 300 000 s while during this time the remaining trapped HIs diffuse twice as deep into the bulk. - Highlights: • Code development to solve numerically the model equations of diffusion and trapping of hydrogen in metals. • Parametrization of the model trapping parameters (detrapping energies and density): fitting of experimental TDS spectrum. • Confrontation model/experiment: evolution of retention with fluence and implantation temperature. • Investigation of period of rest between implantation and TDS on retention and depth profile.

  10. Bayesian estimation of dose rate effectiveness

    International Nuclear Information System (INIS)

    Arnish, J.J.; Groer, P.G.

    2000-01-01

    A Bayesian statistical method was used to quantify the effectiveness of high dose rate 137 Cs gamma radiation at inducing fatal mammary tumours and increasing the overall mortality rate in BALB/c female mice. The Bayesian approach considers both the temporal and dose dependence of radiation carcinogenesis and total mortality. This paper provides the first direct estimation of dose rate effectiveness using Bayesian statistics. This statistical approach provides a quantitative description of the uncertainty of the factor characterising the dose rate in terms of a probability density function. The results show that a fixed dose from 137 Cs gamma radiation delivered at a high dose rate is more effective at inducing fatal mammary tumours and increasing the overall mortality rate in BALB/c female mice than the same dose delivered at a low dose rate. (author)

  11. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  12. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    International Nuclear Information System (INIS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-01-01

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  13. Lithium isotope effects in chemical exchange with (2,2,1) cryptand

    International Nuclear Information System (INIS)

    Jepson, B.E.; Cairns, G.A.

    1979-01-01

    Equilibrium single-stage separation factors were determined for three lithium - (2,2,1) cryptand two-phase chemical exchange systems. The equilibrated phases consisted of an aqueous solution of a lithium salt and a chloroform solution of lithium cryptate salt complex. Lithium-6 concentrated in the organic phase in all cases, and the lithium isotope exchange rate with (2,2,1) cryptand was rapid. The separation factors were α = 1.026 +- 0.006 (LiBr exchange), α = 1.035 +- 0.003 (LiTFA), and α = 1.041 +- 0.006 (LiTFA + HTFA), where TFA represents trifluoroacetate. These values were compared with separation factors of other lithium chemical exchange systems. This work has shown that separation factors are influenced by the choice of chemical species and parameters. It has also demonstrated that significant lithium isotope effects can be obtained without a valence change of the metal exchanging between the aquo and cryptate complexes

  14. Isotope effects in interstellar molecules by chemical hyperfine interaction

    International Nuclear Information System (INIS)

    Haberkorn, R.; Michel-Beyerle, M.E.

    1977-01-01

    If free radicals recombine on grain surfaces, not only the different masses of isotopes but also their differing nuclear spin moments (e.g. 12 C/ 13 C, 14 N/ 15 N, 17 O/ 18 O) may imply variations in the recombination probability due to hyperfine interaction. This mechanism has not been accounted for so far. (orig.) [de

  15. Solvent isotope effect on the fluorescence of azoalkanes

    International Nuclear Information System (INIS)

    Mirbach, M.J.; Mirbach, M.F.; Cherry, W.R.; Turro, N.J.; Engel, P.

    1977-01-01

    A study of fluorescence quantum yields and fluorescence lifetimes of two cyclic azoalkanes reveal a striking dependence of phisub(F) and tausub(F) on solvent and on isotopic substitution (OH → OD). A mechanism involving specific deactivation of the fluorescent state from a hydrogen bonded complex is proposed to rationalize the data. (orig./HK) [de

  16. Radioactive isotope and isomer separation with using light induced drift effect

    International Nuclear Information System (INIS)

    Hradecny, C.; Slovak, J.; Tethal, T.; Ermolaev, I.M.; Shalagin, A.M.

    1991-01-01

    The isotope separation with using light induced drift (LID) is discussed. The basic theoretical characteristics of the method are deduced: separation simultaneously with an arbitrary high enrichment and without significant losses; separation productivity up to 100 μg/h. These characteristics are sufficient and very convenient for separation of expensive radioactive isotopes and isomers which are applied in medicine and science. The first experimental separation of the radioactive isotopes ( 22,24 Na) by using the LID effect is reported. 13 refs.; 5 figs

  17. Competition H(D) kinetic isotope effects in the autoxidation of hydrocarbons.

    Science.gov (United States)

    Muchalski, Hubert; Levonyak, Alexander J; Xu, Libin; Ingold, Keith U; Porter, Ned A

    2015-01-14

    Hydrogen atom transfer is central to many important radical chain sequences. We report here a method for determination of both the primary and secondary isotope effects for symmetrical substrates by the use of NMR. Intramolecular competition reactions were carried out on substrates having an increasing number of deuterium atoms at symmetry-related sites. Products that arise from peroxyl radical abstraction at each position of the various substrates reflect the competition rates for H(D) abstraction. The primary KIE for autoxidation of tetralin was determined to be 15.9 ± 1.4, a value that exceeds the maximum predicted by differences in H(D) zero-point energies (∼7) and strongly suggests that H atom abstraction by the peroxyl radical occurs with substantial quantum mechanical tunneling.

  18. Isotope and Electric Field Effects in Dissociative Recombination of D3+

    International Nuclear Information System (INIS)

    Larsson, M.; Rosen, S.; Danared, H.; Larson, A.; Le Padellec, A.; Semaniak, J.; Stroemholm, C.; Peterson, J.R.

    1997-01-01

    The cross section for dissociative recombination of vibrationally cold D 3 + has been measured at the ion storage ring CRYRING. The rate constant at 300K, α=2.7x10 -8 cm 3 s -1 , is a factor of 4.3 smaller than the corresponding value for H 3 + measured earlier in CRYRING. An electric field of 30V/cm was introduced in the electron-ion interaction region. This had no measurable effect on the dissociative recombination cross section. This suggests that the cross sections measured in storage rings for H 3 + and its isotopic variants can be directly compared with theoretical results once such results become available. copyright 1997 The American Physical Society

  19. Catalytic recruitment in the inactivation of acetylcholinesterase by soman: temperature dependence of the solvent isotope effect

    International Nuclear Information System (INIS)

    Kovach, I.M.; Huber, J.H.A.; Schowen, R.L.

    1988-01-01

    3,3-Dimethyl-2-butyl methylphosphonofluoridate (soman) recruits at least 60-70% of the catalytic power of acetylcholinesterase during phosphonylation of the active-site serine, as compared with the acetylation by acetylcholine. The solvent isotope effect is 1.34 +/- 0.11 and is temperature independent within experimental error between 5 and 45 0 C. This observation is quite similar to what has been found for the reactions of aryl acetates and anilides. Average activation parameters for the same temperature range are ΔH* = 7.3 +/- 0.6 kcal/mol and ΔS* = -4 +/- 2 eu (H 2 O) and ΔH* = 7.1 +/- 0.4 kcal/mol and ΔS* = -6 +/- 1 eu (D 2 O). A rate-limiting process with 50% contribution of an induced-fit conformational change is supported by the data

  20. Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

    Science.gov (United States)

    Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

    2015-05-26

    The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Variability in mesophyll conductance between barley genotypes, and effects on transpiration efficiency and carbon isotope discrimination.

    Science.gov (United States)

    Barbour, Margaret M; Warren, Charles R; Farquhar, Graham D; Forrester, Guy; Brown, Hamish

    2010-07-01

    Leaf internal, or mesophyll, conductance to CO(2) (g(m)) is a significant and variable limitation of photosynthesis that also affects leaf transpiration efficiency (TE). Genotypic variation in g(m) and the effect of g(m) on TE were assessed in six barley genotypes (four Hordeum vulgare and two H. bulbosum). Significant variation in g(m) was found between genotypes, and was correlated with photosynthetic rate. The genotype with the highest g(m) also had the highest TE and the lowest carbon isotope discrimination as recorded in leaf tissue (Delta(p)). These results suggest g(m) has unexplored potential to provide TE improvement within crop breeding programmes.

  2. Rate of uptake and distribution of Hg in dissolved organic carbon compounds in darkwater ecosystems by ICP-MS and enriched stable isotope spiking

    International Nuclear Information System (INIS)

    Telmer, Kevin; Dario Bermudez, Rafael; Veiga, Marcello M.; Souza, Terezinha Cid da

    2001-01-01

    The role of natural organic acids on mercury binding, transportation, net uptake rates and possibly net methylation rates will be evaluated by tracing these processes with isotope enriched mercury and ICP-MS technology. The correlation between dissolved organic matter and Hg in waters is well documented. It appears that organic acids can react with mercury residing in or emitted from different sources such as soils (particularly hydromorphic soils), laterites, natural degassing, forest fires, fuel combustion, gold mining activities, etc. to form soluble Hg-organo-complexes. The formation of these complexes is believed to greatly enhance Hg transport and be an important preliminary step in the formation of Methyl-Hg and biological uptake. The rates of these reactions and the key organic compounds involved in mercury binding will be determined by reacting isotopically-enriched Hg with samples containing a variety of concentrations and types of organic acids and subsequently analysing both reactants and organisms exposed to the reactants (bioassays) for Hg isotopes by ICP-MS. The Hg spike will allow the precise determination of rates of uptake and the most active agents of uptake. Initially, the method will be used to examine total Hg uptake and distribution but if technological limitations are overcome, this same approach can be used to determine net rates of methylation and net MeHg uptake. After the method is validated the experimental design can be altered to test the relative effects of such things as the addition of CO 2 (pH change), or adding a substrate such as Fe-Mn oxyhydroxides. The addition of synthetic materials such as mulched automobile tires, can also be tested with the goal developing a pragmatic remedial method for Hg containment. Ultimately, this research should contribute to an understanding of mercury mobilization, transport and bio-concentration mechanisms, and provide a basis for developing management and treatment strategies. Emphasis will be

  3. Temperature and Pressure Depences on the Isotopic Fractionation Effect in the Thermal Decomposition of Ozone

    Directory of Open Access Journals (Sweden)

    Su-Ju Kim

    1997-12-01

    Full Text Available To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures(30~150C. Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were peformed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.

  4. Determination of enzyme-substrate dissociation rates by dynamic isotope exchange enhancement experiments

    International Nuclear Information System (INIS)

    Kim, S.C.; Raushel, F.M.

    1986-01-01

    A new method for the determination of dissociation rates of enzyme-substrate complexes has been developed. The rate of exchange of a labeled product back into the substrate is measured during catalysis of the forward reaction when the forward reaction is kept far from equilibrium by the enzymatic removal of the nonexchanging product. The ratio of the exchange rate and the net rate for product formation is then determined at various concentrations of the exchanging product. A plot of this ratio is a diagnostic indication of the kinetic mechanism and the relative rates of product dissociation from the binary and ternary enzyme complexes. This technique has been applied to the reaction catalyzed by bovine liver argininosuccinate lyase. The ratio for the rate of exchange of fumarate into argininosuccinate and the net rate for product formation was found to increase with the concentration of fumarate but to reach a limit of 3.3. The ratio of rates was half-maximal at 36 mM fumarate. The data have been interpreted to indicate the argininosuccinate lyase has a random kinetic mechanism. The calculated lower limit for the rate of release of arginine from the enzyme-fumarate-arginine complex is 0.35 times as fast as the Vmax in the reverse direction. The rate of release of arginine from the enzyme-arginine binary complex is 210 times faster than Vmax in the reverse direction

  5. A mechanical system design of the iridium-192 isotope wire in cervical cancer brachytherapy with medium dose rate

    International Nuclear Information System (INIS)

    Ari Satmoko; Sanda; Tri Harjanto; Atang Susila

    2010-01-01

    In 2010, brachytherapy engineering development activities have a purpose to establish a detailed design of the cervical cancer brachytherapy with medium dose rate. The brachytherapy will use an Iridium-92 source with the emitting radiation of 5 to 10 Curies. The source is wrapped in SS-316 capsule and carried by a SS-316 wire having diameter of about 1 mm dan length of 1800 mm. As part of this activity, the preliminary design of the mechanical drive systems for the isotope source has been developed. The technical specifications for the main components of the mechanical drive system have been successfully determined. This is started by studying the concept design, performing calculations, determining technical specifications, and finally defining the main components. From the evaluation, some components were decided: a stepper motor PK264A1-SG10, needle bearing NKI-10/20, spiral tube in SS316-1/8'' with 120 mm in diameter, rubber-based belts with a width of 20 mm, and aluminium drum with a diameter of 100 mm. Not all components could be identified in detail, especially for the components that do not exist in the marketplace and have to be created ourself Since the main components have been identified, the detailed design step of the mechanical drive systems for the isotope source can be performed. (author)

  6. Th isotopes in the Santa Monica basin: temporal variation, long-term mass balance and model rate constants

    International Nuclear Information System (INIS)

    Huh, Chih-An

    1995-01-01

    Distribution and flux of 234 Th, 232 Th and 230 Th in the water column of central Santa Monica basin observed over a period of seven years show seasonal and interannual variabilities. A steady-state model is applied to the integrated data to calculate long term average flux and model rate constants of Th isotopes. Mass balance calculations show that the basin acts like a closed system for short-lived 234 Th, but not for the long-lived isotopes 230 Th and 232 Th. Most 230 Th in the basin is transported from elsewhere. Of the incoming Th, 40-55% of the 230 Th and 14-26% of the 232 Th enter the surface water in dissolved form. In the upper 100m, the residence time of dissolved Th with respect to adsorption onto suspended particulates, 70-80 days, is about one order of magnitude higher than the residence time of suspended particles with respect to aggregation into sinking particles, 7-10 days. (author)

  7. Mechanical Design of the Radio-Isotope Source Driver Module for an Initial Prototype of Medium Dose Rate Brachytherapy

    International Nuclear Information System (INIS)

    Ari Satmoko; Tri Harjanto; Hendra Prasetia

    2012-01-01

    High dose rate brachytherapy equipment for therapy against cervical cancer is developed by empowering local products. An Iridium-192 with 5 Curies of energy is used. The source is wrapped in a capsule and combined with a wire diameter of 1 mm and length 1800 mm. The therapy is carried out by inserting the radiation source into the patient's body through an applicator. The system for loading-unloading the isotope source is divided into three modules: the source driver module, the source container modules, and channel distributor module. In this paper, the discussion is focused on engineering activities of the first module that serves to drive forward and backward position of the Iridium-192 isotope sources. The activity begins with the development of preliminary design sketches that produces drawings of mechanical components required. Furthermore, the calculations are carried out in order to establish the main component specifications. From this stage, a stepper motor type M66-A50K-G10 as a mechanical driver is chosen. The next stage is developing the detailed design and producing detailed drawings for all components. The fabrication of each component refers to the detailed design drawings. All components are assembled completely into the source driver module. Test also shows that the module works manually well. By rotating the manual handle in both directions, the tip of the wire moves alternately in forward and backward directions. (author)

  8. The mechanical system design of the iridium-192 isotope wire in cervical cancer brachytherapy with medium dose rate

    International Nuclear Information System (INIS)

    Ari Satmoko; Sanda; Tri Harjanto; Atang Susila

    2010-01-01

    In 2010, brachytherapy engineering activities have a purpose to establish a detailed design of the cervical cancer brachytherapy with medium dose rate. The brachytherapy will use an Iridium-92 source with the emiting radiation of 5 to 10 Curies. The source is wrapped in SS-316 capsule and carried by a SS-316 wire having diameter of about 1 mm dan length of 1800 mm. As part of this activity, the preliminary design of the mechanical drive systems for the isotope source has been developed. The technical specifications for the main components of the mechanical drive system have been successfully determined. This is started by studying the concept design, performing calculations, determining technical specifications, and finally defining the main components. From the evaluation, some components were decided: a stepper motor PK264A1-SG10, needle bearing NKI-10/20, spiral tube in SS316-1/8'' with 120 mm in diameter, rubber-based belts with a width of 20 mm, and aluminium drum with a diameter of 100 mm. Not all components could be identified in detail, especially for the components that do not exist in the market place and have to be created ourself. Since the main components have been identified, the detailed design step of the mechanical drive systems for the isotope source can be performed. (author)

  9. Stable isotope studies

    International Nuclear Information System (INIS)

    Ishida, T.

    1992-01-01

    The research has been in four general areas: (1) correlation of isotope effects with molecular forces and molecular structures, (2) correlation of zero-point energy and its isotope effects with molecular structure and molecular forces, (3) vapor pressure isotope effects, and (4) fractionation of stable isotopes. 73 refs, 38 figs, 29 tabs

  10. Dose Rate Effects in Linear Bipolar Transistors

    Science.gov (United States)

    Johnston, Allan; Swimm, Randall; Harris, R. D.; Thorbourn, Dennis

    2011-01-01

    Dose rate effects are examined in linear bipolar transistors at high and low dose rates. At high dose rates, approximately 50% of the damage anneals at room temperature, even though these devices exhibit enhanced damage at low dose rate. The unexpected recovery of a significant fraction of the damage after tests at high dose rate requires changes in existing test standards. Tests at low temperature with a one-second radiation pulse width show that damage continues to increase for more than 3000 seconds afterward, consistent with predictions of the CTRW model for oxides with a thickness of 700 nm.

  11. Isotopic incorporation and the effects of fasting and dietary lipid content on isotopic discrimination in large carnivorous mammals

    Science.gov (United States)

    Rode, Karyn D.; Stricker, Craig A.; Erlenbach, Joy; Robbins, Charles T.; Cherry, Seth; Newsome, Seth D.; Cutting, Amy; Jensen, Shannon; Stenhouse, Gordon; Brooks, Matt; Hash, Amy; Nicassio, Nicole

    2016-01-01

    There has been considerable emphasis on understanding isotopic discrimination for diet estimation in omnivores. However, discrimination may differ for carnivores, particularly species that consume lipid-rich diets. Here, we examined the potential implications of several factors when using stable isotopes to estimate the diets of bears, which can consume lipid-rich diets and, alternatively, fast for weeks to months. We conducted feeding trials with captive brown bears (Ursus arctos) and polar bears (Ursus maritimus). As dietary lipid content increased to ∼90%, we observed increasing differences between blood plasma and diets that had not been lipid extracted (∆13Ctissue-bulk diet) and slightly decreasing differences between plasma δ13C and lipid-extracted diet. Plasma Δ15Ntissue-bulk diet increased with increasing protein content for the four polar bears in this study and data for other mammals from previous studies that were fed purely carnivorous diets. Four adult and four yearling brown bears that fasted 120 d had plasma δ15N values that changed by <±2‰. Fasting bears exhibited no trend in plasma δ13C. Isotopic incorporation in red blood cells and whole blood was ≥6 mo in subadult and adult bears, which is considerably longer than previously measured in younger and smaller black bears (Ursus americanus). Our results suggest that short-term fasting in carnivores has minimal effects on δ13C and δ15N discrimination between predators and their prey but that dietary lipid content is an important factor directly affecting δ13C discrimination and indirectly affecting δ15N discrimination via the inverse relationship with dietary protein content.

  12. High Acidification Rate of Norwegian Sea Revealed by Boron Isotopes in the Deep-Sea Coral Madrepora Oculata

    Science.gov (United States)

    Gonzalez, C.; Douville, E.; Hall-Spencer, J.; Montagna, P.; Louvat, P.; Gaillardet, J.; Frank, N.; Bordier, L.; Juillet-Leclerc, A.

    2012-12-01

    Ocean acidification and global warming due to the increase of anthropogenic CO2 are major threats for marine calcifying organisms, such as deep-sea corals, particularly in high-latitude regions. In order to evaluate the current anthropogenic perturbation and to properly assess the impacts and responses of calcifiers to previous changes in pH it is critical to investigate past changes of the seawater carbonate system. Unfortunately, current instrumental records of oceanic pH are limited, covering only a few decades. Scleractinian coral skeletons record chemical parameters of the seawater in which they grow. However, pH variability over multidecadal timescales remains largely unknown in intermediate and deep seawater masses. Here we present a study that highlights the potential of deep-sea-corals to overcome the lack of long-term pH records and that emphasizes a rapid acidification of high latitude subsurface waters of Norwegian Sea during the past decades. We have reconstructed seawater pH and temperature from a well dated deep-sea coral specimen Madrepora oculata collected alive from Røst reef in Norwegian Sea (67°N, 9°E, 340 m depth). This large branching framework forming coral species grew its skeleton over more than four decades determined using AMS 14C and 210Pb dating (Sabatier et al. 2012). B-isotopes and Li/Mg ratios yield an acidification rate of about -0.0030±0.0008 pH-unit.year-1 and a warming of 0.3°C during the past four decades (1967-2007). Overall our reconstruction technique agrees well with previous pH calculations (Hönisch et al., 2007 vs. Trotter et al., 2011 and McCulloch et al., 2012, i.e. the iterative method), but additional corrections are here applied using stable isotope correlations (O, C, B) to properly address kinetic fractionation of boron isotopes used for pH reconstruction. The resulting pH curve strongly anti-correlates with the annual NAO index, which further strengthens our evidence for the ocean acidification rate

  13. Normal coordinate treatment of liquid water and calculation of vapor pressure isotope effects

    International Nuclear Information System (INIS)

    Gellai, B.; Van Hook, W.A.

    1983-01-01

    A vibrational analysis of liquid water is reported, assuming a completely hydrogen-bonded network with continuously varying strengths of the hydrogen bonds. Frequency distribution calculations are made for intramolecular stretching and bending modes and for the intramolecular frequency region. The calculated distributions are compared with the experimental spectroscopic ones. As another test, vapor pressure isotope effects are calculated from the theoretical distributions for some isotopic water molecules. Results are compared with those of other authors obtained from a mixture model. (author)

  14. The effective management of medical isotope production in research reactors

    International Nuclear Information System (INIS)

    Drummond, D.T.

    1993-01-01

    During the 50-yr history of the use of radioisotopes for medical applications, research reactors have played a pivotal role in the production of many if not most of the key products. The marriage between research reactors and production operations is subject to significant challenges on two fronts. The medical applications of the radioisotope products impose some unique constraints and requirements on the production process. In addition, the mandates and priorities of a research reactor are not always congruent with the demands of a production environment. This paper briefly reviews the historical development of medical isotope production, identifies the unique challenges facing this endeavor, and discusses the management of the relationship between the isotope producer and the research reactor operator. Finally, the key elements of a successful relationship are identified

  15. Plasma Protein Turnover Rates in Rats Using Stable Isotope Labeling, Global Proteomics, and Activity-Based Protein Profiling

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Jordan N.; Tyrrell, Kimberly J.; Hansen, Joshua R.; Thomas, Dennis G.; Murphree, Taylor A.; Shukla, Anil K.; Luders, Teresa; Madden, James M.; Li, Yunying; Wright, Aaron T.; Piehowski, Paul D.

    2017-12-06

    Protein turnover is important for general health on cellular and organism scales providing a strategy to replace old, damaged, or dysfunctional proteins. Protein turnover also informs of biomarker kinetics, as a better understanding of synthesis and degradation of proteins increases the clinical utility of biomarkers. Here, turnover rates of plasma proteins in rats were measured in vivo using a pulse-chase stable isotope labeling experiment. During the pulse, rats (n=5) were fed 13C6-labeled lysine (“heavy”) feed for 23 days to label proteins. During the chase, feed was changed to an unlabeled equivalent feed (“light”), and blood was repeatedly sampled from rats over 10 time points for 28 days. Plasma samples were digested with trypsin, and analyzed with liquid chromatography-tandem mass spectrometry (LC-MS/MS). MaxQuant was used to identify peptides and proteins, and quantify heavy:light lysine ratios. A system of ordinary differential equations was used to calculate protein turnover rates. Using this approach, 273 proteins were identified, and turnover rates were quantified for 157 plasma proteins with half-lives ranging 0.3-103 days. For the ~70 most abundant proteins, variability in turnover rates among rats was low (median coefficient of variation: 0.09). Activity-based protein profiling was applied to pooled plasma samples to enrich serine hydrolases using a fluorophosphonate (FP2) activity-based probe. This enrichment resulted in turnover rates for an additional 17 proteins. This study is the first to measure global plasma protein turnover rates in rats in vivo, measure variability of protein turnover rates in any animal model, and utilize activity-based protein profiling for enhancing measurements of targeted, low-abundant proteins, such as those commonly used as biomarkers. Measured protein turnover rates will be important for understanding of the role of protein turnover in cellular and organism health as well as increasing the utility of protein

  16. Investigating the effects of abyssal peridotite alteration on Si, Mg and Zn isotopes

    Science.gov (United States)

    Savage, P. S.; Wimpenny, J.; Harvey, J.; Yin, Q.; Moynier, F.

    2013-12-01

    Around 1/3 of Earth's divergent ridge system is now classified as "slow" spreading [1], exposing ultramafic rocks (abyssal peridotites) at the seafloor. Such material is often highly altered by serpentinisation and steatisation (talc formation). It is crucial to understand such processes in order to access the original composition of the mantle, and to quantify any impact on ocean composition. Here we examine the effect of both serpentinisation and steatisation on Si, Mg and Zn isotopes. Hydrothermal alteration and seafloor weathering are both sources of oceanic Si [2] and weathering of abyssal peridotites is a source of oceanic Mg [3]; hence isotopic fractionation as a result of seafloor alteration could affect oceanic Si and Mg isotope composition. Zinc isotopes can provide complimentary information; the magnitude and direction of fractionation is highly dependent on complexing ligand [4] and can provide compositional information on the fluids driving metasomatism. For this study, two cores from the well-characterised abyssal peridotites recovered on ODP Leg 209 were examined [5]. Hole 1274a peridotites exhibit variable serpentinisation at ~200°C, whereas samples from Hole 1268a have been comprehensively serpentinised and then subsequently steatised to talc facies at ~350°C, by a low Mg/Si, low pH fluid. The Si, Mg and Zn isotope compositions of 1274a samples are extremely homogeneous, identical to that of pristine mantle rocks (BSE) i.e., serpentinisation at this locality was predominantly isochemical [5]. In contrast, samples from 1268a show greater isotopic variability. In all samples, Mg is enriched in the heavier isotopes relative to BSE, consistent with formation of isotopically heavy secondary phases [6]. For Si, serpentinised samples are slightly enriched in the lighter isotopes compared to BSE, again consistent with the behaviour of Si during formation of secondary phases [7]. Within the steatised samples, some exhibit enrichments in the lighter Si

  17. ICP-MS as the method of the determination of gallium, indium and thallium isotope ratios in the studies of isotope effects in the chromatography systems

    International Nuclear Information System (INIS)

    Herdzik, I.

    2006-01-01

    The procedure of the determination of gallium, indium and thallium isotope ratios and its application to the studies of the isotope effects in chromatography systems by the ICP-MS method (inductively coupled plasma-mass spectrometry) are presented. It was shown that it is possible to determine the isotope ratios of gallium ( 69/71 Ga), indium ( 113/115 In) and thallium ( 203/205 Tl) with the relative standard deviation 0.03-0.07%. Such precision appeared to be sufficient to calculate the unit separation factors in the column chromatographic processes. (author) [pl

  18. Lithium isotope effect in the extraction systems of polyethers: effect of salt concentration

    International Nuclear Information System (INIS)

    Fang Shengqiang; Fu Lian

    1991-01-01

    Separation factors of lithium isotopes at 20 deg C were determined in the extraction systems of B15C5-CHCl 3 /LiBr-H 2 O. The initial concentration of LiBr was controlled in the extent of more than 2 mol/l. It may be established that the increase of LiBr concentration causes a remarkable increase of the separation factor. The essence of this effect due to the change in salt concentration was discussed in connection with examination of relevant phenomena in literature. It can be concluded that the relationship between α and Cm, the concentration of lithium salt, is dependent on K Q and K P express respectively, lithium isotope exchange equilibrium constants between Li-crownether complex and hydrated lithium ion for lithium concentration less than 1-2 mol/l, and between lithium salt ion pair and hydrated lithium ion for lithium concentration more than 2 mol/l in aqueous phase

  19. Isotope effects of trapped electron modes in the presence of impurities in tokamak plasmas

    Science.gov (United States)

    Shen, Yong; Dong, J. Q.; Sun, A. P.; Qu, H. P.; Lu, G. M.; He, Z. X.; He, H. D.; Wang, L. F.

    2016-04-01

    The trapped electron modes (TEMs) are numerically investigated in toroidal magnetized hydrogen, deuterium and tritium plasmas, taking into account the effects of impurity ions such as carbon, oxygen, helium, tungsten and others with positive and negative density gradients with the rigorous integral eigenmode equation. The effects of impurity ions on TEMs are investigated in detail. It is shown that impurity ions have substantially-destabilizing (stabilizing) effects on TEMs in isotope plasmas for {{L}ez}\\equiv {{L}ne}/{{L}nz}>0 (TEM turbulences in hydrogenic isotope plasmas with and without impurities are performed. The relations between the maximum growth rate of the TEMs with respect to the poloidal wave number and the ion mass number are given in the presence of the impurity ions. The results demonstrate that the maximum growth rates scale as {γ\\max}\\propto Mi-0.5 in pure hydrogenic plasmas. The scale depends on the sign of its density gradient and charge number when there is a second species of (impurity) ions. When impurity ions have density profiles peaking inwardly (i.e. {{L}ez}\\equiv {{L}ne}/{{L}nz}>0 ), the scaling also depends on ITG parameter {ηi} . The maximum growth rates scale as {γ\\max}\\propto M\\text{eff}-0.5 for the case without ITG ({ηi}=0 ) or the ITG parameter is positive ({ηi}>0 ) but the impurity ion charge number is low (Z≤slant 5.0 ). However, when {ηi}>0 and the impurity ion charge number is moderate (Z=6.0-8.0 ), the scaling law is found as {γ\\max}\\propto M\\text{eff}-1.0 . Here, Z is impurity ion charge number, and the effective mass number, {{M}\\text{eff}}=≤ft(1-{{f}z}\\right){{M}i}+{{f}z}{{M}z} , with {{M}i} and {{M}Z} being the mass numbers of the hydrogenic and impurity ions, respectively, and {{f}z}=Z{{n}0z}/{{n}0e} being the charge concentration of impurity ions. In addition, with regard to the case of {{L}ez}<0 , the maximum growth rate scaling is {γ\\max}\\propto Mi-0.5 . The possible relations of the results

  20. Chemical and isotopic characterisation and sedimentation rates in Princess Charlotte Bay, Queensland

    International Nuclear Information System (INIS)

    Torgersen, T.; Chivas, A.R.; Chapman, A.

    1983-01-01

    Sedimentation rates in Princess Charlotte Bay are in the range 2.3-6.1 mm/yr, with mixed layers up to 10 cm thick, as determined by the 210 Pb method. 137 Cs determinations of sedimentation rate are not in disagreement, but are likely to yield ambiguous results in the Great Barrier Reef Province, because of diffusive redistribution, owing to the low distribution coefficient, K/sub D/ = 420-800, measured in lagoonal sediments

  1. Chemical Ligation and Isotope Labeling to Locate Dynamic Effects during Catalysis by Dihydrofolate Reductase.

    Science.gov (United States)

    Luk, Louis Y P; Ruiz-Pernía, J Javier; Adesina, Aduragbemi S; Loveridge, E Joel; Tuñón, Iñaki; Moliner, Vincent; Allemann, Rudolf K

    2015-07-27

    Chemical ligation has been used to alter motions in specific regions of dihydrofolate reductase from E. coli and to investigate the effects of localized motional changes on enzyme catalysis. Two isotopic hybrids were prepared; one with the mobile N-terminal segment containing heavy isotopes ((2) H, (13) C, (15) N) and the remainder of the protein with natural isotopic abundance, and the other one with only the C-terminal segment isotopically labeled. Kinetic investigations indicated that isotopic substitution of the N-terminal segment affected only a physical step of catalysis, whereas the enzyme chemistry was affected by protein motions from the C-terminal segment. QM/MM studies support the idea that dynamic effects on catalysis mostly originate from the C-terminal segment. The use of isotope hybrids provides insights into the microscopic mechanism of dynamic coupling, which is difficult to obtain with other studies, and helps define the dynamic networks of intramolecular interactions central to enzyme catalysis. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  2. Radioactive Emissions from Fission-Based Medical Isotope Production and Their Effect on Global Nuclear Explosion Detection

    International Nuclear Information System (INIS)

    Bowyer, T.; Saey, P.

    2015-01-01

    The use of medical isotopes, such as Tc-99m, is widespread with over 30 million procedures being performed every year, but the fission-based production of isotopes used for medical procedures causes emissions into the environment. This paper will show that gaseous radioactive isotopes of xenon, such as Xe-133, are released in high quantities, because they have a high fission cross section and they are difficult to scrub from the processes used to produce the medical isotopes due to their largely unreactive nature. Unfortunately, the reasons that large amounts of radioactive xenon isotopes are emitted from isotope production are the same as those that make these isotopes the most useful isotopes for the detection of underground nuclear explosions. Relatively recently, the nuclear explosion monitoring community has established a provisional monitoring network for the Comprehensive Nuclear-Test-Ban Treaty (CTBT) that includes radioactive xenon monitoring as a major component. This community has discovered that emissions from medical isotope production present a more serious problem to nuclear explosion monitoring than thought when the network was first conceived. To address the growing problem, a group of scientists in both the monitoring and the isotope production communities have come together to attempt to find scientific and pragmatic ways to address the emissions problems, recognizing that medical isotope production should not be adversely affected, while monitoring for nuclear explosions should remain effective as isotope production grows, changes, and spreads globally. (author)

  3. Isotope effects in the evaporation of water: a status report of the Craig-Gordon model.

    Science.gov (United States)

    Horita, Juske; Rozanski, Kazimierz; Cohen, Shabtai

    2008-03-01

    The Craig-Gordon model (C-G model) [H. Craig, L.I. Gordon. Deuterium and oxygen 18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperatures, E. Tongiorgi (Ed.), pp. 9-130, Laboratorio di Geologia Nucleare, Pisa (1965).] has been synonymous with the isotope effects associated with the evaporation of water from surface waters, soils, and vegetations, which in turn constitutes a critical component of the global water cycle. On the occasion of the four decades of its successful applications to isotope geochemistry and hydrology, an attempt is made to: (a) examine its physical background within the framework of modern evaporation models, (b) evaluate our current knowledge of the environmental parameters of the C-G model, and (c) comment on a general strategy for the use of these parameters in field applications. Despite its simplistic representation of evaporation processes at the water-air interface, the C-G model appears to be adequate to provide the isotopic composition of the evaporation flux. This is largely due to its nature for representing isotopic compositions (a ratio of two fluxes of different isotopic water molecules) under the same environmental conditions. Among many environmental parameters that are included in the C-G model, accurate description and calculations are still problematic of the kinetic isotope effects that occur in a diffusion-dominated thin layer of air next to the water-air interface. In field applications, it is of importance to accurately evaluate several environmental parameters, particularly the relative humidity and isotopic compositions of the 'free-atmosphere', for a system under investigation over a given time-scale of interest (e.g., hourly to daily to seasonally). With a growing interest in the studies of water cycles of different spatial and temporal scales, including paleoclimate and water resource studies, the importance and utility of the C-G model is also likely to

  4. Isotope effect study of κ-(BEDT-TTF)2Cu(NCS)2: Labeling in the anion

    International Nuclear Information System (INIS)

    Kini, A.M.; Wang, H.H.; Schlueter, J.A.

    1995-01-01

    Since the initial discovery of organic superconductivity in 1979, a large number of organic superconductors have now been synthesized. However, the mechanism of electron-pairing in these novel superconductors has remained largely unresolved. Isotope effect studies constitute an important experimental tool for the investigation of whether or not the electron-pairing mechanism in organic superconductors is phonon-mediated, as in conventional superconductors. Recent isotope effect studies in the authors' laboratory, involving seven different isotopically labeled BEDT-TTF (or ET) derivatives, have demonstrated the following: (1) intramolecular phonon modes involving C double-bond C and Csingle bondS stretching vibrations in the ET donor molecule are not the dominant mediators of electron-pairing, and (2) in κ-(ET) 2 Cu(NCS) 2 , there exist two competing isotope effects--a normal mass effect, i.e., lowering of T c upon isotopic labeling, when the ET molecular mass is increased by concurrent 13 C and 34 S labeling, in addition to an inverse isotope effect upon deuterium labeling in ET. It is of great interest to investigate if there is an isotope effect when the charge-compensating anions, which are also located within the non-conducting layer in the superconducting cation-radical salts, are isotopically labeled. The existence of an isotope effect when the anions are labeled would be indicative of electron-pairing with the mediation of vibrational frequencies associated with the anions. In this paper, the authors present the results of the first isotope effect study in which isotopic labeling in the anion portion of κ-(ET) 2 Cu(NCS) 2 is carried out. The authors find no isotope effect when the carbon and nitrogen atoms of the thiocyanate groups in the anion are replaced with 13 C and 15 N isotopes

  5. Isotope angiocardiography

    International Nuclear Information System (INIS)

    Stepinska, J.; Ruzyllo, W.; Konieczny, W.

    1979-01-01

    Method of technetium isotope 99 m pass through the heart recording with the aid of radioisotope scanner connected with seriograph and computer is being presented. Preliminary tests were carried out in 26 patients with coronary disease without or with previous myocardial infarction, cardiomyopathy, ventricular septal defect and in patients with artificial mitral and aortic valves. The obtained scans were evaluated qualitatively and compared with performed later contrast X-rays of the heart. Size of the right ventricle, volume and rate of left atrial evacuation, size and contractability of left ventricle were evaluated. Similarity of direct and isotope angiocardiographs, non-invasional character and repeatability of isotope angiocardiography advocate its usefulness. (author)

  6. Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

    2013-05-01

    Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

  7. The effects of biomanipulation on the biogeochemistry, carbon isotopic composition and pelagic food web relations of a shallow lake

    Directory of Open Access Journals (Sweden)

    B. M. Bontes

    2006-01-01

    Full Text Available In this study we investigated the effects of experimental biomanipulation on community structure, ecosystem metabolism, carbon biogeochemistry and stable isotope composition of a shallow eutrophic lake in the Netherlands. Three different biomanipulation treatments were applied. In two parts of the lake, isolated from the rest, fish was removed and one part was used as a reference treatment in which no biomanipulation was applied. Stable isotopes have proved useful to trace trophic interactions at higher food web levels but until now methodological limitations have restricted species specific isotope analysis in the plankton community. We applied a new approach based on the combination of fluorescence activated cell sorting (FACS and isotope ratio mass spectrometry (IRMS to trace carbon flow through the planktonic food web. With this method we aimed at obtaining group specific δ13C signatures of phytoplankton and to trace possible shifts in δ13C resulting from fish removal. Biomanipulation led to an increase in transparency and macrophyte biomass and decrease in phytoplankton abundance, but zooplankton numbers did not increase. Fish removal also resulted in high pH, high O2, low CO2 and more negative δ13CDIC values than expected, which is attributed to chemical enhanced diffusion with large negative fractionation. Despite high temporal variation we detected differences between the isotopic signatures of the primary producers and between the different treatments. The fractionation values of green algae (~21 and diatoms (~23 were similar and independent of treatment, while fractionation factors of filamentous cyanobacteria were variable between the treatments that differed in CO2 availability. 13C-labeling of the phytoplankton groups showed that biomanipulation led to increased growth rates of green algae and diatoms at the expense of cyanobacteria. Finally, consumers seemed generalists to the available food sources.

  8. Measurement of loss rates of organic compounds in snow using in situ experiments and isotopically labelled compounds

    Directory of Open Access Journals (Sweden)

    Erika von Schneidemesser

    2012-07-01

    Full Text Available Organic molecular marker compounds are widely used to identify emissions from anthropogenic and biogenic air pollution sources in atmospheric samples and in deposition. Specific organic compounds have been detected in polar regions, but their fate after deposition to snow is poorly characterized. Within this context, a series of exposure experiments were carried out to observe the post-depositional processing of organic compounds under real-world conditions in snow on the surface of the Greenland Ice Sheet, at the Summit research station. Snow was prepared from water spiked with isotopically labelled organic compounds, representative of typical molecular marker compounds emitted from anthropogenic activities. Reaction rate constants and reaction order were determined based on a decrease in concentration to a stable, non-zero, threshold concentration. Fluoranthene-d10, docosane-d46, hexadecanoic acid-d31, docosanoic acid-d43 and azelaic acid-d14 were estimated to have first order loss rates within surface snow with reaction rate constants of 0.068, 0.040, 0.070, 0.067 and 0.047 h−1, respectively. No loss of heptadecane-d36 was observed. Overall, these results suggest that organic contaminants are archived in polar snow, although significant post-depositional losses of specific organic compounds occur. This has implications for the environmental fate of organic contaminants, as well as for ice-core studies that seek to use organic molecular markers to infer past atmospheric loadings, and source emissions.

  9. Estimation of production rates for in-situ cosmogenic isotopes and application to surface exposure dating: certitudes and uncertainties

    International Nuclear Information System (INIS)

    Graham, I.J.

    1996-01-01

    Cosmogenic nuclides, produced in-situ in rocks by the action of cosmic rays on target nuclei, are increasingly being employed by earth scientists in a wide variety of applications. For example, surface exposure dating is used to determine erosion rates, the age of debris flows, alluvial fans, volcanic eruptions, meteoritic impact craters, and glacial deposits, and the timing of recent movement along faults and tectonic uplift. The technique can thus play a vital role in the study of potential hazards from geological processes, by establishing recurrence intervals between them, and establish chronologies and periodicities for major paleoclimatic events. Before surface exposure dating methods using cosmogenic isotopes can be applied even more widely, production rates of the main nuclides of interest must be better known, and their temporal and spatial variabilities determined. This paper summarises the present state of knowledge on production rates of the currently most useful nuclides ( 10 Be, 26 Al, 36 Cl, 14 C, 3 He and 21 Ne), discusses the main areas of concern, and makes suggestions for future improvement. (author). 83 refs., 7 tabs., 11 figs

  10. The stable isotope amount effect: New insights from NEXRAD echo tops, Luquillo Mountains, Puerto Rico

    Science.gov (United States)

    Scholl, Martha A.; Shanley, James B.; Zegarra, Jan Paul; Coplen, Tyler B.

    2009-01-01

    The stable isotope amount effect has often been invoked to explain patterns of isotopic composition of rainfall in the tropics. This paper describes a new approach, correlating the isotopic composition of precipitation with cloud height and atmospheric temperature using NEXRAD radar echo tops, which are a measure of the maximum altitude of rainfall within the clouds. The seasonal differences in echo top altitudes and their corresponding temperatures are correlated with the isotopic composition of rainfall. These results offer another factor to consider in interpretation of the seasonal variation in isotopic composition of tropical rainfall, which has previously been linked to amount or rainout effects and not to temperature effects. Rain and cloud water isotope collectors in the Luquillo Mountains in northeastern Puerto Rico were sampled monthly for three years and precipitation was analyzed for δ18O and δ2H. Precipitation enriched in 18O and 2H occurred during the winter dry season (approximately December–May) and was associated with a weather pattern of trade wind showers and frontal systems. During the summer rainy season (approximately June–November), precipitation was depleted in 18O and 2H and originated in low pressure systems and convection associated with waves embedded in the prevailing easterly airflow. Rain substantially depleted in 18O and 2H compared to the aforementioned weather patterns occurred during large low pressure systems. Weather analysis showed that 29% of rain input to the Luquillo Mountains was trade wind orographic rainfall, and 30% of rainfall could be attributed to easterly waves and low pressure systems. Isotopic signatures associated with these major climate patterns can be used to determine their influence on streamflow and groundwater recharge and to monitor possible effects of climate change on regional water resources.

  11. Large area isotopic silicon targets for astrophysical reaction rate studies in Si-26

    NARCIS (Netherlands)

    Greene, JP; Berg, GPA

    2005-01-01

    For measurements of stellar reaction rates of proton rich nuclei involving resonance levels just above threshold, targets of Si-28 were used in studies of the Si-21(He-4, He-6)Si-26 reaction using the Research Center for Nuclear Physics (RCNP) Ring Cyclotron at Osaka University. Resonance structure

  12. Dew water effects on leaf water using a stable isotope approach

    Science.gov (United States)

    Kim, K.; Lee, X.

    2009-12-01

    The presence of dew is a common meteorological phenomenon in field conditions and takes into account for significant portion of hydrologic processes in terrestrial ecosystems. The isotope composition of leaf water plays an important role in the isotopic water and carbon fluxes between terrestrial plants and the atmosphere. However, the consequence of dew formation in the plant-atmosphere relations has been ignored in many studies. The objective of this study is to improve our understanding of environmental and biological controls on the leaf water in equilibrium with dew water through laboratory experiments. Five species of plants (soybean, corn, sorghum, wheat, cotton) were grown hydroponically with water of a known isotopic content in a greenhouse. On the day of the experiment, they were first moved to ambient environment in full sunlight for at least 6 hr and then into a dark container inside the lab for up to 48 hr in which water vapor isotope ratios, temperature, and humidity were controlled. This arrangement created a step change in the forcing on the plant isotopic exchange. Leaves were sampled prior to the transfer to the dark container and 6 more times every 4 - 12 hr over the experiment. Humidity inside the container was saturated to mimic dew events in field conditions. Water from the leaf samples was extracted by a vacuum line and was analyzed for both δD and δ18O. The dataset will allow us to evaluate leaf water isotopic theories by exploring the transitions of the isotopic ratio of leaf water in response to the step change. Specifically, we are interested in whether the stomatal opening is an effective pathway for gaseous exchange in total darkness and how the transitional behaviors of the isotopic ratio of leaf water differ between the C3 and C4 photosynthesis pathways.

  13. Alternate substrates and isotope effects as a probe of the malic enzyme reaction

    International Nuclear Information System (INIS)

    Gavva, S.R.

    1988-01-01

    Dissociation constants for alternative dinucleotide substrates and competitive inhibitors suggest that the dinucleotide binding site of the Ascaris suum NAD-malic enzyme is hydrophobic in the vicinity of the nicotinamide ring. Changes in the divalent metal ion activator from Mg 2+ to Mn 2+ or Cd 2+ results in a decrease in the dinucleotide affinity and an increase in the affinity for malate. Primary deuterium and 13 C isotope effects obtained with the different metal ions suggest either a change in the transition state structure for the hydride transfer or decarboxylation steps or both. Deuterium isotope effects are finite whether reactants are maintained at saturating or limiting concentrations with all the metal ions and dinucleotide substrates used. For the native enzyme, primary deuterium isotope effects increase with a concomitant decrease in the 13 C effects when NAD is replaced by an alternate dinucleotide substrate different in redox potential

  14. Determination of the mechanism of demethylenation of (methylenedioxy)phenyl compounds by cytochrome P450 using deuterium isotope effects

    International Nuclear Information System (INIS)

    Fukuto, J.M.; Kumagai, Y.; Cho, A.K.

    1991-01-01

    The mechanism of demethylenation of (methylenedioxy)benzene (MDB), (methylenedioxy)amphetamine (MDA), and (methylenedioxy)methamphetamine (MDMA) by purified rabbit liver cytochrome P450IIB4 has been investigated by using deuterium isotope effects. A comparison of the magnitude and direction of the observed kinetic isotope effects indicates that the three compounds are demethylenated by different mechanisms. The different mechanisms of demethylenation have been proposed on the basis of comparisons of the observed biochemical isotope effects with the isotope effects from purely chemical systems

  15. Kinetic isotope effects in reaction of ferment oxidation of tritium-labelled D-galactosamine

    International Nuclear Information System (INIS)

    Akulov, G.P.; Korsakova, N.A.

    1992-01-01

    Primary, secondary and intramolecular kinetic isotopic effects in reaction of ferment oxidation of D-galactosamine labelled by tritium in position 6, were measured. When comparing values of the effects with previously obtained results for similar reaction D-[6- 3 H]galactose, it was ascertained that the presence of aminogroup in galactopyranosyl mainly affects kinetics of substrate-ferment complex formation stage. The possibility to use kinetic isotope effects for increase in molar activity of D-galactosamine, labelled by tritium in position 6, is shown

  16. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Science.gov (United States)

    Kassem, M. E.; Hamed, A. E.; Abulnasr, L.; Abboudy, S.

    1994-11-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat ( Cp) technique. The obtained results showed an interesting dependence of the critical behavior of Cp on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (γ-type) to a first order transition. After γ-irradiation, the behavior of Cp around the phase transition region was essentially affected. The transition temperature, Tc, decreased and Δ Cp depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect.

  17. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    International Nuclear Information System (INIS)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S.

    1994-01-01

    Isotopic effects in pure and γ-irradiated triglycine selenate crystals were investigated using the specific heat (C p ) technique. The obtained results showed an interesting dependence of the critical behavior of C p on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order (λ-type) to a first order transition. After γ-irradiation, the behavior of C p around the phase transition region was essentially affected. The transition temperature, T c , decreased and ΔC p depressed, and the transition became broad. It was noted that the effect of γ-irradiation is opposite to the isotopic effect. (author)

  18. Radium isotopes in Port Phillip Bay: estimation of the rate of bio irrigation of sediments, and water residence time

    International Nuclear Information System (INIS)

    Hancock, G.J.; Webster, I.T.

    1998-01-01

    Recent work has shown that estuarine sediments are a source of radium (Ra) to coastal waters (Bollinger and Moore, 1982, Webster et al., 1994; Hancock et al., 1997). Ra is soluble in saline water (Moore, 1992, Webster et al., 1995) and is rapidly desorbed into porewater from deposited fluvial sediments where it is continuously generated by insoluble Th parents. The rate at which Ra effuses into surface water has been used to determine the rate of surface-water pore water exchange (Hancock and Murray, 1996). Once in the water column, the behaviour of Ra is essentially conservative, enabling the determination of water residence time in a semi-enclosed estuary (Turekian et al., 1996). Here we use measurements of Ra in an estuary to estimate two water mixing processes. Port Phillip Bay (PPB) is a semi-enclosed estuary adjacent to the city of Melbourne, one of the highest density population centres in Australia. The Bay is approximately 50 km in diameter, and has an average depth of 14 m. A recent study found that the potential for eutrophication and algal blooms in the Bay was intricately linked to the fate of nutrients, particularly nitrogen, discharged into the Bay from rivers, drains, and sewage treatment plants (Harris et al. 1996). Two of the most important processes controlling the levels of inorganic N in the water column were identified as bio irrigation of bottom sediments, and the rate of exchange of Bay water with ocean water via Bass Strait. In this paper we describe how Ra isotopes can be used to estimate the rates of these processes, and we compare these rates with estimates made using conventional techniques. Water and sediment samples were collected from five sites in February 1996. Sediment cores were collected by divers, frozen, and sectioned in the laboratory. Surface, mid depth and bottom water samples were collected using a Niskin bottle. Radionuclide activities were determined by alpha spectrometry (Martin and Hancock, 1992) and gamma spectrometry

  19. Passage rates in poultry digestion using stable isotope markers and INAA

    International Nuclear Information System (INIS)

    Dunkley, C.S.; Kim, W.K.; Ricke, S.C.; James, W.D.; Ellis, W.C.; McReynolds, J.L.; Kubena, L.F.; Nisbet, D.J.

    2008-01-01

    A method has been developed for the study of passage rates and mean residence times (MRT) of test rations through the gastrointestinal tracts of layer hens. The use of rare earth elements as stable indigestible markers monitored by neutron activation analysis has been previously demonstrated in numerous species. In this study hafnium was used to mark corn and alfalfa rations as well as a combination ration made up of 90% alfalfa and 10% corn. The primary goal of the study was to evaluate the potential for use of rare earth stable markers in poultry digestion and to determine efficiency of meal marking, optimum exposure rates and determination limits for use in the design of future experimental protocols. Three groups of 10 hens each were fed a particular marked meal with fecal droppings monitored for 24 hours. The hens were sacrificed after a second dosed feeding and a delay of two or seven hours, and digesta was collected from each portion of the gastrointestinal tract. Fecal dry matter as well as digesta collected was then prepared for analysis and the elemental concentrations of hafnium were measured with instrumental neutron activation analysis (INAA). Element adsorption on alfalfa was far less efficient than on the corn ration, limiting the applicability of much of the alfalfa data to digestion studies. Passage rate curves were prepared for corn. The marker was found to primarily concentrate in the ileum at both sacrifice times. (author)

  20. Primary and secondary kinetic isotope effects in the acid-catalyzed dehydration of 1,1'-diadamantylmethylcarbinol in aqueous acetic acid

    International Nuclear Information System (INIS)

    Lomas, J.S.

    1981-01-01

    The sulfuric acid catalyzed dehydration of 1,1'-diadamantyl-methylcarbinol in anhydrous acetic acid proceeds exclusively to 1,1'-bis(1-adamantyl)ethylene. The secondary deuterium isotope effect of 1.32 found for this reaction shows that carbonium ion formation from the protonated alcohol is rate determining. In the presence of water, however, capture of the carbonium ion competes with deprotonation, introducing a primary isotope effect. Consequently, the overall KIE rises, reaching 3.18 for 80% aqueous acetic acid. Analysis of the KIE for 80 to 100% aqueous acetic acid is consistent with a simple classical mechanism involving reversible formation of the intermediate carbonium ion. The primary isotope effect upon deprotonation is at the most 2.98, indicative of an asymmetric transition state close to the carbonium ion

  1. The nitrogen isotope effect of benthic remineralization-nitrification-denitrification coupling in an estuarine environment

    Directory of Open Access Journals (Sweden)

    M. Alkhatib

    2012-05-01

    Full Text Available The nitrogen (N stable isotopic composition of pore water nitrate and total dissolved N (TDN was measured in sediments of the St. Lawrence Estuary and the Gulf of St. Lawrence. The study area is characterized by gradients in organic matter reactivity, bottom water oxygen concentrations, as well as benthic respiration rates. N isotope effects on the water column associated with the benthic exchange of nitrate (εapp and TDN (εsed during benthic nitrification-denitrification coupling were investigated. The sediments were a major sink for nitrate and a source of reduced dissolved N (RDN = DON + NH4+. We observed that both the pore water nitrate and RDN pools were enriched in 15N relative to the water column, with increasing δ15N downcore in the sediments. As in other marine environments, the biological nitrate isotope fractionation of net fixed N loss was barely expressed at the scale of sediment-water exchange, with ϵapp values <3‰. The strongest under-expression (i.e. lowest εapp of the biological N isotope fractionation was observed at the most oxygenated sites with the least reactive organic matter, indicating that, through their control on the depth of the denitrification zone, bottom water oxygen concentrations and the organic matter reactivity can modulate εapp. For the first time, actual measurements of δ15N of pore water RDN were included in the calculations of εsed. We argue that large fractions of the sea-floor-derived DON are reactive and, hence, involved in the development of the δ15N of dissolved inorganic N (DIN in the water column. In the St. Lawrence sediments, the combined benthic N transformations yield a flux of 15N-enriched RDN that can significantly elevate εsed above εapp. Calculated εsed values were within the range of 4.6 ± 2

  2. Some measurements of H/D polarizability isotope effects using differential refractometry

    Energy Technology Data Exchange (ETDEWEB)

    Foster Smith, M; Van Hook, W A [Tennessee Univ., Knoxville (USA). Dept. of Chemistry

    1989-05-01

    Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.).

  3. Some measurements of H/D polarizability isotope effects using differential refractometry

    International Nuclear Information System (INIS)

    Foster Smith, M.; Van Hook, W.A.

    1989-01-01

    Refractive index differences between the H and D isomers of some common molecules in the liquid phase were measured between 404.7 and 690.0 nm. The data are combined with information on molar volume isotope effects to yield values for H/D isotope effects on the static polarizability, the vibrational contribution to the static and frequency dependent parts of the polarizability, and the H/D isotope effect on the second moment of the electronic charge distribution. The present results suffice to demonstrate the practicability of this technique to measure the components of the polarizability listed above. However for accurate resolution of the vibrational and second moment contributions, refractive index data of still greater precision will be required. (orig.)

  4. A multielement isotopic study of refractory FUN and F CAIs: Mass-dependent and mass-independent isotope effects

    Science.gov (United States)

    Kööp, Levke; Nakashima, Daisuke; Heck, Philipp R.; Kita, Noriko T.; Tenner, Travis J.; Krot, Alexander N.; Nagashima, Kazuhide; Park, Changkun; Davis, Andrew M.

    2018-01-01

    Calcium-aluminum-rich inclusions (CAIs) are the oldest dated objects that formed inside the Solar System. Among these are rare, enigmatic objects with large mass-dependent fractionation effects (F CAIs), which sometimes also have large nucleosynthetic anomalies and a low initial abundance of the short-lived radionuclide 26Al (FUN CAIs). We have studied seven refractory hibonite-rich CAIs and one grossite-rich CAI from the Murchison (CM2) meteorite for their oxygen, calcium, and titanium isotopic compositions. The 26Al-26Mg system was also studied in seven of these CAIs. We found mass-dependent heavy isotope enrichment in all measured elements, but never simultaneously in the same CAI. The data are hard to reconcile with a single-stage melt evaporation origin and may require reintroduction or reequilibration for magnesium, oxygen and titanium after evaporation for some of the studied CAIs. The initial 26Al/27Al ratios inferred from model isochrons span a range from <1 × 10-6 to canonical (∼5 × 10-5). The CAIs show a mutual exclusivity relationship between inferred incorporation of live 26Al and the presence of resolvable anomalies in 48Ca and 50Ti. Furthermore, a relationship exists between 26Al incorporation and Δ17O in the hibonite-rich CAIs (i.e., 26Al-free CAIs have resolved variations in Δ17O, while CAIs with resolved 26Mg excesses have Δ17O values close to -23‰). Only the grossite-rich CAI has a relatively enhanced Δ17O value (∼-17‰) in spite of a near-canonical 26Al/27Al. We interpret these data as indicating that fractionated hibonite-rich CAIs formed over an extended time period and sampled multiple stages in the isotopic evolution of the solar nebula, including: (1) an 26Al-poor nebula with large positive and negative anomalies in 48Ca and 50Ti and variable Δ17O; (2) a stage of 26Al-admixture, during which anomalies in 48Ca and 50Ti had been largely diluted and a Δ17O value of ∼-23‰ had been achieved in the CAI formation region; and (3

  5. Use of Isotopic Data to Determine Influence of Seasonal Effects in Rivers

    Energy Technology Data Exchange (ETDEWEB)

    Michel, R. L. [US Geological Survey, Menlo Park, CA (United States); Aggarwal, P. K.; Araguas Araguas, L.; Newman, B.; Kurttas, T. [International Atomic Energy Agency, Vienna (Austria)

    2013-07-15

    In 2002 the International atomic energy agency and its Member states initiated a programme for the collection and measurement of isotopes (stable isotopes of water and tritium) in river waters. The purpose of this programme is to establish a long term database (GNIR) similar to the global database currently available for precipitation. These isotopic data provide a baseline for studying parameters in hydrologic basins that can be used to monitor any changes in the basin response due to shifts in future climatic or land use factors. Below, selected {sup 18}O and tritium data sets where measurements from several years of routine sampling are available are analysed. A ratio of the average monthly isotopic concentration divided by the average yearly concentration is used to normalize data and makes it possible to compare data from different sites. In general, high flow periods are strongly influenced by younger water whereas baseflow is primarily composed of water of greater age (probably decadal). Using this approach and flow rates, it should be possible to estimate the isotopic concentrations of baseflow. This data set will make it possible to track changes in baseflow concentrations occurring due to future changes in climate or land use. (author)

  6. The common property of isotope anomalies in meteorites

    International Nuclear Information System (INIS)

    Robert, F.

    2004-01-01

    The treatment proposed to account for the non-mass-dependent isotopic fractionation effect observed for oxygen isotopes during the synthesis of ozone (Robert and Camy-Peyret 2001) is applied to other chemical elements. A numerical treatment to calculate isotopic reaction rate ratios is proposed. This treatment yields non-mass-dependent isotopic effects in other chemical elements, qualitatively similar to those observed in some of the high temperature minerals found in the carbonaceous meteorites. This treatment may reflect the numerical consequences of an unrecognized quantum mechanical effect, linked to a property of chemical reactions involving indistinguishable isotopes. (author)

  7. Strain rate effects of AM60

    International Nuclear Information System (INIS)

    Rehkopf, J.D.; Krause, A.R.

    2002-01-01

    Magnesium is seeing increasing use in the automotive industry due to its high strength-to-weight ratio and its ability to be cast to tight dimensional tolerances. Presently, main applications include interior components such as instrument panels, steering wheels and seat frames. Consequently, there is a strong need for understanding the rate effect on the behaviour of magnesium under impact type loading. In this work the effect of strain rate on AM60 tensile behaviour was investigated through both high and cold temperature testing, at ranges relevant to the automotive environment. Microstructural analysis, presented in this paper, includes porosity, grain size and fracture surface analyses. (author)

  8. Unusually large secondary deuterium isotope effect. Thermal trans-cis isomerization of trans-1-phenylcyclohexene

    International Nuclear Information System (INIS)

    Caldwell, R.A.; Misawa, H.; Healy, E.F.; Dewar, M.J.S.

    1987-01-01

    The magnitudes of secondary deuterium isotope effects (SDIE) are generally in the range of 0.9 < k/sub H//k/sub D/ < 1.25, and are often satisfactorily rationalized by the zero-point energy (ZPE) change on going from reactant to transition state due to C-H rehybridization. They now report a far larger SDIE for the title reaction. Its rationalization on the basis of transition state theory suggests that it more closely resembles a primary isotope effect

  9. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...

  10. Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

    Science.gov (United States)

    Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

    2006-12-15

    The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

  11. Correlation of the vapor pressure isotope effect with molecular force fields in the liquid state

    International Nuclear Information System (INIS)

    Pollin, J.S.; Ishida, T.

    1976-07-01

    The present work is concerned with the development and application of a new model for condensed phase interactions with which the vapor pressure isotope effect (vpie) may be related to molecular forces and structure. The model considers the condensed phase as being represented by a cluster of regularly arranged molecules consisting of a central molecule and a variable number of molecules in the first coordination shell. The methods of normal coordinate analysis are used to determine the modes of vibration of the condensed phase cluster from which, in turn, the isotopic reduced partition function can be calculated. Using the medium cluster model, the observed vpie for a series of methane isotopes has been successfully reproduced with better agreement with experiment than has been possible using the simple cell model. We conclude, however, that insofar as the medium cluster model provides a reasonable picture of the liquid state, the vpie is not sufficiently sensitive to molecular orientation to permit an experimental determination of intermolecular configuration in the condensed phase through measurement of isotopic pressure ratios. The virtual independence of vapor pressure isotope effects on molecular orientation at large cluster sizes is a demonstration of the general acceptability of the cell model assumptions for vpie calculations

  12. Dynamical barrier and isotope effects in the simplest substitution reaction via Walden inversion mechanism

    Science.gov (United States)

    Zhao, Zhiqiang; Zhang, Zhaojun; Liu, Shu; Zhang, Dong H.

    2017-02-01

    Reactions occurring at a carbon atom through the Walden inversion mechanism are one of the most important and useful classes of reactions in chemistry. Here we report an accurate theoretical study of the simplest reaction of that type: the H+CH4 substitution reaction and its isotope analogues. It is found that the reaction threshold versus collision energy is considerably higher than the barrier height. The reaction exhibits a strong normal secondary isotope effect on the cross-sections measured above the reaction threshold, and a small but reverse secondary kinetic isotope effect at room temperature. Detailed analysis reveals that the reaction proceeds along a path with a higher barrier height instead of the minimum-energy path because the umbrella angle of the non-reacting methyl group cannot change synchronously with the other reaction coordinates during the reaction due to insufficient energy transfer from the translational motion to the umbrella mode.

  13. Secondary deuterium isotope effects and transition state structure in the aromatic claisen rearrangement

    International Nuclear Information System (INIS)

    McMichael, K.D.; Korver, G.L.

    1979-01-01

    Kinetic experiments were carried out simultaneously on separate methyl salicylate solutions of allyl phenyl ether and its deuterated phenyl analogues at 170 to 195 0 C. Gas chromatographic analysis for allyl phenyl ether using an internal standard (anisole) and mechanical integration produced concentration/time data which were fitted to the exponential form of the first-order rate equation by a standard and nonlinear least-square program. At least 15 points were obtained for each run, covering 10 to 85% reaction. The derived isotope effects show no temperature dependence. Averages for 6 runs with each compound are k/sub H//k/sub α-D 2 / = 1.18 and K/sub H//k/sub γ-D 2 / = 0.95. An equilibrium α effect of 1.30 and a γ effect of 0.87 may be calculated for both deuterium atoms at 185 0 C. These results show that the C--H vibration frequencies are approximately (1.18 - 1)/(1.27 - 1) or 57 to 77% of the way from those of allyl phenyl ether to those of the cyclohexadiene intermediate. The C--H frequencies of the γ carbon in the transition state are about (0.95 - 1)/(0.88 - 1) or 22 to 62% of the way to those of the intermediate. The structure of the transition state, as far as these bonding frequencies are concerned, is consistent with the Claisen rearrangement

  14. Isotopic effects in the neon fixed point: uncertainty of the calibration data correction

    Science.gov (United States)

    Steur, Peter P. M.; Pavese, Franco; Fellmuth, Bernd; Hermier, Yves; Hill, Kenneth D.; Seog Kim, Jin; Lipinski, Leszek; Nagao, Keisuke; Nakano, Tohru; Peruzzi, Andrea; Sparasci, Fernando; Szmyrka-Grzebyk, Anna; Tamura, Osamu; Tew, Weston L.; Valkiers, Staf; van Geel, Jan

    2015-02-01

    The neon triple point is one of the defining fixed points of the International Temperature Scale of 1990 (ITS-90). Although recognizing that natural neon is a mixture of isotopes, the ITS-90 definition only states that the neon should be of ‘natural isotopic composition’, without any further requirements. A preliminary study in 2005 indicated that most of the observed variability in the realized neon triple point temperatures within a range of about 0.5 mK can be attributed to the variability in isotopic composition among different samples of ‘natural’ neon. Based on the results of an International Project (EUROMET Project No. 770), the Consultative Committee for Thermometry decided to improve the realization of the neon fixed point by assigning the ITS-90 temperature value 24.5561 K to neon with the isotopic composition recommended by IUPAC, accompanied by a quadratic equation to take the deviations from the reference composition into account. In this paper, the uncertainties of the equation are discussed and an uncertainty budget is presented. The resulting standard uncertainty due to the isotopic effect (k = 1) after correction of the calibration data is reduced to (4 to 40) μK when using neon of ‘natural’ isotopic composition or to 30 μK when using 20Ne. For comparison, an uncertainty component of 0.15 mK should be included in the uncertainty budget for the neon triple point if the isotopic composition is unknown, i.e. whenever the correction cannot be applied.

  15. Effect of Air Injection on Nucleation Rates

    DEFF Research Database (Denmark)

    Capellades Mendez, Gerard; Kiil, Søren; Dam-Johansen, Kim

    2017-01-01

    From disruption of the supersaturated solution to improved mass transfer in the crystallizing suspension, the introduction of a moving gas phase in a crystallizer could lead to improved rates of nucleation and crystal growth. In this work, saturated air has been injected to batch crystallizers...... to study the effects on formation of the first crystal and subsequent turbidity buildup. To account for the typically large sample-to-sample variation, nucleation rates were evaluated for a large number of replicates using probability distributions of induction times. The slope and the intercept...... was reduced from 69 to 13 min, and the mean induction time decreased from 128 to 36 min. The effect on aqueous solutions of l-arginine was less apparent, with a detection delay reduction from 15 to 3 min, and no significant changes on the rate of primary nucleation. These results demonstrate the potential...

  16. Solvent 1H/2H isotopic effects in the reaction of the L-Tyrosine oxidation catalyzed by Tyrosinase

    International Nuclear Information System (INIS)

    Kozlowska, M.; Kanska, M.

    2006-01-01

    Tyrosinase is well known catalyst in the oxidation of L-Tyrosine to L-DOPA and following oxidation of L-DOPA to dopachinone. The aim of communication is to present the results of studies on the solvent isotopic effects (SIE) in the above reactions for the 1 H/ 2 H in the 3',5' and 2',6' substituted tyrosine. Obtained dependence of the reaction rate on the substrate concentration were applied for optimization of the kinetic parameters, k cat and k cat /K m , in the Michaelis-Menten equation. As a result - better understanding of the L-DOPA creation can be achieved

  17. Lead isotope in mineral exploration

    International Nuclear Information System (INIS)

    Gulson, B.L.

    1986-01-01

    This book provides an up-to-date state-of-the-art review of lead isotopes in mineral exploration. Beginning with an historical review on suggested uses of lead isotopes in mineral exploration, the author then outlines the theoretical aspects of lead isotopes and illustrates that the method is based on well-known principles of radioactive decay, from which isotopic signatures for different styles of mineralization are derived. The varying isotopic signatures are then introduced. The major part of the book details over 40 case histories for base and precious metals, uranium and tin using sampling media such as sulfides, gossans, soils, weathered bedrock, vegetation and groundwaters. Advantages and disadvantages of each are discussed. Examples are given of the use of lead isotopes in testing conceptual models for exploration. The success rate and cost-effectiveness of the method are illustrated by actual exploration examples. Analytical advances which should lower the cost of the method and future uses are outlined. Many of the case histories use recently published or unpublished data, 27 tables of which are given in an appendix. Details of sampling, the methods for obtaining the isotope ratios, and a commercially-available integrated lead isotope service are also provided. (Auth.)

  18. Effect of isotopic substitution on the collisional quenching of vibronically excited CO+

    International Nuclear Information System (INIS)

    Katayama, D.H.; Welsh, J.A.

    1983-01-01

    Rovibronic levels of the A 2 Pi/sub i/ state for 12 C 16 O + and 13 C 16 O + have been selectively excited by a pulsed, tunable dye laser and their time resolved fluorescence obtained as a function of helium pressure. These ions are formed by reaction of neutral carbon monoxide with helium metastable atoms created in a dc discharge. Since 13 CO + has essentially the same potential energy curves as 12 CO + , but differs primarily in its vibrational energy spacings, this experiment accentuates the role, in the collisional deactivation process, of the high lying ground state vibrational levels which are adjacent to the laser populated vibronic levels of the A 2 Pi/sub i/ state. Quenching rates are determined for the v' = 0, 1, and 2 levels which have relatively insignificant isotope shifts of a few wave numbers for the two isotopes. The difference in rates for the two isotopic ions demonstrates the importance of the positions for the high lying v'' = 10 and 11 ground state levels which have large isotope shifts of hundreds of wave numbers. A discussion of the deactivation process is given in terms of perturbations, Franck--Condon factors, energy gaps, and other considerations

  19. Zone edge effects with variable rate irrigation

    Science.gov (United States)

    Variable rate irrigation (VRI) systems may offer solutions to enhance water use efficiency by addressing variability within a field. However, the design of VRI systems should be considered to maximize application uniformity within sprinkler zones, while minimizing edge effects between such zones alo...

  20. Kinetic solvent isotope effects in the additions of bromine and 4-chlorobenzenesulfenyl chloride to alkenes and alkynes

    International Nuclear Information System (INIS)

    Modro, A.; Schmid, G.H.; Yates, K.

    1979-01-01

    The rates of bromination of selected alkenes and alkynes in methanol/methanol-d, acetic acid/acetic acid-d, and formic acid/formic acid-d have a nearly constant value of k/sub H//k/sub D/ = 1.23 +- 0.02. This kinetic solvent isotope effect is attributed to specific electrophilic solvation of the incipient bromide anion by hydrogen bonding in the rate-determining transition state. The rates of bromination were measured in two solvents having the same values of the solvent parameter Y but different nucleophilicities in order to assess the importance of nucleophilic solvation. Significant nucleophilic solvent assistance is found for only alkylacetylenes. The kinetic solvent isotope effects of the addition of 4-chlorobenzenesulfenyl chloride to selected alkenes and alkynes in acetic acid/acetic acid-d vary from 1.00 to 1.28. These data are consistent with two mechanisms: one involves a tetravalent sulfur intermediate while the second is the sulfur analogue of the S/sub N/2 mechanism

  1. Isotopic and spin-nuclear effects in solid hydrogens (Review Article)

    Science.gov (United States)

    Freiman, Yuri A.; Crespo, Yanier

    2017-12-01

    The multiple isotopic family of hydrogens (H2, HD, D2, HT, DT, T2) due to large differences in the de Boer quantum parameter and inertia moments displays a diversity of pronounced quantum isotopic solid-state effects. The homonuclear members of this family (H2, D2, T2) due to the permutation symmetry are subjects of the constraints of quantum mechanics which link the possible rotational states of these molecules to their total nuclear spin giving rise to the existence of two spin-nuclear modifications, ortho- and parahydrogens, possessing substantially different properties. Consequently, hydrogen solids present an unique opportunity for studying both isotope and spin-nuclear effects. The rotational spectra of heteronuclear hydrogens (HD, HT, DT) are free from limitations imposed by the permutation symmetry. As a result, the ground state of these species in solid state is virtually degenerate. The most dramatic consequence of this fact is an effect similar to the Pomeranchuk effect in 3He which in the case of the solid heteronuclear hydrogens manifests itself as the reentrant broken symmetry phase transitions. In this review article we discuss thermodynamic and kinetic effects pertaining to different isotopic and spin-nuclear species, as well as problems that still remain to be solved.

  2. Quantifying chemical weathering rates along a precipitation gradient on Basse-Terre Island, French Guadeloupe: new insight from U-series isotopes in weathering rinds

    Science.gov (United States)

    Engel, Jacqueline M.; May, Linda; Sak, Peter B.; Gaillardet, Jerome; Ren, Minghua; Engle, Mark A.; Brantley, Susan L.

    2016-01-01

    . This is the first time that multiple weathering clasts from the same watershed were analyzed for U-series isotope disequlibrian and show consistent results. The U-series disequilibria allowed for the determination of rind formation ages and weathering advance rates with a U-series mass balance model. The weathering advance rates generally decreased with decreasing curvature: ∼0.17 ± 0.10 mm/kyr for high curvature, ∼0.12 ± 0.05 mm/kyr for medium curvature, and ∼0.11 ± 0.04, 0.08 ± 0.03, 0.06 ± 0.03 mm/kyr for low curvature locations. The observed positive correlation between the curvature and the weathering rates is well supported by predictions of weathering models, i.e., that the curvature of the rind-core boundary controls the porosity creation and weathering advance rates at the clast scale.At the watershed scale, the new weathering advance rates derived on the low curvature transects for the relatively dry Deshaies watershed (average rate of 0.08 mm/kyr; MAP = 1800 mm and MAT = 23 °C) are ∼60% slower than the rind formation rates previously determined in the much wetter Bras David watershed (∼0.18 mm/kyr, low curvature transect; MAP = 3400 mm and MAT = 23 °C) also on Basse-Terre Island. Thus, a doubling of MAP roughly correlates with a doubling of weathering advance rate. The new rind study highlights the effect of precipitation on weathering rates over a time scale of ∼100 kyr. Weathering rinds are thus a suitable system for investigating long-term chemical weathering across environmental gradients, complementing short-term riverine solute fluxes.

  3. Memory Effects Study of Measuring Radioactive Xenon Isotopes With β-γ Coincidence Method

    International Nuclear Information System (INIS)

    Jia Huaimao; Wang Shilian; Wang Jun; Li Qi; Zhao Yungang; Fan Yuanqing; Zhang Xinjun

    2010-01-01

    The β-γ coincidence technique is a kind of the key important method to detect radioactive xenon isotopes for the Comprehensive Nuclear-Test-Ban Treaty (CTBT). This paper describes noble gases memory effects of β-γ coincidence detector. Xenon memory effects were measured and its influence on detector's minimum detectable activity (MDA) was evaluated. The methods of reducing xenon memory effects were studied. In conclusion, aluminium coated plastic scintillator and YAP scintillator can remarkably decrease xenon memory effects. (authors)

  4. Effect of massing on larval growth rate.

    Science.gov (United States)

    Johnson, Aidan P; Wallman, James F

    2014-08-01

    Estimation of minimum postmortem interval commonly relies on predicting the age of blowfly larvae based on their size and an estimate of the temperatures to which they have been exposed throughout their development. The majority of larval growth rate data have been developed using small larval masses in order to avoid excess heat generation. The current study collected growth rate data for larvae at different mass volumes, and assessed the temperature production of these masses, for two forensically important blow fly species, Chrysomya rufifacies and Calliphora vicina. The growth rate of larvae in a small mass, exposed to the higher temperatures equivalent to those experienced by large masses, was also assessed to determine if observed differences were due to the known temperature effects of maggot masses. The results showed that temperature production increased with increasing mass volume, with temperature increases of 11 °C observed in the large Ch. rufifacies masses and increases of 5 °C in the large C. vicina masses. Similarly, the growth rate of the larvae was affected by mass size. The larvae from small masses grown at the higher temperatures experienced by large masses displayed an initial delay in growth, but then grew at a similar rate to those larvae at a constant 23 °C. Since these larvae from masses of equivalent sizes displayed similar patterns of growth rate, despite differing temperatures, and these growth rates differed from larger masses exposed to the same temperatures, it can be concluded that larval growth rate within a mass may be affected by additional factors other than temperature. Overall, this study highlights the importance of understanding the role of massing in larval development and provides initial developmental data for mass sizes of two forensically important blowfly species commonly encountered in Australian forensic casework. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  5. Study on the Effect of the Separating Unit Optimization on the Economy of Stable Isotope Separation

    Directory of Open Access Journals (Sweden)

    YANG Kun

    2015-01-01

    Full Text Available An economic criterion called as yearly net profit of single separating unit (YNPSSU was presented to evaluate the influence of structure optimization on the economy. Using YNPSSU as a criterion, economic analysis was carried out for the structure optimization of separating unit in the case of separating SiF4 to obtain the 28Si and 29Si isotope. YNPSSU was calculated and compared with that before optimization. The results showed that YNPSSU was increased by 12.3% by the structure optimization. Therefore, the structure optimization could increase the economy of the stable isotope separation effectively.

  6. Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

    DEFF Research Database (Denmark)

    Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

    2012-01-01

    -labeled water and 18O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed......In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and “Aromatoleum aromaticum strain EbN1” were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. 18O...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

  7. Stable carbon and nitrogen isotope variation in the northern lampfish and Neocalanus, marine survival rates of pink salmon, and meso-scale eddies in the Gulf of Alaska

    Science.gov (United States)

    Kline, Thomas C., Jr.

    2010-10-01

    Northern lampfish (NLF), Stenobrachius leucopsarus (Myctophidae), the dominant pelagic fish taxon of the subarctic North Pacific Ocean, were sampled opportunistically in MOCNESS tows made on continental slope waters of the Gulf of Alaska (GOA) as well as in deep areas of Prince William Sound (PWS) during 1997-2006. The overall mean whole-body lipid-corrected stable carbon isotope value of NLF from the GOA was -21.4 (SD = 0.7) whereas that from PWS was -19.5 (SD = 0.9). This pattern is similar to that observed for late feeding stage Neocalanus cristatus copepods thus confirming a mean cross-shelf carbon stable isotope gradient. As well, there was a statistically significant positive correlation between the considerable temporal variation in the monthly mean carbon stable isotope composition of GOA Neocalanus and GOA NLF ( r = 0.69, P food chain length whereas carbon stable isotopes reflect organic carbon production. The carbon stable isotope values of NLF, measured in May, were positively correlated to marine survival rate of PWS hatchery salmon cohorts entering the marine environment the same year ( r = 0.84, P < 0.001). The carbon stable isotope values for Neocalanus in May were also positively correlated to salmon marine survival ( r = 0.82, P < 0.001). Processes thus manifested through the carbon stable isotope value of biota from the continental slope more closely predicted marine survival rate than that of the salmon themselves. The incipient relationships suggested by the correlations are consistent with the hypothesis that exchange between coastal and oceanic waters in the study area is driven by meso-scale eddies. These eddies facilitate the occurrence of slope phytoplankton blooms as well as drive oceanic zooplankton subsidies into coastal waters. The strong as well as more significant correlations of salmon marine survival rate to NLF as well as slope Neocalanus carbon stable isotope values point to processes taking place at the slope (i.e., interactions

  8. Hemodynamic effects of metoprolol and nifedipine in angina pectoris measured by isotope technique

    Energy Technology Data Exchange (ETDEWEB)

    Bostroem, P.A.

    1988-01-01

    In order to evaluate the therapeutic effects of metoprolol, nifedipine, and their combination, 11 patients with secondary angina pectoris and with thallium tomographic findings indicating coronary artery disease were studied before and after these three treatment regimes in a single-blind cross-over study. The therapeutic effect was measured by standardized working test and isotope angiocardiography, which enabled evaluation of left ventricular ejection fraction, stroke volume, and phase analysis of left ventricular contraction. Treatment with metoprolol and combination therapy increased work performance. Ejection fraction did not differentiate the treatment regimes, whereas stroke volume was significantly lower at work and heart rate higher at rest and at work during nifedipine treatment compared to either metoprolol or combination treatment (p less than 0.05). Cardiac output was significantly reduced during nifedipine and metoprolol treatment during work (p less than 0.05). Phase improved after all therapeutic regimes, but reached significance only during the metoprolol treatment period at rest (p less than 0.05).

  9. Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

    International Nuclear Information System (INIS)

    Markham, G.D.; Parkin, D.W.; Schramm, V.L.

    1986-01-01

    S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

  10. Anomalous H/D isotope effect on 35Cl NQR frequencies and H/D isotope effect on 1H MAS NMR spectra in pyrrolidinium p-chlorobenzoate

    International Nuclear Information System (INIS)

    Nakano, Ryo; Honda, Hisashi; Nakata, Eiichi; Takamizawa, Satoshi; Noro, Sumiko; Kimura, Taiki; Kyo, Shin-shin; Ishimaru, Shin'ichi; Miyake, Ryosuke

    2010-01-01

    An anomalous isotope effect was observed in the 35 Cl NQR frequency of pyrrolidinium p-chlorobenzoate (C 4 H 8 NH 2 + ·ClC 6 H 4 COO - ) by deuterium substitution of hydrogen atoms which form two kinds of N-H...O type hydrogen bonds. Large negative frequency shifts of the 35 Cl resonance lines, reaching 309 kHz at 77 K and 267 kHz at 293 K, were obtained upon deuteration, although the Cl atom in the molecule formed no hydrogen bonds in the crystal. 1 H MAS NMR lines showed significant changes by the deuterium substitution, while in contrast, small shifts of 13 C CP/MAS NMR signals were obtained. Our measurements of 1 H NMR spin-lattice relaxation times (T 1 ) suggested that the H/D isotope shifts detected from the 35 Cl NQR frequencies and 1 H NMR spectra are due to structural changes rather than molecular dynamics. Single-crystal X-ray diffraction measurements showed two remarkable H/D isotope differences in the molecular arrangements, (1) the N-H length along the crystallographic a axis became 1 pm shorter, and (2) the dihedral angle between benzene and the pyrrolidine ring changed by 1.1(2)deg upon deuteration. Using density functional theory estimations, the anomalous 35 Cl NQR frequency shifts and 1 H MAS NMR line-shape changes could be explained by the dihedral angle change rather than the N-H length difference. (author)

  11. Fine print in isotope effects: the glucose anomeric equilibrium and binding of glucose to human brain hexokinase

    International Nuclear Information System (INIS)

    Lewis, B.E; Schramm, V.L.

    2002-01-01

    Binding isotope effects are a sensitive measure of changes in molecular vibrational character that occur during ligand-receptor binding. In this study, we have measured isotope effects on the binding of glucose to human brain hexokinase using the ultrafiltration method, with the following results: 0.991±0.001, 0.908±0.003, 1.010±0.001, 0.974±0.002, 1.022±0.002 for [ 14 C]-glucose mixed with [1- 3 H]-, [2- 3 H]-, [3- 3 H]-, [5- 3 H]-, [6,6- 3 H]-glucose, respectively. Comparing the observed data with isotope effects on the anomeric equilibrium in glucose reported previously proves the existence of binding isotope effects in this system. Preliminary computational results are presented to explain the observed binding isotope effects in terms of hydrogen bond patterns and molecular crowding found in the binary complex of sugar and enzyme. (author)

  12. Kinetic secondary deuterium isotope effect in addition of nucleophile to m-bromobenzaldehyde

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1985-01-01

    The kinetic secondary deuterium isotope effects, KD/KH for hydrated proton catalyzed addition of semicarbazide, methoxyamine and hydroxylamine to m-bromobenzaldehyde is studied. The nature of the nucleophile, addition of the carbonyl group and the chemical reactions are evaluated. (M.J.C.) [pt

  13. Studies on the magnetic after-effect of hydrogen isotopes in hexagonal crystals

    International Nuclear Information System (INIS)

    Herbst, G.

    1979-01-01

    The behaviour of hydrogen isotopes in hexagonal gadolinium, in intermetallic compounds of the RECo 5 type (RE = rare earth metal), and in cobalt alloys with small concentrations of alloyed impurity atoms was studied using the magnetic after-effect method in the temperature range between 4.2 K and 300 K. (orig./WBU) [de

  14. Synthesis of seven deuteromethyl-caffeine analogues observation of deuterium isotope effects on CMR analysis

    Energy Technology Data Exchange (ETDEWEB)

    Falconnet, J.B.; Brazier, J.L.; Desage, M.

    1986-03-01

    The synthesis of all 7 N-trideuteromethyl isotopomers of caffeine by reaction of trideuteromethyl iodide (C/sup 2/H/sub 3/I) with the appropriate xanthine molecules is described. The use of proton, deuterium and carbon-13-NMR as a first step in purity assessment revealed /sup 13/C-NMR deuterium isotope effects on the resonance of perdeuteromethyl carbons.

  15. Kinetic isotope effect in the reaction of dehydration of fructose into 5-hydroxymethylfurfural

    International Nuclear Information System (INIS)

    Grin', S.A.; Tsimbaliev, S.R.; Gel'fand, S.Yu.

    1993-01-01

    Kinetic isotopic effect in the reaction of fructose dehydration into 5- hydroxymethylfurfural was determined. The results suggest hydrogen participation in the limiting stage of the process. The assumption that proton addition to 4, 5, 6 -trihydroxy - 2- on - hexal is the limiting stage is made

  16. A new cascade method for studying isotope effect in chemical exchange system without valance change

    International Nuclear Information System (INIS)

    Wen Xiaoning; Luo Wenzong

    1987-01-01

    A new cascade method for studying isotope effect in chemical exchange system without valance change is developed and described. This method is simple to use and consumes less extractant as compared with the commonly used Woodward method. It is also convenient for unstable systems

  17. Stable isotope enrichment in laboratory ant colonies: effects of colony age, metamorphosis, diet, and fat storage

    Science.gov (United States)

    Ecologists use stable isotopes to infer diets and trophic levels of animals in food webs, yet some assumptions underlying these inferences have not been thoroughly tested. We used laboratory-reared colonies of Solenopsis invicta Buren (Formicidae: Solenopsidini) to test the effects of metamorphosis,...

  18. Strain rate effects in stress corrosion cracking

    Energy Technology Data Exchange (ETDEWEB)

    Parkins, R.N. (Newcastle upon Tyne Univ. (UK). Dept. of Metallurgy and Engineering Materials)

    1990-03-01

    Slow strain rate testing (SSRT) was initially developed as a rapid, ad hoc laboratory method for assessing the propensity for metals an environments to promote stress corrosion cracking. It is now clear, however, that there are good theoretical reasons why strain rate, as opposed to stress per se, will often be the controlling parameter in determining whether or not cracks are nucleated and, if so, are propagated. The synergistic effects of the time dependence of corrosion-related reactions and microplastic strain provide the basis for mechanistic understanding of stress corrosion cracking in high-pressure pipelines and other structures. However, while this may be readily comprehended in the context of laboratory slow strain tests, its extension to service situations may be less apparent. Laboratory work involving realistic stressing conditions, including low-frequency cyclic loading, shows that strain or creep rates give good correlation with thresholds for cracking and with crack growth kinetics.

  19. Calcium isotope effects in ion exchange electromigration and calcium isotope analysis by thermo-ionization mass spectrometry

    International Nuclear Information System (INIS)

    Fujii, Y.; Hoshi, J.; Iwamoto, H.; Okamoto, M.; Kakihana, H.

    1985-01-01

    Calcium ions were made to electromigrate along a cation exchange membrane. The abundance ratios of the calcium isotopes (Ca-40, 42, 43, 44, 48) in the migrated bands were measured by thermo-ionization mass spectrometry. The lighter isotopes were enriched in the front part of the migrated band. The increments in the isotope abundance ratios were found to be proportional to the mass difference of the isotopes. The observed epsilon-values per unit mass difference (epsilon/ΔM) were 1.26 x 10 -4 (at 20 0 C), 1.85 x 10 -4 (at 25 0 C) and 2.4 x 10 -4 (at 40 0 C). The mass spectrometry was improved by using a low temperature for the evaporation of CaI 2 . (orig.)

  20. β-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    International Nuclear Information System (INIS)

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F.

    1995-01-01

    β-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 degrees C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6- 2 H 2 ]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 ± 0.01. These values support the B AC 2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other β-lactams. The measured β-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 ± 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A AC 1 mechanism with an intermediate acylium ion. If this were so, the calculated β-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 ± 0.01. This suggests an early A AC 1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A AC 1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 ± 0.00 in 1 M HCl and 0.22 ± 0.01 in 33.3 wt % H 2 SO 4 . 1 fig., 3 tabs

  1. Strain rate effects for spallation of concrete

    Science.gov (United States)

    Häussler-Combe, Ulrich; Panteki, Evmorfia; Kühn, Tino

    2015-09-01

    Appropriate triaxial constitutive laws are the key for a realistic simulation of high speed dynamics of concrete. The strain rate effect is still an open issue within this context. In particular the question whether it is a material property - which can be covered by rate dependent stress strain relations - or mainly an effect of inertia is still under discussion. Experimental and theoretical investigations of spallation of concrete specimen in a Hopkinson Bar setup may bring some evidence into this question. For this purpose the paper describes the VERD model, a newly developed constitutive law for concrete based on a damage approach with included strain rate effects [1]. In contrast to other approaches the dynamic strength increase is not directly coupled to strain rate values but related to physical mechanisms like the retarded movement of water in capillary systems and delayed microcracking. The constitutive law is fully triaxial and implemented into explicit finite element codes for the investigation of a wide range of concrete structures exposed to impact and explosions. The current setup models spallation experiments with concrete specimen [2]. The results of such experiments are mainly related to the dynamic tensile strength and the crack energy of concrete which may be derived from, e.g., the velocity of spalled concrete fragments. The experimental results are compared to the VERD model and two further constitutive laws implemented in LS-Dyna. The results indicate that both viscosity and retarded damage are required for a realistic description of the material behaviour of concrete exposed to high strain effects [3].

  2. Strain rate effects for spallation of concrete

    Directory of Open Access Journals (Sweden)

    Häussler-Combe Ulrich

    2015-01-01

    Full Text Available Appropriate triaxial constitutive laws are the key for a realistic simulation of high speed dynamics of concrete. The strain rate effect is still an open issue within this context. In particular the question whether it is a material property – which can be covered by rate dependent stress strain relations – or mainly an effect of inertia is still under discussion. Experimental and theoretical investigations of spallation of concrete specimen in a Hopkinson Bar setup may bring some evidence into this question. For this purpose the paper describes the VERD model, a newly developed constitutive law for concrete based on a damage approach with included strain rate effects [1]. In contrast to other approaches the dynamic strength increase is not directly coupled to strain rate values but related to physical mechanisms like the retarded movement of water in capillary systems and delayed microcracking. The constitutive law is fully triaxial and implemented into explicit finite element codes for the investigation of a wide range of concrete structures exposed to impact and explosions. The current setup models spallation experiments with concrete specimen [2]. The results of such experiments are mainly related to the dynamic tensile strength and the crack energy of concrete which may be derived from, e.g., the velocity of spalled concrete fragments. The experimental results are compared to the VERD model and two further constitutive laws implemented in LS-Dyna. The results indicate that both viscosity and retarded damage are required for a realistic description of the material behaviour of concrete exposed to high strain effects [3].

  3. Isotope puzzle in sputtering

    International Nuclear Information System (INIS)

    Zheng Liping

    1998-01-01

    Mechanisms affecting multicomponent material sputtering are complex. Isotope sputtering is the simplest in the multicomponent materials sputtering. Although only mass effect plays a dominant role in the isotope sputtering, there is still an isotope puzzle in sputtering by ion bombardment. The major arguments are as follows: (1) At the zero fluence, is the isotope enrichment ejection-angle-independent or ejection-angle-dependent? (2) Is the isotope angular effect the primary or the secondary sputter effect? (3) How to understand the action of momentum asymmetry in collision cascade on the isotope sputtering?

  4. An unusual isotope effect in a high-transition-temperature superconductor

    International Nuclear Information System (INIS)

    Gweon, G.-H.; Sasagawa, T.; Zhou, S.Y.; Graf, J.; Takagi, H.; Lee, D.-H.; Lanzara, A.

    2004-01-01

    In conventional superconductors, the electron pairing that allows superconductivity is caused by exchange of virtual phonons, which are quanta of lattice vibration. For high-transition-temperature (high-Tc) superconductors, it is far from clear that phonons are involved in the pairing at all. For example, the negligible change in Tc of optimally doped Bi2Sr2CaCu2O8 (Bi2212) upon oxygen isotope substitution (16O to 18O leads to Tc decreasing from 92 to 91 K) has often been taken to mean that phonons play an insignificant role in this material. Here we provide a detailed comparison of the electron dynamics of Bi2212 samples containing different oxygen isotopes, using angle-resolved photoemission spectroscopy. Our data show definite and strong isotope effects. Surprisingly, the effects mainly appear in broad high-energy humps, commonly referred to as ''incoherent peaks''. As a function of temperature and electron momentum, the magnitude of the isotope effect closely correlates with the superconducting gap--that is, the pair binding energy. We suggest that these results can be explained in a dynamic spin-Peierls picture, where the singlet pairing of electrons and the electron-lattice coupling mutually enhance each other

  5. Structural and kinetic isotope effect studies of nicotinamidase (Pnc1) from Saccharomyces cerevisiae.

    Science.gov (United States)

    Smith, Brian C; Anderson, Mark A; Hoadley, Kelly A; Keck, James L; Cleland, W Wallace; Denu, John M

    2012-01-10

    Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD(+) salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from Saccharomyces cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction in which ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogues acting as inhibitors or substrates were examined, revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehyde and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary (15)N and (13)C kinetic isotope effects (KIEs) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased, indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was indicative of a stronger commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid, is discussed. These results will aid in the design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity.

  6. Structural and Kinetic Isotope Effect Studies of Nicotinamidase (Pnc1) from S. cerevisiae†

    Science.gov (United States)

    Smith, Brian C.; Anderson, Mark A.; Hoadley, Kelly A.; Keck, James L.; Cleland, W. Wallace; Denu, John M.

    2011-01-01

    Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD+ salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from S. cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction where ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogs acting as inhibitors or substrates were examined revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehyde and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary 15N and 13C kinetic isotope effects (KIE) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was observed indicative of a higher commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism is discussed involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid. These results will aid design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity. PMID:22229411

  7. Deuterium isotope effect on metabolism of N-nitrosodimethylamine in vivo in rat

    International Nuclear Information System (INIS)

    Swann, P.F.; Mace, R.; Angeles, R.M.; Keefer, L.K.

    1983-01-01

    The maximal rates of metabolic oxidation of N-nitrosodimethylamine (NDMA) and N-nitrosodimethylamine-d6 (NDMA-d6) in vivo (VH and VD, respectively) have been measured by following 14CO2 exhalation in rats after intraperitoneal injection of the two 14C-labelled carcinogens at high doses (20 or 40 mg/kg). Complete deuteration of NDMA reduced only slightly the maximal rate of metabolism when the two substrates were administered separately (VH/VD approximately 1.2). However, much larger (approximately 4-fold) deuterium isotope effects were observed when mixtures of NDMA with NDMA-d6 were injected. These results are tentatively interpreted as evidence that C-H bond cleavage is not a rate limiting feature of overall metabolism, but that the complex between NDMA and the principal enzyme(s) metabolizing it in vivo freely equilibrates with unbound substrate. Single, large, intraperitoneal doses of NDMA and NDMA-d6 produced a similar alkylation of rat liver DNA and also of kidney DNA. However, a small oral dose (54 micrograms/kg) of NDMA-d6 produced 1/3 less alkylation of liver DNA and 3 times as much alkylation of kidney DNA as did an equimolar dose of NDMA. The reduction in alkylation of liver DNA correlates well with, and possibly explains, the decreased ability of NDMA-d6 to induce liver tumors in rats. The associated increase in the alkylation of kidney DNA suggests that this change is due to a decrease in the amount of nitrosamine removed from the portal blood on the first pass through the liver

  8. Structural and Kinetic Isotope Effect Studies of Nicotinamidase (Pnc1) from Saccharomyces cerevisiae

    International Nuclear Information System (INIS)

    Smith, Brian C.; Anderson, Mark A.; Hoadley, Kelly A.; Keck, James L.; Cleland, W. Wallace; Denu, John M.

    2012-01-01

    Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD + salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from Saccharomyces cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction in which ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogues acting as inhibitors or substrates were examined, revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehyde and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary 15 N and 13 C kinetic isotope effects (KIEs) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased, indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was indicative of a stronger commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid, is discussed. These results will aid in the design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity.

  9. Structural and Kinetic Isotope Effect Studies of Nicotinamidase (Pnc1) from Saccharomyces cerevisiae

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Brian C.; Anderson, Mark A.; Hoadley, Kelly A.; Keck, James L.; Cleland, W. Wallace; Denu, John M. (UW)

    2012-05-08

    Nicotinamidases catalyze the hydrolysis of nicotinamide to nicotinic acid and ammonia. Nicotinamidases are absent in mammals but function in NAD{sup +} salvage in many bacteria, yeast, plants, protozoa, and metazoans. We have performed structural and kinetic investigations of the nicotinamidase from Saccharomyces cerevisiae (Pnc1). Steady-state product inhibitor analysis revealed an irreversible reaction in which ammonia is the first product released, followed by nicotinic acid. A series of nicotinamide analogues acting as inhibitors or substrates were examined, revealing that the nicotinamide carbonyl oxygen and ring nitrogen are critical for binding and reactivity. X-ray structural analysis revealed a covalent adduct between nicotinaldehyde and Cys167 of Pnc1 and coordination of the nicotinamide ring nitrogen to the active-site zinc ion. Using this structure as a guide, the function of several residues was probed via mutagenesis and primary {sup 15}N and {sup 13}C kinetic isotope effects (KIEs) on V/K for amide bond hydrolysis. The KIE values of almost all variants were increased, indicating that C-N bond cleavage is at least partially rate limiting; however, a decreased KIE for D51N was indicative of a stronger commitment to catalysis. In addition, KIE values using slower alternate substrates indicated that C-N bond cleavage is at least partially rate limiting with nicotinamide to highly rate limiting with thionicotinamide. A detailed mechanism involving nucleophilic attack of Cys167, followed by elimination of ammonia and then hydrolysis to liberate nicotinic acid, is discussed. These results will aid in the design of mechanism-based inhibitors to target pathogens that rely on nicotinamidase activity.

  10. Excitation functions and isotopic effects in (n, p) reactions for stable nickel isotopes from reaction threshold to 20 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Lalremruata, B. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: marema@physics.unipune.ernet.in; Ganesan, S. [Reactor Physics Design Division, BARC, Mumbai 58 (India); Bhoraskar, V.N. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: vnb@physics.unipune.ernet; Dhole, S.D. [Department of Physics, University of Pune, Ganeshkhind, Pune-411007, Maharashtra (India)], E-mail: sanjay@physics.unipune.ernet.in

    2009-05-01

    The excitation function for (n, p) reactions from reaction threshold to 20 MeV on five nickel isotopes viz; {sup 58}Ni, {sup 60}Ni, {sup 61}Ni, {sup 62}Ni and {sup 64}Ni were calculated using Talys-1.0 nuclear model code involving the fixed set of global parameters. A good agreement between the calculated and measured data is obtained with minimum effort on parameter fitting and only one free parameter called 'Shell damping factor'. This is of importance to the validation of nuclear model approaches with increased predictive power. The systematic decrease in (n, p) cross-sections with increasing neutron number in reactions induced by neutrons on isotopes of nickel is explained in terms of the proton separation energy and the pre-equilibrium model. The compound nucleus and pre-equilibrium reaction mechanism as well as the isotopic effects were also studied.

  11. Probing Reversible Chemistry in Coenzyme B12-Dependent Ethanolamine Ammonia Lyase with Kinetic Isotope Effects

    Science.gov (United States)

    Jones, Alex R; Rentergent, Julius; Scrutton, Nigel S; Hay, Sam

    2015-01-01

    Coenzyme B12-dependent enzymes such as ethanolamine ammonia lyase have remarkable catalytic power and some unique properties that enable detailed analysis of the reaction chemistry and associated dynamics. By selectively deuterating the substrate (ethanolamine) and/or the β-carbon of the 5′-deoxyadenosyl moiety of the intrinsic coenzyme B12, it was possible to experimentally probe both the forward and reverse hydrogen atom transfers between the 5′-deoxyadenosyl radical and substrate during single-turnover stopped-flow measurements. These data are interpreted within the context of a kinetic model where the 5′-deoxyadenosyl radical intermediate may be quasi-stable and rearrangement of the substrate radical is essentially irreversible. Global fitting of these data allows estimation of the intrinsic rate constants associated with CoC homolysis and initial H-abstraction steps. In contrast to previous stopped-flow studies, the apparent kinetic isotope effects are found to be relatively small. PMID:25950663

  12. High secondary [alpha]-deuterium kinetic isotope effect in the acetolysis and formolysis of dideuterioferrocenylmethyl benzoate

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, S. (Research Center of the Croatian Academy of Sciences and Arts, Zagreb (Croatia)); Kukric, Z.; Sutic, D. (Sarajevo Univ. (Yugoslavia). Faculty of Natural Sciences and Mathematics); Saunders, W.H. Jr. (Rochester Univ., NY (United States). Dept. of Chemistry)

    1992-02-01

    Acetolysis and formolysis of dideuterioferrocenylmethyl benzoate exhibit large secondary deuterium kinetic isotope effects and an abnormal temperature dependence. In the presence of LiClO[sub 4], which prevents the reversion from solvent-separated to contact ion-pairs, K[sub H]/K[sub D] at 25 [sup o]C amount to 1.53 [+-] 0.02 (acetolysis) and 1.48 [+-] 0.03 (formolysis). In the presence of LiClO[sub 4] the ratios of Arrhenius pre-exponential factors, A[sub H]/A[sub D], are significantly less than unity and amount to 0.49 [+-] 0.01 (acetolysis) and 0.38 [+-] 0.04 (formolysis). In the absence of LiClO[sub 4] the A[sub H]/A[sub D] ratios are much smaller (0.02 both in acetolysis and formolysis). We suggest that these surprisingly low values result from a change in rate-determining step over the temperature range, from formation of the solvent-separated ion-pair at low temperatures to reaction of the dissociated carbocation with solvent at the highest temperatures. Whether tunnelling plays any role in these solvolyses is discussed. (Author).

  13. The kinetic isotope effect of hydrogen, deuterium and tritium absorbed and desorbed by titanium

    International Nuclear Information System (INIS)

    Huang Gang; Cao Xiaohua; Long Xinggui

    2008-06-01

    p-t curves of hydrogen, deuterium and tritium absorption at 550-750 degree C and desorption at 350-550 degree C by titanium were investigated. The rate constants of absorption and desorption for hydrogen, deuterium and tritium on each temperature are determined and the activation energy values obtained by this analysis are (55.6 ± 2.4) kJ·mol -1 , (110.2 ± 3.0) kJ·mol -1 and (155.5 ± 3.2) kJ·mol -1 for absorption and (27.1±0.4) KJ·mol -1 , (42.3 ± 1.9) kJ·mol -1 and (62.1±1.6) kJ·mol -1 for desorption respectively. The activation energy value of tritium absorption is highest which shows titanium tritiation is hardest. The activation energy value of tritium desorption is highest and it also can prove that titanium tritide is stablest. There are remarkable kinetic hydrogen isotope effects when titanium absorb and desorb hydrogen, deuterium and tritium. (authors)

  14. Transmission of Helium Isotopes through Graphdiyne Pores: Tunneling versus Zero Point Energy Effects.

    Science.gov (United States)

    Hernández, Marta I; Bartolomei, Massimiliano; Campos-Martínez, José

    2015-10-29

    Recent progress in the production of new two-dimensional (2D) nanoporous materials is attracting considerable interest for applications to isotope separation in gases. In this paper we report a computational study of the transmission of (4)He and (3)He through the (subnanometer) pores of graphdiyne, a recently synthesized 2D carbon material. The He-graphdiyne interaction is represented by a force field parametrized upon ab initio calculations, and the (4)He/(3)He selectivity is analyzed by tunneling-corrected transition state theory. We have found that both zero point energy (of the in-pore degrees of freedom) and tunneling effects play an extraordinary role at low temperatures (≈20-30 K). However, both quantum features work in opposite directions in such a way that the selectivity ratio does not reach an acceptable value. Nevertheless, the efficiency of zero point energy is in general larger, so that (4)He tends to diffuse faster than (3)He through the graphdiyne membrane, with a maximum performance at 23 K. Moreover, it is found that the transmission rates are too small in the studied temperature range, precluding practical applications. It is concluded that the role of the in-pore degrees of freedom should be included in computations of the transmission probabilities of molecules through nanoporous materials.

  15. Secondary deuterium isotope effects for acid-catalyzed hydrolysis of inosine and adenosine

    International Nuclear Information System (INIS)

    Romero, R.; Stein, R.; Bull, H.G.; Cordes, E.H.

    1978-01-01

    Kinetic α deuterium isotope effects have been measured for acid-catalyzed hydrolysis of inosine and adenosine. For inosine hydrolysis, values of k/sub H/k/sub D/ follow: in 1.0 M HCl, 1.21 and 1.20 at 25 and 50 0 C, respectively; in 0.1 M HCl, 1.19 and 1.18 at 25 and 50 0 C, respectively. For adenosine hydrolysis, k/sub H/k/sub D/ is 1.23 in 0.1 M HCl at 25 0 C. The values require that the transition states for hydrolysis of both the monocation and dication of inosine and the dication of adenosine have marked oxocarbonium ion character. Detailed mechanisms which accord with this and other experimental observations include (1) a classical Al mechanism in which the C--N bond is largely cleaved in the transition state; (2) a mechanism involving some form of nucleophilic participation by solvent in which bond cleavage is advanced relative to bond formation in the transition state; or (3) complete C--N bond cleavage with rate-determining diffusion apart of oxocarbonium ion and purine base. 53 references, 1 figure, 2 tables

  16. Mechanistic Insights into Dye-Decolorizing Peroxidase Revealed by Solvent Isotope and Viscosity Effects

    Energy Technology Data Exchange (ETDEWEB)

    Shrestha, Ruben [Department; Huang, Gaochao [Department; Meekins, David A. [Department; Geisbrecht, Brian V. [Department; Li, Ping [Department

    2017-08-18

    Dye-decolorizing peroxidases (DyPs) are a family of H2O2-dependent heme peroxidases that have shown potential applications in lignin degradation and valorization. However, the DyP kinetic mechanism remains underexplored. Using structural biology and solvent isotope (sKIE) and viscosity effects, many mechanistic characteristics have been determined for the B-class ElDyP from Enterobacter lignolyticus. Its structure revealed that a water molecule acts as the sixth axial ligand and two channels at diameters of ~3.0 and 8.0 Å lead to the heme center. A conformational change of ERS* to ERS, which have identical spectral characteristics, was proposed as the final step in DyPs’ bisubstrate Ping-Pong mechanism. This step is also the rate-determining step in ABTS oxidation. The normal KIE of wild-type ElDyP with D2O2 at pD 3.5 suggested that compound 0 deprotonation by the distal aspartate is rate-limiting in the formation of compound I, which is more reactive under acidic pH than under neutral or alkaline pH. The viscosity effects and other biochemical methods implied that the reducing substrate binds with compound I instead of the free enzyme. The significant inverse sKIEs of kcat/KM and kERS* suggested that the aquo release in ElDyP is mechanistically important and may explain the enzyme’s adoption of two-electron reduction for compound I. The distal aspartate is catalytically more important than the distal arginine and plays key roles in determining ElDyP’s optimum acidic pH. The kinetic mechanism of D143H-ElDyP was also briefly studied. The results obtained will pave the way for future protein engineering to improve DyPs’ lignolytic activity.

  17. Isotope effect of optical activity measurements on L-α-alanine

    International Nuclear Information System (INIS)

    Darge, W.; Laczko, I.; Thiemann, W.

    1976-01-01

    If an optically active organic substance is labelled in the chirality center with another isotopic species (such as 15 N for 14 N) a pronounced variation of rotatory power is predicted. It was tried to varify this idea experimentally on L-α-alanine and found an isotope effect in ORD (optical rotatory dispersion). The magnitude of the rotation is mainly dependent on the pH of the solvent. The ratio of the optical activity alanine- 14 N/alanine- 15 N is about 1.02. It can be seen that the ratios of the molecular rotations are consistently lower than the corresponding ratios of the specific rotations. This is of course due to the fact that the molecular mass 15 M is larger than 14 M. This means tthat the mass difference is already taken into account so that the ratio of the molecular rotations could be defined as the ''net'' isotope effect in the ORDs of 15 N-substitued alanine. From the fact the ORD is different for the isotope-substitued alanine, one can reasonably assume that the absorption coefficient is also different. This leads to speculations about certain problems in the chemical evolution of the biosphere, such as the origin of optical activity. (T.G.)

  18. Isotope analysis of diamond-surface passivation effect of high-temperature H2O-grown atomic layer deposition-Al2O3 films

    International Nuclear Information System (INIS)

    Hiraiwa, Atsushi; Saito, Tatsuya; Matsumura, Daisuke; Kawarada, Hiroshi

    2015-01-01

    The Al 2 O 3 film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H 2 O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D 2 O instead of H 2 O in the ALD and found that the Al 2 O 3 film formed at a conventional temperature (100 °C) incorporates 50 times more CH 3 groups than the high-temperature film. This CH 3 is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H 2 O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H 2 O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D 2 O-oxidant ALD but found that the mass density and dielectric constant of D 2 O-grown Al 2 O 3 films are smaller than those of H 2 O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al 2 O 3 films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD

  19. Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence

    Energy Technology Data Exchange (ETDEWEB)

    Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joël [Laboratoire de Glaciologie et Géophysique de l’Environnement, CNRS, F-38041 Grenoble (France); Univ. Grenoble Alpes, LGGE, F-38041 Grenoble (France); Meusinger, Carl; Johnson, Matthew S. [Copenhagen Center for Atmospheric Research (CCAR), Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Jost, Rémy [Laboratoire de Interdisciplinaire de Physique (LIPHY) Univ. de Grenoble, Grenoble (France); Bhattacharya, S. K. [Research Center for Environmental Changes, Academia Sinica, Nangang, Taipei 115, Taiwan (China)

    2014-06-28

    Atmospheric nitrate is preserved in Antarctic snow firn and ice. However, at low snow accumulation sites, post-depositional processes induced by sunlight obscure its interpretation. The goal of these studies (see also Paper I by Meusinger et al. [“Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry,” J. Chem. Phys. 140, 244305 (2014)]) is to characterize nitrate photochemistry and improve the interpretation of the nitrate ice core record. Naturally occurring stable isotopes in nitrate ({sup 15}N, {sup 17}O, and {sup 18}O) provide additional information concerning post-depositional processes. Here, we present results from studies of the wavelength-dependent isotope effects from photolysis of nitrate in a matrix of natural snow. Snow from Dome C, Antarctica was irradiated in selected wavelength regions using a Xe UV lamp and filters. The irradiated snow was sampled and analyzed for nitrate concentration and isotopic composition (δ{sup 15}N, δ{sup 18}O, and Δ{sup 17}O). From these measurements an average photolytic isotopic fractionation of {sup 15}ε = (−15 ± 1.2)‰ was found for broadband Xe lamp photolysis. These results are due in part to excitation of the intense absorption band of nitrate around 200 nm in addition to the weaker band centered at 305 nm followed by photodissociation. An experiment with a filter blocking wavelengths shorter than 320 nm, approximating the actinic flux spectrum at Dome C, yielded a photolytic isotopic fractionation of {sup 15}ε = (−47.9 ± 6.8)‰, in good agreement with fractionations determined by previous studies for the East Antarctic Plateau which range from −40 to −74.3‰. We describe a new semi-empirical zero point energy shift model used to derive the absorption cross sections of {sup 14}NO{sub 3}{sup −} and {sup 15}NO{sub 3}{sup −} in snow at a chosen temperature. The nitrogen isotopic fractionations obtained by applying

  20. Preliminary Failure Modes, Effects and Criticality Analysis (FMECA) of the conceptual Brayton Isotope Power System (BIPS) Flight System

    International Nuclear Information System (INIS)

    Miller, L.G.

    1976-01-01

    A failure modes, effects and criticality analysis (FMECA) was made of the Brayton Isotope Power System Flight System (BIPS-FS) as presently conceived. The components analyzed include: Mini-BRU; Heat Source Assembly (HSA); Mini-Brayton Recuperator (MBR); Space Radiator; Ducts and Bellows, Insulation System; Controls; and Isotope Heat Source (IHS)

  1. Using Beads and Divided Containers to Study Kinetic and Equilibrium Isotope Effects in the Laboratory and in the Classroom

    Science.gov (United States)

    Campbell, Dean J.; Brewer, Emily R.; Martinez, Keri A.; Fitzjarrald, Tamara J.

    2017-01-01

    The purpose of this laboratory experiment is to study fundamental concepts of kinetics and equilibria and the isotope effects associated with both of these concepts. The concepts of isotopes in introductory and general chemistry courses are typically used within the contexts of atomic weights and radioactivity. Kinetic and equilibrium isotope…

  2. Solvent effects and secondary isotope effects for probing diradical character in the thermal decarboxylation of β-peroxylactones

    International Nuclear Information System (INIS)

    Adam, W.; Cueto, O.; Guedes, L.N.; Rodriguez, L.O.

    1978-01-01

    The lack of solvent effects in the activation parameters and product distribution and the lack of secondary deuterium isotope effects at the α-carbon and β-alkyl migrant substantiates that the thermal decarboxylation of β-peroxy lactones proceeds via a 1,5-diradical

  3. Large effect of irradiance on hydrogen isotope fractionation of alkenones in Emiliania huxleyi

    Science.gov (United States)

    van der Meer, Marcel T. J.; Benthien, Albert; French, Katherine L.; Epping, Eric; Zondervan, Ingrid; Reichart, Gert-Jan; Bijma, Jelle; Sinninghe Damsté, Jaap S.; Schouten, Stefan

    2015-07-01

    The hydrogen isotopic (δD) composition of long-chain alkenones produced by certain haptophyte algae has been suggested as a potential proxy for reconstructing paleo sea surface salinity. However, environmental parameters other than salinity may also affect the δD of alkenones. We investigated the impact of the level of irradiance on hydrogen isotopic fractionation of alkenones versus growth water by cultivating two strains of the cosmopolitan haptophyte Emiliania huxleyi at different light intensities. The hydrogen isotope fractionation decreased by approximately 40‰ when irradiance was increased from 15 to 200 μmol photons m-2 s-1 above which it was relatively constant. The response is likely a direct effect of photosystem I and II activity as the relationship of the fractionation factor α versus light intensity can be described by an Eilers-Peeters photosynthesis model. This irradiance effect is in agreement with published δD data of alkenones derived from suspended particulate matter collected from different depths in the photic zone of the Gulf of California and the eastern tropical North Pacific. However, haptophyte algae tend to bloom at relatively high light intensities (>500 μmol photons m-2 s-1) occurring at the sea surface, at which hydrogen isotope fractionation is relatively constant and not affected by changes in light intensity. Alkenones accumulating in the sediment are likely mostly derived from these surface water haptophyte blooms, when the largest amount of biomass is produced. Therefore, the observed irradiance effect is unlikely to affect the applicability of the hydrogen isotopic composition of sedimentary long chain alkenones as a proxy for paleosalinity.

  4. Solvent isotope effects upon the thermodynamics of some transition-metal redox couples in aqueous media

    International Nuclear Information System (INIS)

    Weaver, M.J.; Nettles, S.M.

    1980-01-01

    The effects of substituting D 2 O for H 2 O as solvent upon the formal potentials of a number of transition-metal redox couples containing aquo, ammine, and simple chelating ligands have been investigated with the intention of evaluating the importance of specific solvation factors in the thermodynamics of such couples. The solvent liquid junction formed between H 2 O and D 2 O was shown to have a negligible effect on the measured formal potentials. Substantial solvent isotope effects were observed for a number of these systems, particularly for couples containing aquo ligands. The effects of separately deuterating the ligands and the surrounding solvent were investigated for some ammine couples. Possible origins of the solvent isotope effects are discussed in terms of changes in metal-ligand and ligand-solvent interactions. It is tentatively concluded that the latter influence provides the predominant contribution to the observed effects for aquo couples arising from increases in the extent of hydrogen bonding between the aquo ligands and surrounding solvent when D 2 O replaces H 2 O. The implications of these results in unraveling the solvent isotope effects upon the kinetics of simple redox reactions are also considered

  5. Rate effects in resistive plate chambers

    International Nuclear Information System (INIS)

    Lippmann, C.; Riegler, W.; Kalweit, A.

    2006-01-01

    The resistive plates in RPCs cause a drop of the electric field in the gas gap at high particle rates or large gas gain, which affects efficiency and time resolution. This effect is typically estimated by assuming the particle flux to be a DC current that causes a voltage drop when it passes through the resistive plate. In an improved model by Abbrescia (Nucl. Instr. Meth. A 533 (2004) 7), the fluctuation of the field in the gas gap is modelled by assuming that the avalanche partially discharges a small capacitor which gets recharged with a time constant characteristic for the given RPC. In our approach, the effect is calculated by using the exact analytic solution for the time dependent electric field of a point charge sitting on the surface of a resistive plate in an RPC. This is, by definition, the best possible approximation to reality. The solution is obtained using the quasi-static approximation of Maxwell's equations. The formulas are presented as integral representations with 'cured' integrands, which allow easy numerical evaluation for Monte Carlo simulations. The solutions show that the charges in RPCs are 'destroyed' with a continuous distribution of time constants which are related in a very intuitive way to some limiting cases. Using these formulas we present a Monte Carlo simulation of rate effects, proving the applicability of this approach. Finally, we compare the Monte Carlo results to analytical calculations, similar to the ones proposed by Gonzalez-Diaz et al. (see proceedings of this conference)

  6. Environmental effects on the stable carbon and oxygen isotopic ...

    African Journals Online (AJOL)

    1999-11-10

    The timing of band formation and linear skeletal growth rate based on environmental changes were investigated using alizarin red S (ARS) in Porites lutea coral at Khang Khao Island, the Gulf of Thailand from November 10, 1999 to March 15, 2001. The X-radiograph of the vertical section of the Porites coral skeleton was ...

  7. Evaluation of the effects of microscale chemical and isotopic ...

    Indian Academy of Sciences (India)

    of organic matter; therefore, analyzing the SFS only would probably be favourable for paleotemperature reconstruction. ... On the other hand, application of secondary ion ... into which various minor and trace elements are .... Volume fraction of calcium-carbonate material in the COC ..... sion rate and architecture; Geochem.

  8. Dose formation and hematologic effects with prolonged internal exposure of rats by isotope 131I

    International Nuclear Information System (INIS)

    Sova, O.A.; Drozd, Yi.P.

    2013-01-01

    Processes in single dose formation and long-term domestic revenue 131 I in rats was investigated. Original method of estimating absorbed doses in hemacyte for macro-dosemeters indicators was proposed. Dose factors for hemacyte and the dynamics of the blood-forming organs doses for prolonged two cases of prolonged exposure was calculated. Hematologic effects were studied for two variants of entry of the isotope. Peculiarities of doses formation and identified hematological effects are discussed

  9. The effect of zero-point energy differences on the isotope dependence of the formation of ozone: a classical trajectory study.

    Science.gov (United States)

    Schinke, Reinhard; Fleurat-Lessard, Paul

    2005-03-01

    The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.

  10. Isotope effect on the zero point energy shift upon condensation. I. Formulation and application to ethylene, methane, and fluoromethanes

    International Nuclear Information System (INIS)

    Kornblum, Z.C.; Ishida, T.

    1978-01-01

    A method of evaluating the isotope effect (IE) on the zero point energy (ZPE) shift upon condensation due to the London dispersion forces in the liquid has been formulated. It is expressed to the first order, as a product of an isotope-independent liquid factor and a factor of isotopic differences in gas-phase properties. The theory has been tested by calculating the effective atomic charges for carbon and hydrogen in ethylene, according to the CNDO/2 molecular orbital algorithm, and it correctly predicts the magnitude of the IE on the ZPE shift and the first-order sum rules involving the isotopic ethylenes. However, it fails to explain the difference in vapor pressures of isotopic isomers. The theory has also been applied to the D/H and to the 13 C/ 12 C isotope effects in methane and fluoromethanes. The results obtained from the CNDO/2 calculations have been compared with the experimental values of the total infrared absorption intensities and of the IE on the ZPE shift of isotopic methanes. Based on these calculations, the molecular properties that enhance the stronger dispersion forces in the liquid phase between the lighter molecules than between the isotopically heavier molecules, and hence favor a large IE on the ZPE shift, have been deduced

  11. First-principles theory of anharmonicity and the inverse isotope effect in superconducting palladium-hydride compounds.

    Science.gov (United States)

    Errea, Ion; Calandra, Matteo; Mauri, Francesco

    2013-10-25

    Palladium hydrides display the largest isotope effect anomaly known in the literature. Replacement of hydrogen with the heavier isotopes leads to higher superconducting temperatures, a behavior inconsistent with harmonic theory. Solving the self-consistent harmonic approximation by a stochastic approach, we obtain the anharmonic free energy, the thermal expansion, and the superconducting properties fully ab initio. We find that the phonon spectra are strongly renormalized by anharmonicity far beyond the perturbative regime. Superconductivity is phonon mediated, but the harmonic approximation largely overestimates the superconducting critical temperatures. We explain the inverse isotope effect, obtaining a -0.38 value for the isotope coefficient in good agreement with experiments, hydrogen anharmonicity being mainly responsible for the isotope anomaly.

  12. Tungsten isotopic compositions of iron meteorites: Chronological constraints vs. cosmogenic effects

    Science.gov (United States)

    Markowski, A.; Quitté, G.; Halliday, A. N.; Kleine, T.

    2006-02-01

    High-precision W isotopic compositions are presented for 35 iron meteorites from 7 magmatic groups (IC, IIAB, IID, IIIAB, IIIF, IVA, and IVB) and 3 non-magmatic groups (IAB, IIICD, and IIE). Small but resolvable isotopic variations are present both within and between iron meteorite groups. Variations in the 182W/ 184W ratio reflect either time intervals of metal-silicate differentiation, or result from the burnout of W isotopes caused by a prolonged exposure to galactic cosmic rays. Calculated apparent time spans for some groups of magmatic iron meteorites correspond to 8.5 ± 2.1 My (IID), 5.1 ± 2.3 My (IIAB), and 5.3 ± 1.3 My (IVB). These time intervals are significantly longer than those predicated from models of planetesimal accretion. It is shown that cosmogenic effects can account for a large part of the W isotopic variation. No simple relationship exists with exposure ages, compromising any reliable method of correction. After allowance for maximum possible cosmogenic effects, it is found that there is no evidence that any of the magmatic iron meteorites studied here have initial W isotopic compositions that differ from those of Allende CAIs [ ɛ182W = - 3.47 ± 0.20; [T. Kleine, K. Mezger, H. Palme, E. Scherer and C. Münker, Early core formation in asteroids and late accretion of chondrite parent bodies: evidence from 182Hf- 182W in CAIs, metal-rich chondrites and iron meteorites, Geochim. Cosmochim. Acta (in press)]. Cosmogenic corrections cannot yet be made with sufficient accuracy to obtain highly precise ages for iron meteorites. Some of the corrected ages nevertheless require extremely early metal-silicate segregation no later than 1 My after formation of CAIs. Therefore, magmatic iron meteorites appear to provide the best examples yet identified of material derived from the first planetesimals that grew by runaway growth, as modelled in dynamic simulations. Non-magmatic iron meteorites have a more radiogenic W isotopic composition than magmatic

  13. Isotope and fast ions turbulence suppression effects: Consequences for high-β ITER plasmas

    Science.gov (United States)

    Garcia, J.; Görler, T.; Jenko, F.

    2018-05-01

    The impact of isotope effects and fast ions on microturbulence is analyzed by means of non-linear gyrokinetic simulations for an ITER hybrid scenario at high beta obtained from previous integrated modelling simulations with simplified assumptions. Simulations show that ITER might work very close to threshold, and in these conditions, significant turbulence suppression is found from DD to DT plasmas. Electromagnetic effects are shown to play an important role in the onset of this isotope effect. Additionally, even external ExB flow shear, which is expected to be low in ITER, has a stronger impact on DT than on DD. The fast ions generated by fusion reactions can additionally reduce turbulence even more although the impact in ITER seems weaker than in present-day tokamaks.

  14. Gamma-radiation and isotopic effect on the critical behavior in triglycine selenate crystals

    Energy Technology Data Exchange (ETDEWEB)

    Kassem, M.E.; Hamed, A.E.; Abulnasr, L.; Abboudy, S. [Alexandria Univ. (Egypt). Dept. of Physics

    1994-11-01

    Isotopic effects in pure and {gamma}-irradiated triglycine selenate crystals were investigated using the specific heat (C{sub p}) technique. The obtained results showed an interesting dependence of the critical behavior of C{sub p} on the deuterium content. With increasing content of deuterium, the character of the phase transition changed from a second order ({lambda}-type) to a first order transition. After {gamma}-irradiation, the behavior of C{sub p} around the phase transition region was essentially affected. The transition temperature, T{sub c}, decreased and {Delta}C{sub p} depressed, and the transition became broad. It was noted that the effect of {gamma}-irradiation is opposite to the isotopic effect. (author).

  15. Improved constraints on in situ rates and on quantification of complete chloroethene degradation from stable carbon isotope mass balances in groundwater plumes

    Science.gov (United States)

    Höhener, Patrick; Elsner, Martin; Eisenmann, Heinrich; Atteia, Olivier

    2015-11-01

    Spills of chloroethenes (CEs) at industrial and urban sites can create groundwater plumes in which tetrachloro- and trichloroethene sequentially degrade to dichloroethenes, vinyl chloride (VC) and ethene, or ethane under reducing conditions. For detoxification, degradation must go beyond VC. Assessments based on ethene and ethane, however, are difficult because these products are volatile, may stem from alternative sources, can be further transformed and are not always monitored. To alternatively quantify degradation beyond VC, stable carbon isotope mass balances have been proposed where concentration-weighted CE isotope ratios are summed up and compared to the original source isotope ratio. Reported assessments, however, have provided not satisfactorily quantified results entailing greatly differing upper and lower estimates. This work proposes an integrative approach to better constrain the extent of total chloroethene degradation in groundwater samples. It is based on fitting of measured concentration and compound-specific stable carbon isotope data to an analytical reactive transport equation simulating steady-state plumes in two dimensions using an EXCEL spreadsheet. The fitting also yields estimates of degradation rates, of source width and of dispersivities. The approach is validated using two synthetic benchmark cases where the true extent of degradation is well known, and using data from two real field cases from literature.

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

    Science.gov (United States)

    Hamuro, Yoshitomo

    2017-03-01

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

  17. Dissolution rates of unirradiated UO2, UO2 doped with 233U, and spent fuel under normal atmospheric conditions and under reducing conditions using an isotope dilution method

    International Nuclear Information System (INIS)

    Ollila, Kaija; Albinsson, Yngve; Oversby, Virginia; Cowper, Mark

    2003-10-01

    The experimental results given in this report allow us to draw the following conclusions. 1) Tests using unirradiated fuel pellet materials from two different manufacturers gave very different dissolution rates under air atmosphere testing. Tests for fragments of pellets from different pellets made by the same manufacturer gave good agreement. This indicates that details of the manufacturing process have a large effect on the behavior of unirradiated UO 2 in dissolution experiments. Care must be taken in interpreting differences in results obtained in different laboratories because the results may be affected by manufacturing effects. 2) Long-term tests under air atmosphere have begun to show the effects of precipitation. Further testing will be needed before the samples reach steady state. 3) Testing of unirradiated UO 2 in systems containing an iron strip to produce reducing conditions gave [U] less than detection limits ( 235 U added as spike was recovered, indicating that 90% of the spike had precipitated onto the solid sample or the iron strip. 9) Tests of UO 2 pellet materials containing 233 U to provide an alpha decay activity similar to that expected for spent fuel 3000 and 10,000 years after disposal showed that the pellet materials behaved as expected under air atmosphere conditions, showing that the manufacturing method was successful. 10) Early testing of the 233 U-doped materials under reducing conditions showed relatively rapid (30 minute) dissolution of small amounts of U at the start of the puff test procedure. Results of analyses of an acidified fraction of the same solutions after 1 or 2 weeks holding indicate that the solutions were inhomogeneous, indicating the presence of colloidal material or small grains of solid. 11) Samples from the 233 U-doped tests initially indicated dissolution of solid during the first week of testing, with some indication of more rapid dissolution of the material with the higher doping. 12) The second cycle of testing

  18. Kinetic isotope effects and tunnelling in the proton-transfer reaction between 4-nitrophenylnitromethane and tetramethylguanidine in various aprotic solvents

    International Nuclear Information System (INIS)

    Caldin, E.F.; Mateo, S.

    1975-01-01

    Rates and equilibrium constants have been determined for the proton-transfer reaction of 4-nitrophenylnitromethane, NO 2 C 6 H 4 CH 2 NO 2 , and its αα-deuterated analogue NO 2 C 6 H 4 CD 2 NO 2 , with the strong base tetramethylguanidine [HN=C(NMe 2 ) 2 ), at temperatures between -60 0 C and +65 0 in a range of aprotic solvents. Spectrophotometry and the stopped-flow technique were used. The reaction is a simple proton-transfer process leading to an ion-pair. The kinetic isotope effects are correlated with the polarity of the solvents, as measured by the dielectric constant or by the empirical parameter Esub(T). In the less polar solvents they are exceptionally large. In toluene, for example, at 25 0 C the rate ratio ksup(H)/ksup(D) = 45 +- 2, the activation energy difference Esub(a)sup(D) - Esub(a)sup(H) =4.3 +- 0.3 kcal molsup(-1) (16 kJ molsup(-1), and the ratio of the pre-exponential factors logsub(10) (Asup(D)/Asup(H)) = 1.5 +- 0.2+ and even larger values of logsub(10)(Asup(D)/Asup(H)) are found for mesitylene (1.94 +- 0.06) and cyclohexane (2.4 +- 0.2). Positive deviations from linear Arrhenius plots are found for these solvents. Tunnelling is the only interpretation that cannot account for these results. For the more polar solvents (dielectric constant 7 to 37), the isotope effects are closer to the range predicted by semi-classical theory. The isotope effects in all solvents have been fitted to Bell's equation for a parabolic barrier, and the barrier dimensions calculated for each solvent. The suggested interpretation of the results is that the solvent-solute interactions affect the height of the barrier and that motions of solvent molecules are coupled with the motion of the proton in the more polar solvents but not in the less polar ones; reorganization of solvent molecules accompanies the proton-transfer in the more polar solvents, but only electron-polarization in the less polar. Tunnelling has large effects in the less polar solvents, where the

  19. Study on the effect of different fertilizer on the stable nitrogen isotope of soil, leaf and cucumber

    International Nuclear Information System (INIS)

    Yuan Yuwei; Zhang Zhiheng; Xu Mingfei; Yang Guiling; Zheng Jici; Wang Qiang; Zhao Ming

    2010-01-01

    The effect of combined application of organic and chemical fertilizers on stable nitrogen isotope abundance (δ 15 N-%), nitrate and nitrate reductase active was studied for the soil, cucumber and leaf,respectively. The results showed that the δ 15 N of cucumber was with the trend of low, high and low as the application rate of organic manure decreased, and it was significantly different (P 0.05) for the other treatments. The δ 15 N of cucumber was not significantly different during different harvest time (P>0.05) for the same treatment. The correlation of δ 15 N between the cucumber and the leaf was 0.9836 for the different treatment, whose δ 15 N was more affected more by the fertilizer and less by the soil. The content of nitrate in cucumber was reducing with the rate of organic manure decreasing, which had a bad correlation (r=0.6568) with the δ 15 N of cucumber; however the active of nitrate reductase was increasing which had a positive correlation with the treatments of control treatment, 100%, 80% and 60% of organic manure applied (r=0.9187), and a negative correlation with the treatments of 60%, 40%, 20% of organic manure and 100% chemical fertilizer applied (r=-0.9773). To sum up, the δ 15 N can be used as marks to discriminate the cucumbers grown with organic manure and chemical fertilizer, but the pattern of fractionation and distribution of the stable nitrogen isotope should be further studied. (authors)

  20. Oxygen isotope effect in 55Mn and 95Mo NMR spectra of the permanganate and molybdate ion

    International Nuclear Information System (INIS)

    Buckler, K.U.; Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.

    1977-01-01

    By Fourier transform NMR spectroscopy the 55 Mn and 95 Mo resonance lines in the different permanganate and molybdate species Mn 16 Osub(4-n) 18 Osub(n) - and Mo 16 Osub(4-n) 18 Osub(n) 2- (n = 0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate and sodium molybdate. An isotopic effect on the Larmor frequency for 55 Mn of (0.59+-0.02)ppm and for 95 Mo of (0.25+-0.01)ppm to lower frequency has been found for the substitution of one 16 O atom by one 18 O atom. The relaxation rates 1/T 1 of 55 Mn in the different lines of the permanganate solution are equal within the limits of error. The oxygen exchange rate for the water-permanganate system has been evaluated. (orig.) [de

  1. Effect of thyroid hormone on the protein turnover rate of mouse pancreas

    International Nuclear Information System (INIS)

    He Xinjun; Zhou Hui; Wang Shizhen; Zhou Zhonming; Li Liangxue; Wei Huaiwei; Sun Xiaomiao; Wang Yanli

    1986-01-01

    The effects of thyroid hormone on the protein turnover of pancreas in mice were studied using labelled amino acid incorporation, double isotopic and labelled protein decay methods. After injection of L-thyroxine (100 μ g/mouse) for 5 days, the amino acid incorporation into pancreatic proteins of mice was profoundly decreased, the ratio of 3 H/ 14 C in labelled proteins and the fractional turnover rate of pancreatic proteins were also decreased, the protein half-lives being consequently prolonged. These findings suggest that large doses of thyroid hormone may reduce the trunover rate of pancreatic proteins, by inhibiting not only the synthesis but also the degradation

  2. Rates of carbonate soil evolution from carbon, U- and Th-series isotope studies: Example of the Astian sands (SE France)

    Science.gov (United States)

    Barbecot, Florent; Ghaleb, Bassam; Hillaire-Marcel, Claude

    2015-04-01

    In carbonate rich soils, C-isotopes (14C, 13C) and carbonate mass budget may inform on centennial to millennial time scale dissolution/precipitation processes and weathering rates, whereas disequilibria between in the U- and Th-decay series provide tools to document high- (228Ra-228Th-210Pb) to low- (234U, 230Th, 231Pa, 226Ra) geochemical processes rate, covering annual to ~ 1Ma time scales, governing both carbonate and silicate soil fractions. Because lithology constitutes a boundary condition, we intend to illustrate the behavior of such isotopes in soils developed over Astian sands formation (up to ~ 30% carbonate) from the Béziers area (SE France). A >20 m thick unsaturated zone was sampled firstly along a naturally exposed section, then in a cored sequence. Geochemical and mineralogical analyses, including stable isotopes and 14C-measurements, were complemented with 228U, 234U, 230Th, 226Ra, 210Pb and 228Th, 232Th measurements. Whereas the upper 7 m depict geochemical and isotopic features forced by dissolution/precipitation processes leading to variable radioactive disequilibria, but overall deficits in more soluble elements of the decay series, the lower part of the sequence shows strong excesses in 234U and 230Th over parent isotopes (i.e., 238U and 234U, respectively). These features might have been interpreted as the result of successive phases of U-loss and gains. However, 226Ra and 230Th are in near-equilibrium, thus leading to conclude at a more likely slow enrichment process in both 234Th(234U) and 230Th, which we link to dissolved U-decay during groundwater recharge events. In addition, 210Pb deficits (vs parent 226Ra) are observed down to 12 m along the natural outcropping section and below the top-soil 210Pb-excess in the cored sequence, due to gaseous 222Rn-diffusion over the cliff outcrop. Based on C-isotope and chemical analysis, reaction rates at 14C-time scale are distinct from those estimates at the short- or long-lived U-series isotopes

  3. Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses

    Science.gov (United States)

    Peter, A.; Steinbach, A.; Liedl, R.; Ptak, T.; Michaelis, W.; Teutsch, G.

    2004-07-01

    In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods—the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both—were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of δ13C time series by an inversion algorithm to obtain spatially

  4. Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

    Science.gov (United States)

    Deng, Yuying; Li, Yingzhou; Li, Long

    2018-04-01

    Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

  5. Study of isotope effects in the hydrogen transport of an 8% CrWVTa martensitic steel

    International Nuclear Information System (INIS)

    Esteban, G.A.; Sedano, L.A.; Perujo, A.; Douglas, K.

    2001-01-01

    A time-dependent gas-phase isovolumetric desorption technique has been used to assess the isotope effects in the diffusive transport parameters of hydrogen in an 8% CrWVTa reduced activation martensitic steel in the temperature range of 423-892 K and driving pressures from 4 x 10 4 - 1 x 10 5 Pa. The experiments have been run with both protium and deuterium obtaining their respective transport parameters, diffusivity (D), Sieverts' constant (K S ), permeability (Φ), trap site density (η t ) and the trapping activation energy (E t ). Isotope effects on steel are analysed and compared with α-iron. A new way to derive more accurate tritium transport parameters is proposed. (orig.)

  6. A study on the isotope effects in the reduction of carbon dioxide by zinc

    International Nuclear Information System (INIS)

    Senegacnik, M.

    1957-06-01

    We have determined the isotope effects which occur in the reduction of carbon dioxide by zinc. It has been shown that in the case of irreversible surface reactions, Bernstein's equation which permits the calculation of the fractionation factor is still valid. These experimental factors are in good agreement with those obtained by calculating the partition functions of the adsorbed activated complexes. In the reaction mechanism used, the model of the activated complex corresponds to the dissociation of one of the carbon oxygen bonds CO 2 → CO + O. Perturbations arising from the slight reversibility of the reaction Zn + CO 2 ↔ ZnO + CO on the isotope effects on the carbon and oxygen atoms have also been calculated. (author) [fr

  7. Isotope exchange reaction on solid breeder materials

    International Nuclear Information System (INIS)

    Baba, A.; Nishikawa, M.; Eguchi, T.; Kawagoe, T.

    2000-01-01

    Lithium ceramic materials such as Li 2 O, LiAlO 2 , Li 2 ZrO 3 , Li 2 TiO 3 and Li 4 SiO 4 are considered to be as candidate for the tritium breeding material in a deuterium-tritium (D-T) fusion reactor. In the recent blanket designs, helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas to reduce tritium inventory and promote tritium release from the breeding material. In addition, the rate of isotope exchange reaction between hydrogen isotopes in the purge gas and tritium on the surface of the breeding material is necessary to analyze the tritium release behavior from the breeding materials. However, the rate of isotope exchange reactions between hydrogen isotopes in the purge gas and tritium on the surface of those materials has not been quantified until recently. Recently, the present authors quantified the rate of isotope exchange reaction on Li 2 O and Li 2 ZrO 3 . The overall mass transfer coefficients representing the isotope exchange reaction between H 2 and D 2 O on breeding materials or the same between D 2 and H 2 O are experimentally obtained in this study. Comparison to isotope exchange reaction rates on various breeding materials is also performed in this study. Discussions about the effects of temperature, concentration of hydrogen in the purge gas or flow rate of the purge gas on the conversion of tritiated water to tritium gas are also performed

  8. Transition-state analysis of a Vmax mutant of AMP nucleosidase by the application of heavy-atom kinetic isotope effects

    International Nuclear Information System (INIS)

    Parkin, D.W.; Mentch, F.; Banks, G.A.; Horenstein, B.A.; Schramm, V.L.

    1991-01-01

    The transition state of the V max mutant of AMP nucleosidase from Azotobacter vinelandii has been characterized by heavy-atom kinetic isotope effects in the presence and absence of MgATP, the allosteric activator. The enzyme catalyzes hydrolysis of the N-glycosidic bond of AMP at approximately 2% of the rate of the normal enzyme with only minor changes in the K m for substrate, the activation constant for MgATP, and the K i for formycin 5'-phosphate, a tight-binding competitive inhibitor. Isotope effects were measured as a function of the allosteric activator concentration that increases the turnover number of the enzyme from 0.006 s -1 . The kinetic isotope effects were measured with the substrates [1'- 3 H]AMP, [2'- 2 H]AMP, [9- 15 N]AMP, and [1',9- 14 C, 15 N]AMP. All substrates gave significant kinetic isotope effects in a pattern that establishes that the reaction expresses intrinsic kinetic isotope effects in the presence or absence of MgATP. Transition-state analysis using bond-energy and bond-order vibrational analysis indicated that the transition state for the mutant enzyme has a similar position in the reaction coordinate compared to that for the normal enzyme. The mutant enzyme is less effective in stabilizing the carbocation-like intermediate and in the ability to protonate N7 of adenine to create a better leaving group. This altered transition-state structure was confirmed by an altered substrate specificity for the mutant protein

  9. Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

    International Nuclear Information System (INIS)

    Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

    1994-01-01

    CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

  10. pH-Free Measurement of Relative Acidities, Including Isotope Effects.

    Science.gov (United States)

    Perrin, Charles L

    2017-01-01

    A powerful pH-free multicomponent NMR titration method can measure relative acidities, even of closely related compounds, with excellent accuracy. The history of the method is presented, along with details of its implementation and a comparison with earlier NMR titrations using a pH electrode. Many of its areas of applicability are described, especially equilibrium isotope effects. The advantages of the method, some practical considerations, and potential pitfalls are considered. © 2017 Elsevier Inc. All rights reserved.

  11. Kinetic Isotope Effects (KIE) and Density Functional Theory (DFT): A Match Made in Heaven?

    DEFF Research Database (Denmark)

    Christensen, Niels Johan; Fristrup, Peter

    2015-01-01

    Determination of experimental kinetic isotope effects (KIE) is one of the most useful tools for the exploration of reaction mechanisms in organometallic chemistry. The approach has been further strengthened during the last decade with advances in modern computational chemistry. This allows for th...... reaction). The approach is highlighted by using recent examples from both stoichiometric and catalytic reactions, homogeneous and heterogeneous catalysis, and enzyme catalysis to illustrate the expected accuracy and utility of this approach....

  12. Environmental effects on the stable carbon and oxygen isotopic ...

    African Journals Online (AJOL)

    USER

    2010-08-16

    Aug 16, 2010 ... which may be influenced by the river run-off due to heavy rainfall. The coral skeleton was ... including cloud cover (Weber and Woodhead, 1972;. Muscatine et al. ..... The effect of colony topography on climate signals in coral ...

  13. Modelling of rate effects at multiple scales

    DEFF Research Database (Denmark)

    Pedersen, R.R.; Simone, A.; Sluys, L. J.

    2008-01-01

    , the length scale in the meso-model and the macro-model can be coupled. In this fashion, a bridging of length scales can be established. A computational analysis of  a Split Hopkinson bar test at medium and high impact load is carried out at macro-scale and meso-scale including information from  the micro-scale.......At the macro- and meso-scales a rate dependent constitutive model is used in which visco-elasticity is coupled to visco-plasticity and damage. A viscous length scale effect is introduced to control the size of the fracture process zone. By comparison of the widths of the fracture process zone...

  14. Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

    International Nuclear Information System (INIS)

    Hansen, P.E.; Langgard, M.; Bolvig, S.

    1998-01-01

    Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

  15. Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

    International Nuclear Information System (INIS)

    Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

    1982-01-01

    The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

  16. Solvent and solute isotope effects in the aqueous solution of gases. Progress report, July 1, 1978-October 31, 1979

    International Nuclear Information System (INIS)

    Benson, B.B.; Krause, D. Jr.

    1979-10-01

    After developing a 3 He/ 4 He dual beam collection system for the mass spectrometer, the isotopic fractionation factor was determined for helium dissolved in H 2 O, D 2 O, seawater and ethanol. In all solvents the temperature dependence of the fractionation is different from that for a simple isotope vapor pressure effect. Addition of salt to H 2 O increases the fractionation, and the relative salting-out coefficient changes with temperature. A double isotopic effect occurs - the fractionations in D 2 O and H 2 O differ. In ethanol the fractionation is 25% less than in H 2 O

  17. Kinetic α-deuterium isotope effect as a probe of transition state structure and reaction mechanism in nucleoside hydrolysis

    International Nuclear Information System (INIS)

    Stein, R.L.

    1978-01-01

    Theoretical equilibrium α-deuterium isotope effects were calculated for systems modeling nucleoside and glycoside hydrolyses using a computer program (Burton, G.W., Sims, L.B., Wilson, J.C., and Fry, A.J., J. Amer. Chem. Soc., 99, 3374(1977)) which computes isotope effects directly from the expression of Biegeleisen and Mayer (Biegeleisen, J. and Mayer, M.G., J. Chem. Phys., 17, 675(1949)). For nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate, KH/KD = 1.21 to 1.25; while for nucleoside hydrolysis proceeding through an oxocarbonium ion intermediate KH/KD = 1.15 to 1.19. The models used in the calculations were generated systematically and involved a minimum of subjectivity in the selection of molecular parameters. The isotope effects calculated formed the basis for the interpretation of experimental kinetic α-deuterium isotope effects for nucleoside and glycoside hydrolysis

  18. Communication: Isotopic effects on tunneling motions in the water trimer

    International Nuclear Information System (INIS)

    Videla, Pablo E.; Rossky, Peter J.; Laria, D.

    2016-01-01

    We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H 2 O] 3 and [D 2 O] 3 , at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H 2 O] 3 than in [D 2 O] 3 . Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments

  19. Communication: Isotopic effects on tunneling motions in the water trimer

    Energy Technology Data Exchange (ETDEWEB)

    Videla, Pablo E. [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Rossky, Peter J. [Department of Chemistry, Rice University, Houston, Texas 77251-1892 (United States); Laria, D., E-mail: dhlaria@cnea.gov.ar [Departamento de Química Inorgánica Analítica y Química-Física e INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires (Argentina); Departamento de Física de la Materia Condensada, Comisión Nacional de Energía Atómica, Avenida Libertador 8250, 1429 Buenos Aires (Argentina)

    2016-02-14

    We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H{sub 2}O]{sub 3} and [D{sub 2}O]{sub 3}, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O–O–O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H{sub 2}O]{sub 3} than in [D{sub 2}O]{sub 3}. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments.

  20. On the Isotopic Altitude Effect of Precipitation in the Northern Adriatic (Croatia)

    Energy Technology Data Exchange (ETDEWEB)

    Roller-Lutz, Z.; Mance, D.; Hunjak, T., E-mail: Roller@medri.hr [Stable Isotope Laboratory, Medical Faculty, University of Rijeka, Rijeka (Croatia); Lutz, H. O. [Stable Isotope Laboratory, Medical Faculty, University of Rijeka, Rijeka (Croatia); Physics Faculty, Bielefeld University, Bielefeld (Germany)

    2013-07-15

    The upper (northern) Adriatic is very rich in precipitation. This input into the water system and its stable isotope composition is a basic factor, knowledge of which is required for proper use and management of water resources. The geomorphology of the region (e.g., mountains of 1400 m next to the sea) can cause specific local conditions. The isotopic composition of precipitation has been measured in various locations at different altitudes. For {delta}{sup 18}O this 'altitude effect' is found to lie around -0.2 per mille /100 m; its exact value depends on the specific location and the season. The {delta}{sup 2}H values and the d-excess vary correspondingly. (author)

  1. Sensitized charge carrier injection into organic crystals studied by isotope effects in weak magnetic fields

    International Nuclear Information System (INIS)

    Bube, W.; Michel-Beyerle, M.E.; Haberkorn, R.; Steffens, E.

    1977-01-01

    The magnetic field (H approximately 50 Oe) dependence of the rhodamine sensitized triplet exciton density in anthracene crystals is influenced by isotopic substitution. This confirms the hyperfine interaction as mechanism explaining the change of the spin multiplicity in the initially formed singlet state of the radical pair. The isotope effect occurs in the sensitizing dye ( 14 N/ 15 N) rather than at the molecular site of the injected charge within the crystal. This can be understood in terms of the high hopping frequency of the charge carriers as compared to the time constant of the hyperfine induced singlet-triplet transition. Since the dye molecules adsorb in an oriented fashion, the angular dependence of the magnetic field modulation of the triplet exciton density can be interpreted without assuming any additional interactions. (Auth.)

  2. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2016-05-01

    The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  3. Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using 13C NMR hydrogen/deuterium isotope shifts

    International Nuclear Information System (INIS)

    Henry, G.D.; Weiner, J.H.; Sykes, B.D.

    1987-01-01

    Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a 13 C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D 2 O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H 2 O solutions; in 1:1 H 2 O/D 2 O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with 13 C at the peptide carbonyls of alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results

  4. Isotopic spin effect in three-pion Bose-Einstein correlations

    International Nuclear Information System (INIS)

    Suzuki, N.

    1998-01-01

    Bose-Einstein (BE) correlations of identical particles in multiple production processes are extensively studied last years because they give an information on the space-time region of interaction. The basic effect is analogous to Hanbury-Brown - Twiss (HBT) interferometry in optics and suggests statistical production of the particles (mainly π mesons). The possible presence of coherent pionic component (for example, in the case of disoriented chiral condensate formation) modifies the HBT effect. On the other hand, the pions (contrary to photons) are subject to isotopic spin (and electric charge) conservation and so they can not be emitted independently. While the corresponding change of the statistical part is not essential for large multiplicities, the coherent part changes substantially when isotopic spin conservation is taken into account. BE correlations of the pions in the presence of both statistical and coherent components are reconsidered taking into account isotopic spin conservation in the coherent part. That will result in appearance of additional contribution to pionic correlation function. (author)

  5. The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

    Science.gov (United States)

    Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

    1994-01-01

    Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

  6. Effect of complexing reagents on the ionization constant of boric acid and its relation to isotopic exchange separation factor

    International Nuclear Information System (INIS)

    Sharma, B.K.; Subramanian, R.; Mathur, P.K.

    1991-01-01

    The effect of change in concentration of complexing reagents having two or more hydroxyl groups, viz., ethylene glycol, propylene glycol, dextrose and mannitol on the ionization constant of boric acid has been studied by pH-metric titration method. The effect of increase in ionization constant of boric acid on isotopic exchange separation factor for the separation of isotopes of boron by ion exchange chromatography has been studied by the batch method. (author). 9 refs

  7. A normalised seawater strontium isotope curve. Possible implications for Neoproterozoic-Cambrian weathering rates and the further oxygenation of the Earth

    International Nuclear Information System (INIS)

    Shields, G.A.

    2007-01-01

    The strontium isotope composition of seawater is strongly influenced on geological time scales by changes in the rates of continental weathering relative to ocean crust alteration. However, the potential of the seawater 87 Sr/ 86 Sr curve to trace globally integrated chemical weathering rates has not been fully realised because ocean 87 Sr/ 86 Sr is also influenced by the isotopic evolution of Sr sources to the ocean. A preliminary attempt is made here to normalise the seawater 87 Sr/ 86 Sr curve to plausible trends in the 87 Sr/ 86 Sr ratios of the three major Sr sources: carbonate dissolution, silicate weathering and submarine hydrothermal exchange. The normalised curve highlights the Neoproterozoic-Phanerozoic transition as a period of exceptionally high continental influence, indicating that this interval was characterised by a transient increase in global weathering rates and/or by the weathering of unusually radiogenic crustal rocks. Close correlation between the normalised 87 Sr/ 86 Sr curve, a published seawater δ 34 S curve and atmospheric pCO 2 models is used here to argue that elevated chemical weathering rates were a major contributing factor to the steep rise in seawater 87 Sr/ 86 Sr from 650 Ma to 500 Ma. Elevated weathering rates during the Neoproterozoic-Cambrian interval led to increased nutrient availability, organic burial and to the further oxygenation of Earth's surface environment. Use of normalised seawater 87 Sr/ 86 Sr curves will, it is hoped, help to improve future geochemical models of Earth System dynamics. (orig.)

  8. Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Bruce S. [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Lollar, Barbara Sherwood [Earth Sciences Department, University of Toronto, 22 Russell Street, Toronto, ON M5S 3B1 (Canada); Passeport, Elodie [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada); Chemical Engineering and Applied Chemistry Department, University of Toronto, 200 College Street, Toronto, ON M5S 3E5 (Canada); Sleep, Brent E., E-mail: sleep@ecf.utoronto.ca [Civil Engineering Department, University of Toronto, 35 St George Street, Toronto, ON M5S 1A4 (Canada)

    2016-04-15

    Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C{sub 0}), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D{sub mech}/D{sub eff}). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C{sub 0}/MDL ratios of 50 or higher. Much larger C{sub 0}/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D{sub mech}/D{sub eff} is

  9. Diffusion related isotopic fractionation effects with one-dimensional advective–dispersive transport

    International Nuclear Information System (INIS)

    Xu, Bruce S.; Lollar, Barbara Sherwood; Passeport, Elodie; Sleep, Brent E.

    2016-01-01

    Aqueous phase diffusion-related isotope fractionation (DRIF) for carbon isotopes was investigated for common groundwater contaminants in systems in which transport could be considered to be one-dimensional. This paper focuses not only on theoretically observable DRIF effects in these systems but introduces the important concept of constraining “observable” DRIF based on constraints imposed by the scale of measurements in the field, and on standard limits of detection and analytical uncertainty. Specifically, constraints for the detection of DRIF were determined in terms of the diffusive fractionation factor, the initial concentration of contaminants (C_0), the method detection limit (MDL) for isotopic analysis, the transport time, and the ratio of the longitudinal mechanical dispersion coefficient to effective molecular diffusion coefficient (D_m_e_c_h/D_e_f_f). The results allow a determination of field conditions under which DRIF may be an important factor in the use of stable carbon isotope measurements for evaluation of contaminant transport and transformation for one-dimensional advective–dispersive transport. This study demonstrates that for diffusion-dominated transport of BTEX, MTBE, and chlorinated ethenes, DRIF effects are only detectable for the smaller molar mass compounds such as vinyl chloride for C_0/MDL ratios of 50 or higher. Much larger C_0/MDL ratios, corresponding to higher source concentrations or lower detection limits, are necessary for DRIF to be detectable for the higher molar mass compounds. The distance over which DRIF is observable for VC is small (less than 1 m) for a relatively young diffusive plume (< 100 years), and DRIF will not easily be detected by using the conventional sampling approach with “typical” well spacing (at least several meters). With contaminant transport by advection, mechanical dispersion, and molecular diffusion this study suggests that in field sites where D_m_e_c_h/D_e_f_f is larger than 10, DRIF

  10. Effect of temperature on kinetics of phosphorus isotope sorption by soils

    International Nuclear Information System (INIS)

    Osztoics, E.; Konya, J.; Nagy, N.; Varallyay, L.

    1994-01-01

    Sorption of water soluble P by soils may be approximated by a rapid plus a slow processes. The rapid process of P sorption was studied on samples of five characteristic Hungarian soil types (meadow soil from Hajduboszormeny, brown forest soil from Keszthely, chernozem soil from Oroshaza and sandy soil from Orbottyan), using 32 P isotope technique. Kinetics of 32 P sorption and the effect of temperature (0, 25, and 40 o C) on the processes were investigated. The kinetic data were evaluated using the Christiansen equation. The activation energy and activation entropy of the processes were calculated from the temperature-dependence of the kinetic constants. The following conclusions were drawn: 1. The amount of sorbed P increases with increasing temperature, the increase is different in different soil types depending on soil characteristics. 2. Two processes of different velocity may be distinguished in the rapid P sorption under our experimental conditions. 3. The activation energy of the faster process is 25-50 kJ/mol. This suggests that film diffusion of phosphorus is the rate-limiting process in the first step of P sorption. 4. The activation energy of the slower process of rapid sorption is less than that of the faster process. 5. In contrast, the activation entropy of the slower process is twice as high (in absolute values) as that of the first, instantaneous process. The slower process is probably connected with a structural rearrangement of the sorption layer, i.e. the phosphorus becomes more firmly held. 6. This rearrangement is supported also by our previous studies on the reversibility of 32 P sorption. (author)

  11. Evaluating cleansing effects on trace elements and stable isotope values in feathers of oiled birds.

    Science.gov (United States)

    Valladares, Sonia; Moreno, Roćio; Jover, Lluis; Sanpera, Carola

    2010-01-01

    Feathers of seabirds are widely used as a nondestructive tissue for pollution monitoring of trace elements, as well as convenient samples for trophic ecology studies by means of stable isotope analysis (SIA). Nevertheless, feathers can be occasionally impregnated with oil from deliberate ship discharges and from massive oil spill accidents. The feather structure makes them effective traps for particles and are subject to external contamination. It is unknown to what extent the oil adhered to feathers can change trace element concentrations or stable isotope signatures. This study has two primary objectives: (1) to assess if there are differences between trace element concentrations and stable isotope signatures of oiled and clean feathers, and (2) to determine if the cleansing of oiled feathers using commonly applied techniques such as sodium hydroxide (NaOH) washes in combination with an organic solvent (hexane) is more effective than using NaOH alone. In order to do this, we analysed trace elements (Se, Hg, Pb, Cu and Zn) and stable isotopes (delta(13)C and delta(15)N) of individual feathers of yellow-legged gulls (Larus michahellis) which were affected by the 2002 Prestige oil spill in Galicia (NW Spain). Two sets of feathers were analysed, one group were oil-free (Control group) and the other had oil adhered to its surface (Oiled group). We expected to find differences between control and oiled feathers when cleaning exclusively with NaOH and no differences when using hexane. Our results did not show significant differences between Control and Oiled groups as a consequence of the cleansing method used. Unexpectedly, the additional cleansing with hexane resulted in decreasing selenium concentrations and increasing zinc and delta(15)N values in all groups of feathers.

  12. Laser assisted aerodynamic isotope separation

    International Nuclear Information System (INIS)

    Berg, H. van den

    1985-01-01

    It is shown that the efficiency of conventional aerodynamic isotope seperation can be improved by two orders of magnitude with the aid of a relatively weak cw infrared laser which is used to induce isotopically selective condensation. Overall isotope enrichment factors in excess of 2 are obtained as compared to about 1.02 in the conventional seperation. Sulphur isotopes in SF 6 as well as Silicon isotopes in SiF 4 and Bromine isotopes in CF 3 Br are seperated on a laboratory scale. Infrared vibrational predissociation by itself and in combination with isotopically selective condensation are also shown to be effective new ways of isotope separation. (orig.) [de

  13. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  14. Measurement of the isotope effect of the diffusion of silver and gold in gold and of silver in silver-gold alloys

    International Nuclear Information System (INIS)

    Wolter, D.

    1974-01-01

    The silver isotopes Ag 105 and Agsup(110m) and the gold isotopes Au 195 and Au 199 were used for isotope effect measurements. The isotope effect of the gold self-diffusion was measured on four monocrystals samples at about 850 0 C, that of silver in gold monocrystals at five different temperatures between 731 0 C and 1050 0 C. Furthermore, the isotope effect for silver at 904 0 C was measured on seven silver-gold alloys of varying silver concentration. The correlation factor was determined from the measurements. (HPOE/LH) [de

  15. Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

    Science.gov (United States)

    Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

    2016-06-22

    An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

  16. Secondary α-deuterium isotope effects as a probe to the relationship between structure and mechanism of pyrolysis of secondary azoalkanes

    International Nuclear Information System (INIS)

    Grizzle, P.L.

    1975-01-01

    This study was carried out to investigate the mechanism of azoalkane thermolysis and the effect of molecular structure on the potential-energy hypersurface for pyrolysis utilizing secondary α-deuterium isotope effects. Since the magnitude of the α-effect for 1,1'-diphenylazoethane is of singular importance in the interpretation of those for related compounds, it has been redetermined. To investigate the effect of molecular structure on the potential-energy hypersurface for thermolysis, α-effects have been determined for 2,2,2',2'-tetramethyl-1,1'-diphenylazoethane and (2,2-dimethyl-1-phenylpropyl)azomethane; the inability to prepare these compounds by conventional methods necessitated the development of a new method for synthesis of secondary azoalkanes. A convenient synthesis of secondary azo compounds is reported. Secondary α-deuterium isotope effects were obtained for the thermal decomposition of 1,1'-diphenylazoethane (III) and 1,1'-diphenylazoethane-1,1'-d 2 (III-d 2 ). The isotope effect is entirely consistent with a simultaneous one-step thermolysis mechanism. Secondary α-deuterium isotope effects and activation parameters were obtained in the thermolysis of 2,2,2',2'-tetramethyl-1,1'-diphenylazopropane (VIII) and (2,2-dimethyl-1-phenylpropyl)azomethane (IX). The data for VIII is considered in terms of both a one- and two-step thermolysis mechanism. The α-effect and activation energy for VIII are not obviously reconcilable with a one-step mechanism. The α-effects, activation energies, and rates of thermolysis for VIII, IX, and (1-phenylethyl)azomethane are most easily rationalized by a two-step mechanism

  17. Accuracy in activation analysis: count rate effects

    International Nuclear Information System (INIS)

    Lindstrom, R.M.; Fleming, R.F.

    1980-01-01

    The accuracy inherent in activation analysis is ultimately limited by the uncertainty of counting statistics. When careful attention is paid to detail, several workers have shown that all systematic errors can be reduced to an insignificant fraction of the total uncertainty, even when the statistical limit is well below one percent. A matter of particular importance is the reduction of errors due to high counting rate. The loss of counts due to random coincidence (pulse pileup) in the amplifier and to digitization time in the ADC may be treated as a series combination of extending and non-extending dead times, respectively. The two effects are experimentally distinct. Live timer circuits in commercial multi-channel analyzers compensate properly for ADC dead time for long-lived sources, but not for pileup. Several satisfactory solutions are available, including pileup rejection and dead time correction circuits, loss-free ADCs, and computed corrections in a calibrated system. These methods are sufficiently reliable and well understood that a decaying source can be measured routinely with acceptably small errors at a dead time as high as 20 percent

  18. Deuterium isotope effects during formation of phenols by hepatic monoxygenases. Evidence for an alternative to the arene oxide pathway

    International Nuclear Information System (INIS)

    Tomaszewski, J.E.; Jerina, D.M.; Daly, J.W.

    1975-01-01

    The in vivo and in vitro metabolisms of normal and deuterated aromatic substrates have been investigated in rats. Significant isotope effects (k/ sub H//k/sub D/ equals 1.3-1.75) were associated with in vivo formation of meta-hydroxylated metabolites from 1:1 mixtures of normal and perdeuterio-(arylring) nitrobenzene, methyl phenyl sulfide, and methyl phenyl sulfone. Since isotope effects of this magnitude are incompatible with arene oxides as intermediates in the formation of phenols, the results provide evidence that multiple pathways are responsible for the formation of phenols in mammals. Significant isotope effects were not associated with the formation of the other phenolic isomers of nitrobenzene, methyl phenyl sulfone, or methyl phenyl sulfide or with the formation of phenolic products from anisole, bromobenzene, chlorobenzene, fluorobenzene, benzonitrile, naphthalene, zoxazolamine, acetanilide, biphenyl, diphenylhydantoin, benzene, o- and p-xylene, toluene, and mesitylene. Significant isotope effects might not be observable with the latter substrates if the kinetic parameters for oxidation of substrate change or if the arene oxide pathway greatly predominates. Furthermore, extensive in vivo metabolism of any substrate would make isotope effects unobservable by the procedure employed, namely the analysis of isotope content in metabolites formed from 1:1 mixtures of normal and deuterated substrates. (U.S.)

  19. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, L.W.; DeNiro, M.J. (Univ. of California, Los Angeles (United States))

    1989-12-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leaf water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.

  20. Impurity effects of hydrogen isotope retention on boronized wall in LHD

    International Nuclear Information System (INIS)

    Oya, Yasuhisa; Okuno, Kenji; Ashikawa, Naoko; Nishimura, Kiyohiko; Sagara, Akio

    2010-11-01

    The impurity effect on hydrogen isotopes retention in the boron film deposited in LHD was evaluated by means of XPS and TDS. It was found that the impurity concentrations in boron film were increased after H-H main plasma exposure in LHD. The ratio of hydrogen retention trapped by impurity to total hydrogen retention during H-H main plasma exposure was reached to 70%, although that of deuterium retention by impurity in D 2 + implanted LHD-boron film was about 35%. In addition, the dynamic chemical sputtering of hydrogen isotopes with impurity as the form of water and / or hydrocarbons was occurred by energetic hydrogen isotopes irradiation. It was expected that the enhancement of impurity concentration during plasma exposure in LHD would induce the dynamic formation of volatile molecules and their re-emission to plasma. These facts would prevent stable plasma operation in LHD, concluding that the dynamic impurity behavior in boron film during plasma exposure is one of key issues for the steady-state plasma operation in LHD. (author)

  1. The effect of natural weathering on the chemical and isotopic composition of biotites

    International Nuclear Information System (INIS)

    Clauer, N.; Bonnot-Courtois, C.

    1982-01-01

    The effect of progressive natural weathering on the isotopic (Rb-Sr, K-Ar, deltaD, delta 18 O) and chemical (REE, H 2 O + ) compositions of biotite has been studied on a suite of migmatitic biotites from the Chad Republic. During the early stages of weathering the Rb-Sr system is strongly affected, the hydrogen and oxygen isotope compositions change markedly, the minerals are depleted in light REE, the water content increases by a factor of two, and the K-Ar system is relatively little disturbed. During intensive weathering the K-Ar system is more strongly disturbed than the Rb-Sr system. Most of the isotopic and chemical modifications take place under nonequilibrium conditions and occur before newly formed kaolinite and/or smectite can be detected. These observations suggest that (a) 'protominerals' may form within the biotite structure during the initial period of weathering, and (b) only when chemical equilibrium is approached in the weathering profile are new minerals able to form. (author)

  2. Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

    Science.gov (United States)

    Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

    2014-07-01

    In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral

  3. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    International Nuclear Information System (INIS)

    Cooper, L.W.; DeNiro, M.J.

    1989-01-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  4. N-loss isotope effects in the Peru oxygen minimum zone studied using a mesoscale eddy as a natural tracer experiment

    Science.gov (United States)

    Bourbonnais, Annie; Altabet, Mark A.; Charoenpong, Chawalit N.; Larkum, Jennifer; Hu, Haibei; Bange, Hermann W.; Stramma, Lothar

    2015-06-01

    Mesoscale eddies in Oxygen Minimum Zones (OMZs) have been identified as important fixed nitrogen (N) loss hotspots that may significantly impact both the global rate of N-loss as well as the ocean's N isotope budget. They also represent "natural tracer experiments" with intensified biogeochemical signals that can be exploited to understand the large-scale processes that control N-loss and associated isotope effects (ɛ; the ‰ deviation from 1 in the ratio of reaction rate constants for the light versus heavy isotopologues). We observed large ranges in the concentrations and N and O isotopic compositions of nitrate (NO3-), nitrite (NO2-), and biogenic N2 associated with an anticyclonic mode-water eddy in the Peru OMZ during two cruises in November and December 2012. In the eddy's center where NO3- was nearly exhausted, we measured the highest δ15N values for both NO3- and NO2- (up to ~70‰ and 50‰) ever reported for an OMZ. Correspondingly, N deficit and biogenic N2-N concentrations were also the highest near the eddy's center (up to ~40 µmol L-1). δ15N-N2 also varied with biogenic N2 production, following kinetic isotopic fractionation during NO2- reduction to N2 and, for the first time, provided an independent assessment of N isotope fractionation during OMZ N-loss. We found apparent variable ɛ for NO3- reduction (up to ~30‰ in the presence of NO2-). However, the overall ɛ for N-loss was calculated to be only ~13-14‰ (as compared to canonical values of ~20-30‰) assuming a closed system and only slightly higher assuming an open system (16-19‰). Our results were similar whether calculated from the disappearance of DIN (NO3- + NO2-) or from the appearance of N2 and changes in isotopic composition. Further, we calculated the separate ɛ values for NO3- reduction to NO2- and NO2- reduction to N2 of ~16-21‰ and ~12‰, respectively, when the effect of NO2- oxidation could be removed. These results, together with the relationship between N and O of NO

  5. 20 CFR 655.207 - Adverse effect rates.

    Science.gov (United States)

    2010-04-01

    ... 20 Employees' Benefits 3 2010-04-01 2010-04-01 false Adverse effect rates. 655.207 Section 655.207... Agricultural Employment § 655.207 Adverse effect rates. (a) Except as otherwise provided in this section, the adverse effect rates for all agricultural and logging employment shall be the prevailing wage rates in the...

  6. Generalized transition state theory. Quantum effects for collinear reactions of hydrogen molecules and isotopically substituted hydrogen molecules

    International Nuclear Information System (INIS)

    Garrett, B.C.; Truhlar, D.G.

    1979-01-01

    Canonical variational transition state theory, microcanonical variational transition state theory, and Miller's unified statistical theory were used in an attempt to correct two major deficiencies of the conventional transition state theory. These are: (1) the necessity of extra assumptions to include quantum mechanical tunneling effects and (2) the fundamental assumption that trajectories crossing a dividing surface in phase space proceed directly to products. The accuracy of these approximate methods were tested by performing calculations for several collinear reactions of hydrogen, deuterium, chlorine, or iodine, with five isotopes of hydrogen molecules and comparison of these results with those from accurate quantitative calculations of the reaction probabilities as functions of energy and of the thermal rate constants as functions of temperature. 49 references, 28 figures, 17 tables

  7. Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

    International Nuclear Information System (INIS)

    Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

    1985-01-01

    The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

  8. Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

    Energy Technology Data Exchange (ETDEWEB)

    Khadka, Nimesh [Department of Chemistry; Milton, Ross D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Shaw, Sudipta [Department of Chemistry; Lukoyanov, Dmitriy [Department; Dean, Dennis R. [Department of Biochemistry, Virginia Tech, Blacksburg, Virginia 24061, United States; Minteer, Shelley D. [Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States; Raugei, Simone [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Hoffman, Brian M. [Department; Seefeldt, Lance C. [Department of Chemistry

    2017-09-15

    Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio, revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.

  9. Study of the matrix specific mass discrimination effects during inductively coupled plasma mass spectrometry isotope ratio measurements

    International Nuclear Information System (INIS)

    Vassileva, E.; Quetel, Ch.R.

    2004-01-01

    Sample matrix related effects on mass discrimination during inductively coupled plasma mass spectrometry (ICP-MS) isotope ratio measurements have only been rarely reported. However, they can lead to errors larger than the uncertainty claimed on the ratio results when not properly taken into account or corrected for. These matrix specific affects were experienced during an Isotope Dilution Mass Spectrometry (IDMS) campaign we carried out for the certification of the Cd amount content in some food digest samples (7% acidity and salts content around 450μg g -1 ). Dilution was not possible for Cd only present at the low ng g -1 level. Up to 1% difference was observed on Cd isotope ratio results between measurements performed directly or after matrix separation. This was a significant difference considering that less than 1.5% relative combined uncertainty was eventually estimated for these IDMS measurements. Similar results could be obtained either way after the implementation of necessary corrections. The direct measurement approach associated to a correction for mass discrimination effects using the food digest sample itself (and the IUPAC table values as reference for the natural Cd isotopic composition) was preferred as it was the easiest. Consequently, the impact of matrix effects on mass discrimination during isotope ratio measurements with two types of ICP- MS (quadrupole and magnetic sector instruments) was studied for 4 elements (Li, Cu, Cd and Tl). Samples of varying salinity (up to 0.25%) and acidity (up to 7%) characteristics were prepared using isotopic certified reference materials of these elements. The long term and short-term stability, respectively reproducibility and repeatability, of the results, as well as the evolution of the difference to certified ratio values were monitored. As expected the 13 investigated isotopic ratios were all sensitive to variations in salt and acid concentrations. Our experiments also showed that simultaneous variation

  10. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

    Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

    1977-01-01

    A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

  11. Brazilian exchange rate complexity: Financial crisis effects

    Science.gov (United States)

    Piqueira, José Roberto C.; Mortoza, Letícia Pelluci D.

    2012-04-01

    With the financial market globalization, foreign investments became vital for the economies, mainly in emerging countries. In the last decades, Brazilian exchange rates appeared as a good indicator to measure either investors' confidence or risk aversion. Here, some events of global or national financial crisis are analyzed, trying to understand how they influenced the "dollar-real" rate evolution. The theoretical tool to be used is the López-Mancini-Calbet (LMC) complexity measure that, applied to real exchange rate data, has shown good fitness between critical events and measured patterns.

  12. Effects of arbuscular mycorrhizal fungi on gas exchange and stable isotope ratio of δ13C, δ15N of leymus chinensis plant

    International Nuclear Information System (INIS)

    Shi Weiqi; Wang Guoan; Li Xiaolin

    2008-01-01

    Leymus chinensis, one of dominant species in Inner Mongolia grassland, was selected to evaluate the effects of arbuscular mycorrhizal fungi (AMF) on plant gas change parameters and stable isotope ratio in pot culture. The plant was inoculated with two mycorrhizal fungi, Glomus intraradices and Glomus claroidum, and the uninoculated plant was used as the control check. On the 45th , 60th , 75th days after sowing, gas exchange parameters and stable isotope ratio were measured. The results showed that AM infection promoted phosphoms content, stomatal conductance and photosynthetic rate of Leymus chinensis, reduced host δ 15 N, however, it did not influence host intrinsic water using efficiency and δ 13 C. It was the growth time that significantly affected the gas exchange and stable isotope ratio of δ 13 C and δ 15 N. And the interaction of inoculation and growth time also influenced on the net photosynthetic rate, δ 13 C and δ 15 N of the host. Stomatal conductance and photosynthetic rate were always changed the same direction by arbuscular mycorrhizal fungi causing no significant difference between mycorrhizal and non-mycorrhizal plant. AMF absorbed nitrogen and accumulated δ 15 N, thus, it transformed less 15 N into the host, and as a result, the mycorrhizal plant had lower δ 15 N. Therefore, the results gave a new way and reference to know of the grass balance of carbon gain and water cost and the nitrogen cycle in grassland. (authors)

  13. A Longitudinal Examination of Rater and Ratee Effects in Performance Ratings.

    Science.gov (United States)

    Vance, Robert J.; And Others

    1983-01-01

    Investigated the consistency and loci of leniency, halo, and range restriction effects in performance ratings in a longitudinal study. Policy supervisors (N=90) rated 350 subordinates on five occasions. Concluded that reliable variance in mean ratings is partly attributable to ratees, but mainly introduced by raters. (JAC)

  14. Mechanism of the reaction catalyzed by dihydrofolate reductase from Escherichia coli: pH and deuterium isotope effects with NADPH as the variable substrate

    International Nuclear Information System (INIS)

    Morrison, J.F.; Stone, S.R.

    1988-01-01

    The variations with pH of the kinetic parameters and primary deuterium isotope effects for the reaction of NADPH with dihydrofolate reductase from Escherichia coli have been determined. The aims of the investigations were to elucidate the chemical mechanism of the reaction and to obtain information about the location of the rate-limiting steps. The V and V/K/sub NADPH/ profiles indicate that a single ionizing group at the active center of the enzyme must be protonated for catalysis, whereas the K/sub i/ profiles show that the binding of NADPH to the free enzyme and of ATP-ribose to the enzyme-dihydrofolate complex is pH independent. From the results of deuterium isotope effects on V/K/sub NADPH/, it is concluded that NADPH behaves as a sticky substrate. It is this stickiness that raises artificially the intrinsic pK value of 6.4 for the Asp-27 residue of the enzyme-dihydrofolate complex to an observed value of 8.9. Thus, the binary enzyme complex is largely protonated at neutral pH. The elevation of the intrinsic pK value of 6.4 for the ternary enzyme-NADPH-dihydrofolate complex to 8.5 is not due to the kinetic effects of substrates. Rather, it is the consequence of the lower, pH-independent rate of product release and the faster pH-dependent catalytic step. The data for deuterium isotope and deuterium solvent isotope effects are consistent with the postulate that, for the reduction of dihydrofolate to tetrahydrofolate, protonation precedes hydride transfer. A scheme is proposed for the indirect transfer of a proton from the enzyme to dihydrofolate

  15. A comparative study on the production rates of VFA and bacteria in the rumen of buffalo and goat estimated by isotope dilution technique

    International Nuclear Information System (INIS)

    Verma, D.N.; Mehra, U.R.; Singh, U.B.; Ranjhan, S.K.

    1977-01-01

    Digestibility trials were conducted on Murrah buffaloes and Barbari goats with rumen cannulae in the rumen to determine the digestibility of the feed constituents and the production rates of bacteria and total VFA were estimated in the rumen by isotope dilution technique. The bacterial cells growth in the rumen was more in goats than buffaloes when fed ad libitum and calculated on equal feed intake, where as, in buffaloes fed on restricted diet equal to the goats the production of bacteria and VFA were higher. Goats converted 54.04 percent of their dietary nitrogen into microbial nitrogen which was more than twice of buffaloes. (author)

  16. Count rate effect in proportional counters

    International Nuclear Information System (INIS)

    Bednarek, B.

    1980-01-01

    A new concept is presented explaining changes in spectrometric parameters of proportional counters which occur due to varying count rate. The basic feature of this concept is that the gas gain of the counter remains constant in a wide range of count rate and that the decrease in the pulse amplitude and the detorioration of the energy resolution observed are the results of changes in the shape of original current pulses generated in the active volume of the counter. In order to confirm the validity of this statement, measurements of the gas amplification factor have been made in a wide count rate range. It is shown that above a certain critical value the gas gain depends on both the operating voltage and the count rate. (author)

  17. Transition-state structure in the yeast alcohol dehydrogenase reaction: the magnitude of solvent and alpha-secondary hydrogen isotope effects

    International Nuclear Information System (INIS)

    Welsh, K.M.; Creighton, D.J.; Klinman, J.P.

    1980-01-01

    Solvent and alpha-secondary isotope effects have been measured in the yeast alcohol dehydrogenase reaction, under conditions of a rate-limiting transfer of hydrogen between coenzyme and substrate. Determination of catalytic constants in H20 and D20 as a function of pH(D) has allowed the separation of solvent effects on pKa from kcat. The small effect of D20 on pKa is tentatively assigned to ionization of an active-site ZnOH 2 . The near absence of an isotope effect on kcat in the direction of alcohol oxidation rules out a mechanism involving concerted catalysis by an active-site base of hydride transfer. The near identity of kinetic and equilibrium alpha-secondary isotope effects in the direction of alcohol oxidation implicates a transition-state structure which resembles aldehyde with regard to bond hybridization properties. The result contrasts sharply with previously reported structure - reactivity correlations, which implicate a transition-state structure resembling alcohol with regard to charge properties. The significance of these findings to the mechanism of NAD(P)H-dependent redox reactions is discussed

  18. Dose rate effect in food irradiation

    International Nuclear Information System (INIS)

    Singh, H.

    1991-08-01

    It has been suggested that the minor losses of nutrients associated with radiation processing may be further reduced by irradiating foods at the high dose rates generally associated with electron beams from accelerators, rather than at the low dose rates typical of gamma irradiation (e.g. 60 Co). This review briefly examines available comparative data on gamma and electron irradiation of foods to evaluate these suggestions. (137 refs., 27 tabs., 11 figs.)

  19. Ab initio calculation of the transition-state properties and addition rate constants for H + C2H2 and selected isotopic analogues

    International Nuclear Information System (INIS)

    Harding, L.B.; Wagner, A.F.; Bowman, J.M.; Schatz, G.C.; Christoffel, K.

    1982-01-01

    GVB-POL-CI ab initio calculations of the geometries, energetics, and normal mode frequencies of C 2 H 2 , C 2 H 3 , and the transition state for the addition reaction of H + C 2 H 2 are presented. In addition, normal mode frequencies for the isotopic variants D + C 2 D 2 , D + C 2 H 2 , and H + C 2 D 2 are preented. These results are compared to experimental values for C 2 H 2 and to ab initio values of Hagase and Kern, and semiempirical values of Keil, Lynch, Cowfer, and Michael. The results are also used to calculate the apparent bimolecular addition rate constant using conventional RRKM theory for chemical activation. The calculated rate constants and their isotopic variants are compared as a function of temperature and pressure to available experimental information. The agreement is little different from that obtained by Keil et al. with a similar calculation using semiempirical values for acetylene, transition-state, and vinyl radical properties. In particular, the calculated high-pressure limit of the rate constant appears to be at least 1 order of magnitude higher than the experimental limit. Several possible reasons for this discrepancy are discussed

  20. Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

    Science.gov (United States)

    Managave, S. R.; Jani, R. A.; Narayana Rao, T.; Sunilkumar, K.; Satheeshkumar, S.; Ramesh, R.

    2016-08-01

    Evaporation of rain is known to contribute water vapor, a potent greenhouse gas, to the atmosphere. Stable oxygen and hydrogen isotopic compositions (δ18O and, δD, respectively) of precipitation, usually measured/presented as values integrated over rain events or monthly mean values, are important tools for detecting evaporation effects. The slope ~8 of the linear relationship between such time-averaged values of δD and δ18O (called the meteoric water line) is widely accepted as a proof of condensation under isotopic equilibrium and absence of evaporation of rain during atmospheric fall. Here, through a simultaneous investigation of the isotopic and drop size distributions of seventeen rain events sampled on an intra-event scale at Gadanki (13.5°N, 79.2°E), southern India, we demonstrate that the evaporation effects, not evident in the time-averaged data, are significantly manifested in the sub-samples of individual rain events. We detect this through (1) slopes significantly less than 8 for the δD-δ18O relation on intra-event scale and (2) significant positive correlations between deuterium excess ( d-excess = δD - 8*δ18O; lower values in rain indicate evaporation) and the mass-weighted mean diameter of the raindrops ( D m ). An estimated ~44 % of rain is influenced by evaporation. This study also reveals a signature of isotopic equilibration of rain with the cloud base vapor, the processes important for modeling isotopic composition of precipitation. d-excess values of rain are modified by the post-condensation processes and the present approach offers a way to identify the d-excess values least affected by such processes. Isotope-enabled global circulation models could be improved by incorporating intra-event isotopic data and raindrop size dependent isotopic effects.

  1. Nuclear power's effects on electric rate making

    International Nuclear Information System (INIS)

    Smith, D.S.; Lancaster, A.A.

    1978-01-01

    Government and the electric utility industry are re-evaluating nuclear power's contribution to the total U.S. energy supplies. This article addresses how the recently increased nuclear plant construction and operation costs are translated into the prices that consumers pay for electricity. The electric rates that consumers pay must reflect the costs of producing electricity, as well as the costs of transmission, distribution, metering, and billing. The use of nuclear power for electric production is anticipated to grow rapidly so as to meet a larger portion of our country's electricity needs through the end of the century; so nuclear power costs are expected to be an even larger portion of the total electricity price. There are certain rate-making issues that are actively being discussed in public forums and before state and Federal regulatory bodies. These issues are not unique to nuclear power, but take on added significance when nuclear power is used by utilities to produce electricity because of the technology required and because of the type, timing, and magnitude of the costs involved. These are: (1) inclusion of construction work in progress in the rate base; (2) fuel adjustment clauses and treatment of nuclear fuel cycle costs; (3) treatment of certain taxes under the rate-making method called normalization or deferral accounting (sometimes referred to as ''phantom taxes''); and (4) rate treatment for particular nuclear expense items reflecting costs of delays, plant cancellations, and operational slowdowns

  2. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1988-01-01

    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  3. Isotope effect in the diffusion of hydrogen and deuterium in polymers

    Energy Technology Data Exchange (ETDEWEB)

    Toi, K.; Takeuchi, K.; Tokuda, T.

    1980-02-01

    Temperature dependences of diffusion and permeation coefficients of hydrogen and deuterium in glassy and rubbery polymer films have been measured. The size of the free volume element in rubbery polymers has been calculated according to the theory of Frisch and Rogers for the quantum isotope effect, but the free volume is too large for precise calculation below the glass-transition temperature. The cooperative movement of segments is also discussed using the ratio of preexponential factors for diffusion mechanisms above and below the glass-transition temperature.

  4. Isotope effect with energy-dependent density of states and impurities

    International Nuclear Information System (INIS)

    Williams, P.J.; Carbotte, J.P.

    1992-01-01

    We have calculated the total isotope coefficient β in a model where there is energy-dependent structure in the electronic density of states. We model the structure with a simple Lorentzian. In our calculation, doping has the effect of shifting the Fermi level and broadening the structure in the density of states. We have treated the dopants both as normal and as magnetic impurities. The asymmetry observed in the experimental data is found in our results. However, the complete range of values observed is difficult to reproduce. We question also whether the shifts in Fermi level required in such models are reasonable

  5. The effect of a micro bubble dispersed gas phase on hydrogen isotope transport in liquid metals under nuclear irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Fradera, J., E-mail: jfradera@ubu.es; Cuesta-López, S., E-mail: scuesta@ubu.es

    2013-12-15

    The present work intend to be a first step towards the understanding and quantification of the hydrogen isotope complex phenomena in liquid metals for nuclear technology. Liquid metals under nuclear irradiation in, e.g., breeding blankets of a nuclear fusion reactor would generate tritium which is to be extracted and recirculated as fuel. At the same time that tritium is bred, helium is also generated and may precipitate in the form of nano bubbles. Other liquid metal systems of a nuclear reactor involve hydrogen isotope absorption processes, e.g., tritium extraction system. Hence, hydrogen isotope absorption into gas bubbles modelling and control may have a capital importance regarding design, operation and safety. Here general models for hydrogen isotopes transport in liquid metal and absorption into gas phase, that do not depend on the mass transfer limiting regime, are exposed and implemented in OpenFOAM® CFD tool for 0D–3D simulations. Results for a 0D case show the impact of a He dispersed phase of nano bubbles on hydrogen isotopes inventory at different temperatures as well as the inventory evolution during a He nucleation event. In addition, 1D and 2D axisymmetric cases are exposed showing the effect of a He dispersed gas phase on hydrogen isotope permeation through a lithium lead eutectic alloy and the effect of vortical structures on hydrogen isotope transport at a backward facing step. Exposed results give a valuable insight on current nuclear technology regarding the importance of controlling hydrogen isotope transport and its interactions with nucleation event through gas absorption processes.

  6. Multiple stable isotope fronts during non-isothermal fluid flow

    Science.gov (United States)

    Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

    2018-02-01

    Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

  7. Microbial Oxidation of Hg(0) - Its Effect on Hg Stable Isotope Fractionation and Methylmercury Production

    Energy Technology Data Exchange (ETDEWEB)

    Yee, Nathan [Rutgers Univ., New Brunswick, NJ (United States); Barkay, Tamar [Rutgers Univ., New Brunswick, NJ (United States); Reinfelder, John [Rutgers Univ., New Brunswick, NJ (United States)

    2016-06-28

    relationship between Hg concentrations and rates of denitrification in enrichment cultures. In part III of our project, we examined in more detail the effects of microbial interactions on Hg transformations. We discovered that both sulfate reducing and iron reducing bacteria coexist in freshwater sediments and both microbial groups contribute to mercury methylation. We showed that mercury methylation by sulfate reducing and iron reducing bacteria are temporally and spatially separated processes. We also discovered that methanogens can methylate mercury. We showed that Methanospirillum hungatei JF-1 methylated Hg at comparable rates, but with higher yields, than those observed for sulfate-reducing bacteria and iron-reducing bacteria. Finally, we demonstrated that syntrophic interactions between different microbial groups increase mercury methylation rates. We showed that Hg methylation rates are stimulated via inter-species hydrogen and acetate transfer (i) from sulfate-reducing bacteria to methanogens and (ii) from fermenters to the sulfate-reducing bacteria. In part IV of the project, we studied Hg bioavailability and Hg isotope fractionation. We demonstrated that thiol-bound Hg is bioavailable to mercury resistant bacteria. We found that uptake of Hg from Hg-glutathione and Hg-cysteine complexes does not require functioning glutathione and cystine/cysteine transport systems. We demonstrated that a wide range of methylmercury complexes (e.g. MeHgOH, MeHg-cysteine, and MeHg-glutathione) are bioavailable to mercury resistant bacteria. The rate of MeHg demethylation varies more between different species of mercury resistant bacteria than among MeHg complexes. We showed that microbial demethylation of MeHg depends more on the species of microorganism than on the types and relative concentrations of thiols or other MeHg ligands present. Finally, we demonstrated that Hg methylation by Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132 imparts mass

  8. Oxygen isotopic fractionation during bacterial sulfate reduction

    Science.gov (United States)

    Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.

    2006-12-01

    Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.