Mass-dependent and non-mass-dependent isotope effects in ozone photolysis: Resolving theory and experiments

International Nuclear Information System (INIS)

Cole, Amanda S.; Boering, Kristie A.

2006-01-01

In addition to the anomalous 17 O and 18 O isotope effects in the three-body ozone formation reaction O+O 2 +M, isotope effects in the destruction of ozone by photolysis may also play a role in determining the isotopic composition of ozone and other trace gases in the atmosphere. While previous experiments on ozone photolysis at 254 nm were interpreted as evidence for preferential loss of light ozone that is anomalous (or 'non-mass-dependent'), recent semiempirical theoretical calculations predicted a preferential loss of heavy ozone at that wavelength that is mass dependent. Through photochemical modeling results presented here, we resolve this apparent contradiction between experiment and theory. Specifically, we show that the formation of ozone during the UV photolysis experiments is not negligible, as had been assumed, and that the well-known non-mass-dependent isotope effects in ozone formation can account for the non-mass-dependent enrichment of the heavy isotopologs of ozone observed in the experiment. Thus, no unusual non-mass-dependent fractionation in ozone photolysis must be invoked to explain the experimental results. Furthermore, we show that theoretical predictions of a mass-dependent preferential loss of the heavy isotopologs of ozone during UV photolysis are not inconsistent with the experimental data, particularly if mass-dependent isotope effects in the chemical loss reactions of ozone during the photolysis experiments or experimental artifacts enrich the remaining ozone in 17 O and 18 O. Before the calculated fractionation factors can be quantitatively evaluated, however, further investigation of possible mass-dependent isotope effects in the reactions of ozone with O( 1 D), O( 3 P), O 2 ( 1 Δ), and O 2 ( 1 Σ) is needed through experiments we suggest here

Use of isotope effects to characterize intermediates in mechanism-based inactivation of dopamine beta-monooxygenase by beta-chlorophenethylamine

International Nuclear Information System (INIS)

Bossard, M.J.; Klinman, J.P.

1990-01-01

A mechanism for beta-chlorophenethylamine inhibition of dopamine beta-monooxygenase has been postulated in which bound alpha-aminoacetophenone is generated followed by an intramolecular redox reaction to yield a ketone-derived radical cation as the inhibitory species. Based on the assumption that the ketone radical is the inhibitory intermediate, an analogous system was predicted and verified. In the present study, the role of alpha-aminoacetophenone as the proposed intermediate in the inactivation by beta-chlorophenethylamine was examined in greater detail. From the interdependence of tyramine and alpha-aminoacetophenone concentrations, ketone inactivation is concluded to occur at the substrate site as opposed to potential binding at the reductant-binding site. Using beta-[2-1H]- and beta-[2-2H]chlorophenethylamine, the magnitude of the deuterium isotope effect on inactivation under second-order conditions has been found to be identical to that observed under catalytic turnover, D(kappa inact/Ki) = D(kappa cat/Km) = 6-7. By contrast, the isotope effect on inactivation under conditions of substrate and oxygen saturation, D kappa inact = 2, is 3-fold smaller than that seen on catalytic turnover, D kappa cat = 6. This reduced isotope effect for inactivation is attributed to a normal isotope effect on substrate hydroxylation followed by an inverse isotope effect on the partitioning of the enol of alpha-aminoacetophenone between oxidation to a radical cation versus protonation to regenerate ketone. These findings are unusual in that two isotopically sensitive steps are present in the inactivation pathway whereas only one is observable in turnover

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.

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

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

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

Science.gov (United States)

Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

2016-01-01

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay

Isotopic evidence for the formation of unusually humus-rich soils in the Baltic region

Science.gov (United States)

Leinweber, Peter; Acksel, Andre; Kühn, Peter

2017-04-01

Arable mineral soils in the Pleistocene landscape of Northern Germany usually contain about 4 to 8 kg of organic C (Corg) per m2, most of which is visually recognizable concentrated in the tilled topsoil horizon. Some unusually humus-rich (10 to 20 kg Corg m-2), and deeply (> 70 cm) dark-colored soils in coastal regions with mollic properties have been classified as Chernozems. Their location far away from the middle German and Central European Chernozem regions, absence of steppe vegetation and semi-arid climate conditions make classical pedogenetic theories doubtful. However, non-targeted mass spectrometric analyses of soil organic matter (SOM) composition revealed great similarities with typical Chernozems worldwide (Thiele-Bruhn et al., 2014) and made alternative (e.g. waterlogged) pathways of SOM accumulation unlikely. Subsequent detailed multi-method SOM analyses down the soil profiles revealed relative enrichments in cyclic ("black carbon") and heterocyclic organic compounds in the deeper, bioturbated horizons. These were plausibly explained by the input of combustion residues, likely originating from anthropogenic activities because spots of these soils coincided with archeological artifacts of early settlements (Acksel et al., 2016). However, these finding could not completely explain the genesis of Chernozems in the Baltic region. Therefore, we actually explored isotope analyses (12/13C, 13/14C, 14/15N, 32/34S) to find out the origin of these unusual SOM enrichments and the time period in which it occurred. The results will be compiled to a consistent hypothesis on the formation of these soils in the Baltic and other Northern European regions. References Acksel, A., W. Amelung, P. Kühn, E. Gehrt, T. Regier, P. Leinweber. 2016. Soil organic matter characteristics as indicator of Chernozem genesis in the Baltic Sea region. Geoderma Regional 7, 187-200. Thiele-Bruhn, S., Leinweber P., Eckhardt K.-U., Siem H.K., Blume H.-P. 2014. Identifying Chernozem

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

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

Forecasting the student–professor matches that result in unusually effective teaching

Science.gov (United States)

Gross, Jennifer; Lakey, Brian; Lucas, Jessica L; LaCross, Ryan; R Plotkowski, Andrea; Winegard, Bo

2015-01-01

Background Two important influences on students' evaluations of teaching are relationship and professor effects. Relationship effects reflect unique matches between students and professors such that some professors are unusually effective for some students, but not for others. Professor effects reflect inter-rater agreement that some professors are more effective than others, on average across students. Aims We attempted to forecast students' evaluations of live lectures from brief, video-recorded teaching trailers. Sample Participants were 145 college students (74% female) enrolled in introductory psychology courses at a public university in the Great Lakes region of the United States. Methods Students viewed trailers early in the semester and attended live lectures months later. Because subgroups of students viewed the same professors, statistical analyses could isolate professor and relationship effects. Results Evaluations were influenced strongly by relationship and professor effects, and students' evaluations of live lectures could be forecasted from students' evaluations of teaching trailers. That is, we could forecast the individual students who would respond unusually well to a specific professor (relationship effects). We could also forecast which professors elicited better evaluations in live lectures, on average across students (professor effects). Professors who elicited unusually good evaluations in some students also elicited better memory for lectures in those students. Conclusions It appears possible to forecast relationship and professor effects on teaching evaluations by presenting brief teaching trailers to students. Thus, it might be possible to develop online recommender systems to help match students and professors so that unusually effective teaching emerges. PMID:24953773

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

The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

International Nuclear Information System (INIS)

Khasanov, R; Shengelaya, A; Morenzoni, E; Conder, K; Savic, I M; Keller, H

2004-01-01

Muon spin rotation (μSR) studies of the oxygen isotope ( 16 O/ 18 O) effect (OIE) on the in-plane magnetic field penetration depth λ ab in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T c in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T c . Then, bulk μSR, low-energy μSR, and magnetization studies of the total and site-selective OIE on λ ab are described in some detail. A substantial OIE on λ ab was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T c and λ ab arise from the oxygen sites within the superconducting CuO 2 planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T c and λ ab exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity

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.

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

Structural isotopic effect of the α/β-phase transition in the vanadium hydride and its influence on the equilibrium coefficient of separation of hydrogen isotopes in the gas-solid system

International Nuclear Information System (INIS)

Magomedbekov, Eh.P.; Bochkarev, A.V.

1999-01-01

Equilibrium coefficient of hydrogen isotope separation (α H-D ) in the system of vanadium hydride VH n (solid, n ∼ 0.7)-H 2 (g) is measured by the counterbalancing method in a circulation facility and by the method of laser desorption at 298, 373, and 437 K. It is shown that the combination of highly anharmonic potential in the lattice octahedral sites and in significant difference in the energy of hydrogen atom coordination for tetra- and octahedral sites is the reason for unusual behaviour of the hydrogen isotope separation coefficient and the difference in crystal structures of vanadium hydride and deuteride [ru

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)

Advanced concepts for gamma-ray isotopic analysis and instrumentation

International Nuclear Information System (INIS)

Buckley, W.M.; Carlson, J.B.

1994-07-01

The Safeguards Technology Program at the Lawrence Livermore National Laboratory is developing actinide isotopic analysis technologies in response to needs that address issues of flexibility of analysis, robustness of analysis, ease-of-use, automation and portability. Recent developments such as the Intelligent Actinide Analysis System (IAAS), begin to address these issues. We are continuing to develop enhancements on this and other instruments that improve ease-of-use, automation and portability. Requests to analyze samples with unusual isotopics, contamination, or containers have made us aware of the need for more flexible and robust analysis. We have modified the MGA program to extend its plutonium isotopic analysis capability to samples with greater 241 Am content or U isotopics. We are looking at methods for dealing with tantalum or lead contamination and contamination with high-energy gamma emitters, such as 233 U. We are looking at ways to allow the program to use additional information about the sample to further extend the domain of analyzable samples. These unusual analyses will come from the domain of samples that need to be measured because of complex reconfiguration or environmental cleanup

The oxygen isotope effect on the in-plane penetration depth in cuprate superconductors

Energy Technology Data Exchange (ETDEWEB)

Khasanov, R [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Shengelaya, A [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland); Morenzoni, E [Laboratory for Muon Spin Spectroscopy, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Conder, K [Laboratory for Neutron Scattering, ETH Zuerich and PSI Villigen, CH-5232 Villigen PSI (Switzerland); Savic, I M [Faculty of Physics, University of Belgrade, 11001 Belgrade (Serbia and Montenegro); Keller, H [Physik-Institut der Universitaet Zuerich, CH-8057 Zurich (Switzerland)

2004-10-13

Muon spin rotation ({mu}SR) studies of the oxygen isotope ({sup 16}O/{sup 18}O) effect (OIE) on the in-plane magnetic field penetration depth {lambda}{sub ab} in cuprate high-temperature superconductors (HTS) are presented. First, the doping dependence of the OIE on the transition temperature T{sub c} in various HTS is briefly discussed. It is observed that different cuprate families show similar doping dependences of the OIE on T{sub c}. Then, bulk {mu}SR, low-energy {mu}SR, and magnetization studies of the total and site-selective OIE on {lambda}{sub ab} are described in some detail. A substantial OIE on {lambda}{sub ab} was observed in various cuprate families at all doping levels, suggesting that cuprate HTS are non-adiabatic superconductors. The experiments clearly demonstrate that the total OIE on T{sub c} and {lambda}{sub ab} arise from the oxygen sites within the superconducting CuO{sub 2} planes, demonstrating that the phonon modes involving the movement of planar oxygen are dominantly coupled to the supercarriers. Finally, it is shown that the OIE on T{sub c} and {lambda}{sub ab} exhibit a relation that appears to be generic for different families of cuprate HTS. The observation of these unusual isotope effects implies that lattice effects play an essential role in cuprate HTS and have to be considered in any realistic model of high-temperature superconductivity.

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

Achievements in testing of the MGA and FRAM isotopic software codes under the DOE/NNSA-IRSN cooperation of gamma-ray isotopic measurement systems

International Nuclear Information System (INIS)

Vo, Duc; Wang, Tzu-Fang; Funk, Pierre; Weber, Anne-Laure; Pepin, Nicolas; Karcher, Anna

2009-01-01

DOE/NNSA and IRSN collaborated on a study of gamma-ray instruments and analysis methods used to perform isotopic measurements of special nuclear materials. The two agencies agreed to collaborate on the project in response to inconsistencies that were found in the various versions of software and hardware used to determine the isotopic abundances of uranium and plutonium. IRSN used software developed internally to test the MGA and FRAM isotopic analysis codes for criteria used to stop data acquisition. The stop-criterion test revealed several unusual behaviors in both the MGA and FRAM software codes.

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

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.

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....

Forecasting the Student-Professor Matches That Result in Unusually Effective Teaching

Science.gov (United States)

Gross, Jennifer; Lakey, Brian; Lucas, Jessica L.; LaCross, Ryan; Plotkowski, Andrea R.; Winegard, Bo

2015-01-01

Background: Two important influences on students' evaluations of teaching are relationship and professor effects. Relationship effects reflect unique matches between students and professors such that some professors are unusually effective for some students, but not for others. Professor effects reflect inter-rater agreement that some professors…

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.

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

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

Magnetic and micellar effects on photoreactions. 1. 13C isotopic enrichment of dibenzyl ketone via photolysis in aqueous detergent solution

International Nuclear Information System (INIS)

Turro, N.J.; Chow, M.F.; Chung, C.J.; Kraeutler, B.

1981-01-01

The photolysis of dibenzyl ketone (DBK) in homogeneous organic solutions and in micelle-containing detergent solutions has been investigated from the standpoint of determining the extent and location of 13 C enrichment that occurs. In a series of experiments it is established that for incomplete conversions the residual, recovered DBK is enriched in 13 C relative to the initial unphotolyzed DBK. The efficiency of the 13 C/ 12 C separation is shown to be characterized by an isotope enrichment parameter, α, which is independent of the extent of conversion. A combination of mass spectrometry and nuclear magnetic resonance spectroscopy provides support for the primary location of the 13 C enrichment at C-1 (the carbonyl carbon) with a lesser but significant enrichment at C-2 (the methylene carbon). A very small but experimentally distinct enrichment of the aromatic rings is indicated by 13 C NMR analysis. An isomer of DBK, 1-phenyl-4'-methylacetophenone (PMAP) is formed as a minor product of photolysis in micellar solutions. PMAP, like the recovered, residual DBK, is found to be substantially enriched in 13 C relative to the starting DBK. The magnitude of α is found to be significantly influenced by the application of laboratory magnetic fields to the photolysis sample. The latter result, along with the unusually large magnitude of α, suggests that the mechanism involved in isotopic enrichment is not dominated by kinetic mass isotope effects but rather by nuclear magnetic moment and/or magnetic spin isotope effects

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.

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

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)

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...

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)

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)

Oxygen isotopic anomalies in Allende inclusion HAL

International Nuclear Information System (INIS)

Lee, T.; Mayeda, T.K.; Clayton, R.N.

1980-01-01

The oxygen isotopic composition has been measured on the constituent phases of Allende inclusion HAL, which has unusual mineralogical, chemical, and calcium isotopic compositions. The oxygen in HAL is heterogeneous, with the rim showing more ''normal'' composition and the hibonite core showing large deviation from both the terrestrial material and the usual inclusions. The observed pattern indicates that HAL is a bona fide and more devious member of the rare ''FUN'' family, whose isotopic composition is characterized by correlated nuclear effects and extreme mass fractionation. The data imply that HAL has suffered a large oxygen mass fractionation of 25% 0 per mass unit, followed by exchange with oxygen in a second reservoir. The present experiment supports the identification of two distinct reservoirs from which all refractory inclusions in carbonaceous meteorites derived their oxygen. The required fractionation process seems to operate according to the volatility of various elements and could have been caused by evaporation during a heating event. Nuclear anomalies can be produced in the same heating event if the progenitors of the refractory inclusions were macroscopic aggregates of tiny pre-solar interstellar dust grains and if these grains were destroyed differentially during the evaporation

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.

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.

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.)

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

Water-hydrogen isotope exchange process analysis

International Nuclear Information System (INIS)

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

2008-01-01

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

Laser isotope separation - a new class of chemical process

International Nuclear Information System (INIS)

Woodall, K.B.; Mannik, L.; O'Neill, J.A.; Mader, D.L.; Nickerson, S.B.; Robins, J.R.; Bartoszek, F.E.; Gratton, D.

1983-01-01

Lasers may soon find several applications in chemical processing. The applications that have attracted the most research funding to date involve isotope separation for the nuclear industry. These isotopes have an unusually high value (≥$1000/kg) compared to bulk chemicals (∼$1/kg) and are generally required in very large quantities. In a laser isotope separation process, light is used to convert a separation that is very difficult or even impossible by conventional chemical engineering techniques to one that is readily handled by conventional separation technology. For some isotopes this can result in substantial capital and energy savings. A uranium enrichment process developed at the Lawrence Livermore National Laboratory is the closest to commercialization of the large scale laser isotope separation processes. Of particular interest to the Canadian nuclear industry are the laser separation of deuterium, tritium, zirconium-90 and carbon-14. In this paper, the basic principles behind laser isotope separation are reviewed and brief dscriptions of the more developed processes are given

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.

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

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

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

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...

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)

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

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

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.

An unusual encapsulated collection of urine (urinoma) in an infant with vesicoureteral reflux

International Nuclear Information System (INIS)

Passas, V.; Brountzos, E.; Grilias, D.; Vasilakos, P.

1987-01-01

We describe an unusual case of encapsulated collection of urine (urinoma) in a 7-month-old female infant. The clinical diagnosis was urinary tract infection. The retrograde cysto-urethrogram revealed grade III vesicoureteral reflux, which we believe was the cause of the urinoma. The investigation was completed with isotope and ultrasound studies. High pressure reflux was the cause of the urine extravasation in the perirenal space. (orig.)

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.)

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.

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

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.

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

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...

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

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

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

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)

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

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.

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)

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

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

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)

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).

Contribution to optimisation of Environmental Isotopes tracing in Hydrogeology. Case study of Madagascar

International Nuclear Information System (INIS)

RAJAOBELISON, J.

2003-01-01

The aim of this work is to suggest some improvements on the theory of interpretation and on the methodological approach for the optimum use of environmental isotopes tracing applied to hydrogeological investigation. A review of the theory of environmental isotopes used in hydrogeology has been made. The main constraints have been highlighted and led to some comments and proposals of improvement, in particular with regard to the continental effect on stable isotopes, to the seasonal variation of groundwater 1 4C content, and to the appropriate model for fractured crystalline aquifers. A literature survey on ten specific scientific papers, dealing with isotopic hydrology in miscellaneous types of aquifers and catchments, allowed to draw a synthesis of the hydrogeological, geochemical and isotopic constraints. A proposal of optimum methodological approach, taking into account the above mentioned constraints, have been inferred. The results of an on-going hydrogeological investigation carried out in the Southern crystalline basement and coastal sedimentary aquifers of Madagascar highlights an unusual methodological approach based on the lack of initial basic hydrogeological data. Besides, it shows to what extent the experience of the above mentioned research works can apply in the specific case of the complex aquifers of Madagascar. The lessons gained from this study contribute to enrich the synthesis of environmental isotopes constraints in hydrogeology and lead to a more realistic methodological approach proposal wich is likely to better make profitable the isotope hydrology technology

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

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.

Partitioning of evapotranspiration using a stable isotope technique in an arid and high temperature agricultural production system

KAUST Repository

Lu, Xuefei

2016-08-22

Agricultural production in the hot and arid low desert systems of southern California relies heavily on irrigation. A better understanding of how much and to what extent irrigated water is transpired by crops relative to being lost through evaporation would improve the management of increasingly limited water resources. In this study, we examined the partitioning of evapotranspiration (ET) over a field of forage sorghum (Sorghum bicolor), which was under evaluation as a potential biofuel feedstock, based on isotope measurements of three irrigation cycles at the vegetative stage. This study employed customized transparent chambers coupled with a laser-based isotope analyzer to continuously measure near-surface variations in the stable isotopic composition of evaporation (E, δ), transpiration (T, δ) and ET (δ) to partition the total water flux. Due to the extreme heat and aridity, δ and δ were very similar, which makes this system highly unusual. Contrary to an expectation that the isotopic signatures of T, E, and ET would become increasingly enriched as soils became drier, our results showed an interesting pattern that δ, δ, and δ increased initially as soil water was depleted following irrigation, but decreased with further soil drying in mid to late irrigation cycle. These changes are likely caused by root water transport from deeper to shallower soil layers. Results indicate that about 46% of the irrigated water delivered to the crop was used as transpiration, with 54% lost as direct evaporation. This implies that 28 − 39% of the total source water was used by the crop, considering the typical 60 − 85% efficiency of flood irrigation. The stable isotope technique provided an effective means of determining surface partitioning of irrigation water in this unusually harsh production environment. The results suggest the potential to further minimize unproductive water losses in these production systems.

Helium isotopes in rocks, waters and gases of the earth's crust

International Nuclear Information System (INIS)

Tolstikhin, L.H.

1984-01-01

In this chapter the distribution of helium isotopes in various samples (rocks, minerals, terrestrial fluids, gases etc.) is interpreted from the genetic point of view, namely what sources and processes provide the abundance of helium isotopes observed in a sample. The mixing of mantle, juvenile helium with pure radiogenic helium is the main process responsible for the helium isotope composition in any sample of the earth's crust, the share of each component (reflected in the 3 He/ 4 He ratio) depending on the history of the tectono-magnetic activity in the given region. A specific chemical composition of a rock or mineral, peculiarities of losses or trapping and a peculiar kind of distribution of radioactive elements can lead to unusual isotopic ratios of 3 He/ 4 He in radiogenic helium. Lastly, technogenic radioactive isotopes are widespread in nature; one of them, tritium ( 3 H), yields 3 He excess in terrestrial waters. (orig.)

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

Vital effects vary between species and affect various isotopic systems in unequal proportion. The magnitude of the response of different isotopic systems might thus be key in understanding biologically-mediated disequilibrium, especially in groups that show a tendency to be "repeat offenders" with regards to vital effects. Here we present carbon, oxygen, and clumped isotope data from echinoderm calcite and nannofossil ooze, both of which exhibit strong vital effects in bulk isotopes. Our study is the first to investigate the clumped isotope (dis)equilibrium of echinoids. Results from two echinoids, three marine gastropods and a bivalve mollusk from modern beach deposits of Bali, Indonesia, highlight a significant offset in clumped isotopes of a regular echinoid test from expected values, interpreted as evidence of a similar "vital effect" as observed in surface corals. This is in contrast to the test of an irregular "sand dollar" echinoid, with clumped isotope values within error of expected sea surface temperature. Furthermore, data on the inter-skeletal variability in the clumped isotopic composition of two regular echinoid species shows that the spines of the echinoids are in equilibrium with seawater with respect to clumped isotopes, but the test is not. For the nannofossil material, no clumped isotope vital effects are observed, consistent with previously published studies but at odds with strong vital effects in carbon and oxygen isotopes, often correlated with cell-size. In addition, we reveal that the <63 micron fraction of deep-sea ooze could constitute useful material for clumped isotope studies. An intriguing result of our study is that vital effects are mostly absent in clumped isotopes, even in phylums known for important isotopic effects. It remains to be explained why some parts of the echinoids show clear vital effects, notably enrichment in clumped isotopes of urchin tests. Mechanisms that could explain this include pH effects during calcification

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

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

Unusual motions due to nonlinear effects in a driven vibrating string

Science.gov (United States)

Hanson, Roger J.

2005-09-01

Usual nonlinear effects observed in a sinusoidally driven vibrating string include generation of motion perpendicular to the driving plane, sudden jumps of amplitude and associated hysteresis, and generation of higher harmonics. In addition, under some conditions, there can be a rich variety of unusual, very complex motions of a point on the string, the pattern of which, together with associated harmonic (and sometimes subharmonic) content, can change dramatically with a slight change in driving frequency or sometimes with constant driving frequency and force. Intrinsic string asymmetries can also have a profound effect on the behavior. In a brass harpsichord string (wire) such asymmetries can cause a small splitting of each natural frequency of free vibration into two closely spaced frequencies (relative separation ~0.2% to 2%, strongly dependent on tension.) The two frequency components are associated, respectively, with the transverse motion along two orthogonal characteristic wire axes. Emphasis will be on display of optically detected unusual motion patterns of a point on the string, including an example of a pattern period of 10 s when driving at 50 Hz. See R. J. Hanson et al., J. Acoust. Soc. Am. 117, 400-412 (2005) for a more complete treatment.

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

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)

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

Study of asymmetric fission yield behavior from neutron-deficient Hg isotope

International Nuclear Information System (INIS)

Perkasa, Y. S.; Waris, A.; Kurniadi, R.; Su'ud, Z.

2014-01-01

A study of asymmetric fission yield behavior from a neutron-deficient Hg isotope has been conducted. The fission yield calculation of the neutron-deficient Hg isotope using Brownian Metropolis shape had showed unusual result at decreasing energy. In this paper, this interesting feature will be validated by using nine degree of scission shapes parameterization from Brosa model that had been implemented in TALYS nuclear reaction code. This validation is intended to show agreement between both model and the experiment result. The expected result from these models considered to be different due to dynamical properties that implemented in both models

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).

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

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.

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...

The effect of exposure to employees from mining and milling operations in a uranium mine on lead isotopes--a pilot study.

Science.gov (United States)

Gulson, Brian L; Mizon, Karen J; Dickson, Bruce L; Korsch, Michael J

2005-03-01

Potential exposure during mining and milling of uranium ore has resulted in the industry being highly regulated. Exposure can arise from inhalation of the daughter product radioactive gas radon (222Rn), inhalation of radioactive dust particles from mining and milling, direct irradiation from outside the body, and ingestion of radionuclides (e.g. uranium or radium) in food or water. Making use of the highly unusual lead isotopic signature for uranium ores (high 206Pb/204Pb from the high uranium content, low 208Pb/204Pb from the low Th/U ratio), we undertook a pilot study of nine male mine employees and three controls from the Ranger uranium mine in the Northern Territory Australia to determine if it was feasible to use lead isotopes in blood to identify exposure to uranium-derived materials. The lead isotopic data for the mine employees and controls plot in two distinct fields which are consistent with predicted isotopic patterns. Assuming retention of 10% of the ingested lead, then the increases seen in 206Pb represent intakes of between 0.9 and 15 mg, integrated over the years of exposure. The small amount of lead does not affect blood lead concentrations, but appears to be sufficient to be detectable with sensitive isotopic methods. Further studies, including those on urine, should be undertaken to confirm the veracity of the lead isotope method in monitoring exposure of uranium industry employees.

The effect of exposure to employees from mining and milling operations in a uranium mine on lead isotopes. A pilot study

International Nuclear Information System (INIS)

Gulson, Brian L.; Mizon, Karen J.; Dickson, Bruce L.; Korsch, Michael J.

2005-01-01

Potential exposure during mining and milling of uranium ore has resulted in the industry being highly regulated. Exposure can arise from inhalation of the daughter product radioactive gas radon ( 222 Rn), inhalation of radioactive dust particles from mining and milling, direct irradiation from outside the body, and ingestion of radionuclides (e.g. uranium or radium) in food or water. Making use of the highly unusual lead isotopic signature for uranium ores (high 206 Pb/ 204 Pb from the high uranium content, low 208 Pb/ 204 Pb from the low Th/U ratio), we undertook a pilot study of nine male mine employees and three controls from the Ranger uranium mine in the Northern Territory Australia to determine if it was feasible to use lead isotopes in blood to identify exposure to uranium-derived materials. The lead isotopic data for the mine employees and controls plot in two distinct fields which are consistent with predicted isotopic patterns. Assuming retention of 10% of the ingested lead, then the increases seen in 206 Pb represent intakes of between 0.9 and 15 mg, integrated over the years of exposure. The small amount of lead does not affect blood lead concentrations, but appears to be sufficient to be detectable with sensitive isotopic methods. Further studies, including those on urine, should be undertaken to confirm the veracity of the lead isotope method in monitoring exposure of uranium industry employees

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.)

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

Charge state distribution studies of pure and oxygen mixed krypton ECR plasma - signature of isotope anomaly and gas mixing effect.

Science.gov (United States)

Kumar, Pravin; Mal, Kedar; Rodrigues, G

2016-11-01

We report the charge state distributions of the pure, 25% and 50% oxygen mixed krypton plasma to shed more light on the understanding of the gas mixing and the isotope anomaly [A. G. Drentje, Rev. Sci. Instrum. 63 (1992) 2875 and Y Kawai, D Meyer, A Nadzeyka, U Wolters and K Wiesemann, Plasma Sources Sci. Technol. 10 (2001) 451] in the electron cyclotron resonance (ECR) plasmas. The krypton plasma was produced using a 10 GHz all-permanent-magnet ECR ion source. The intensities of the highly abundant four isotopes, viz. 82 Kr (~11.58%), 83 Kr (~11.49%), 84 Kr (~57%) and 86 Kr (17.3%) up to ~ +14 charge state have been measured by extracting the ions from the plasma and analysing them in the mass and the energy using a large acceptance analyzer-cum-switching dipole magnet. The influence of the oxygen gas mixing on the isotopic krypton ion intensities is clearly evidenced beyond +9 charge state. With and without oxygen mixing, the charge state distribution of the krypton ECR plasma shows the isotope anomaly with unusual trends. The anomaly in the intensities of the isotopes having quite closer natural abundance, viz. 82 Kr, 86 Kr and 83 Kr, 86 Kr is prominent, whereas the intensity ratio of 86 Kr to 84 Kr shows a weak signature of it. The isotope anomaly tends to disappear with increasing oxygen mixing in the plasma. The observed trends in the intensities of the krypton isotopes do not follow the prediction of linear Landau wave damping in the plasma. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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)

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.

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

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.

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...

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).

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

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

Isotope anomalies in oxygen isotope exchange equilibrium systems

International Nuclear Information System (INIS)

Kotaka, M.

1997-01-01

The purpose of the present work is to elucidate the isotope anomalies in oxygen isotope exchange equilibrium systems, according to the calculations of the equilibrium constants for oxygen isotopic exchange reactions, and the calculations of the oxygen isotope separation factors between two phases. The equilibrium constants (K65, K67, K68 and K69) of 16 O- 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O exchange reactions between diatomic oxides were calculated in a wide temperature range on the basis of quantum statistical mechanics. Many equilibrium constants showed the anomalous mass effects, and then had the crossover temperatures and the mass independent fractionation (MIF) temperatures which held K67 = K65, K67 = K68, or K67 = K69, etc. For example, the equilibrium constants for the reactions between OH and the other diatomic oxides (MO) showed the anomalous mass effects, when M was Li, Na, Mg, K, Fe, Al, Ge, Zr, Pt, etc. The 16 O 15 O, 16 O 17 O, 16 O- 18 O, and 16 O- 19 O oxygen isotope separation factors (S65, S67, S68 and S69) between two phases were calculated, when OH and CO were in the first phase, and SiO was in the second phase. Although the oxygen isotopic exchange equilibria in the two phases had no MIF and crossover temperatures, the separation factors showed the anomalous mass effects and had the temperatures. According to what is called the normal mass effects for the equilibrium constant of isotopic exchange reaction, the value of InK68/InK67 is 1.885. Therefore, the value of InS68/InS67 should be 1.885 too. The value calculated, however, widely changed. It can be concluded from the results obtained in the present work that some oxygen isotopic exchange equilibria cause the anomalous mass effects, the anomalous oxygen isotope separation factors, and then isotope anomalies

Stable Isotope Systematics of Martian Perchlorate

Science.gov (United States)

Martin, P.; Farley, K. A.; Archer, D., Jr.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairen, A.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2015-12-01

Chlorine isotopic compositions in HCl released during evolved gas analysis (EGA) runs have been detected by the Sample Analysis at Mars (SAM) instrument on the Curiosity rover ranging from approximately -9‰ to -50‰ δ37Cl, with two spatially and isotopically separated groups of samples averaging -15‰ and -45‰. These extremely low values are the first such detection of any known natural material; common terrestrial values very rarely exceed ±5‰, and the most extreme isotopic signature yet detected elsewhere in the solar system are values of around +24‰ on the Moon. The only other known location in the solar system with large negative chlorine isotopes is the Atacama Desert, where perchlorate with -14‰ δ37Cl has been detected. The Atacama perchlorate has unusual Δ17O signatures associated with it, indicating a formation mechanism involving O3, which suggests an atmospheric origin of the perchlorate and associated large isotopic anomalies. Identification of non-zero positive Δ17O signatures in the O2 released during EGA runs would allow definitive evidence for a similar process having occurred on Mars. Perchlorate is thought to be the most likely source of HCl in EGA runs due to the simultaneous onset of O2 release. If perchlorate is indeed the HCl source, atmospheric chemistry could be responsible for the observed isotopic anomalies, with variable extents of perchlorate production producing the isotopic variability. However, chloride salts have also been observed to release HCl upon heating; if the timing of O2 release is merely coincidental, observed HCl could be coming from chlorides. At thermodynamic equilibrium, the fractionation factor of perchlorate reduction is 0.93, meaning that differing amounts of post-deposition reduction of isotopically normal perchlorate to chloride could account for the highly variable Cl isotopes. Additionally, post-deposition reduction could account for the difference between the two Cl isotopic groups if perchlorate

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.)

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

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.

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.

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.).

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.)

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.

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.

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?

Magnesium isotope evidence for single stage formation of CB chondrules by colliding planetesimals

DEFF Research Database (Denmark)

Olsen, Mia Bjørg Stolberg; Schiller, Martin; Krot, Alexander N.

2013-01-01

Chondrules are igneous spherical objects preserved in chondritic meteorites and believed to have formed during transient heating events in the solar protoplanetary disk. Chondrules present in the metal-rich CB chondrites show unusual chemical and petrologic features not observed in other chondrit...... planetesimals. The inferred μMg* value of -3.87 ± 0.93 ppm for the CB parent body is significantly lower than the bulk solar system value of 4.5 ± 1.1 ppm inferred from CI chondrites, suggesting that CB chondrites accreted material comprising an early formed Al-free component.......Chondrules are igneous spherical objects preserved in chondritic meteorites and believed to have formed during transient heating events in the solar protoplanetary disk. Chondrules present in the metal-rich CB chondrites show unusual chemical and petrologic features not observed in other chondrite......, indicating substantial suppression of isotopic fractionation during evaporative loss of Mg, possibly due to evaporation at high Mg partial pressure. Thus, the Mg-isotope data of skeletal chondrules from HH237 are consistent with their origin as melts produced in the impact-generated plume of colliding...

Effects of soil strength on the relation of water-use efficiency and growth to carbon isotope discrimination in wheat seedlings

International Nuclear Information System (INIS)

Masle, J.; Farquhar, G.D.

1988-01-01

The ratio of carbon accumulation to transpiration, W, of wheat (Triticum aestivum L.) seedlings increased with increasing soil strength, measured as soil penetrometer resistance, and this was already apparent at the two leaf stage. The ratio was negatively correlated with carbon isotope discrimination, in accord with theory. This means that decrease in intercellular partial pressure of CO 2 accounted for an important part of the increase in W with increasing soil strength. Despite a lower CO 2 concentration in the leaves at high soil strength, assimilation rate per unit leaf area was enhanced. Greater ribulose 1,5-bisphosphate carboxylase activity confirmed that photosynthetic capacity was actually increased. This pattern of opposite variation of assimilation rate and of stomatal conductance is unusual. The ratio of plant carbon mass to leaf area increased markedly with increasing soil strength, mainly because of a greater investment of carbon into roots than into shoots. A strong negative correlation was found between this ratio and carbon isotope discrimination. For a given increase in discrimination, decrease in carbon mass per leaf area was proportionally larger than decrease in assimilation rate, so that relative growth rate was positively correlated to carbon isotope discrimination

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)

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

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)

Stable water isotope variation in a Central Andean watershed dominated by glacier and snowmelt

Directory of Open Access Journals (Sweden)

N. Ohlanders

2013-03-01

Full Text Available Central Chile is an economically important region for which water supply is dependent on snow- and ice melt. Nevertheless, the relative contribution of water supplied by each of those two sources remains largely unknown. This study represents the first attempt to estimate the region's water balance using stable isotopes of water in streamflow and its sources. Isotopic ratios of both H and O were monitored during one year in a high-altitude basin with a moderate glacier cover (11.5%. We found that the steep altitude gradient of the studied catchment caused a corresponding gradient in snowpack isotopic composition and that this spatial variation had a profound effect on the temporal evolution of streamflow isotopic composition during snowmelt. Glacier melt and snowmelt contributions to streamflow in the studied basin were determined using a quantitative analysis of the isotopic composition of streamflow and its sources, resulting in a glacier melt contribution of 50–90% for the unusually dry melt year of 2011/2012. This suggests that in (La Niña years with little precipitation, glacier melt is an important water source for central Chile. Predicted decreases in glacier melt due to global warming may therefore have a negative long-term impact on water availability in the Central Andes. The pronounced seasonal pattern in streamflow isotope composition and its close relation to the variability in snow cover and discharge presents a potentially powerful tool to relate discharge variability in mountainous, melt-dominated catchments with related factors such as contributions of sources to streamflow and snowmelt transit times.

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

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)

Calculation of isotope selective excitation of uranium isotopes using spectral simulation method

International Nuclear Information System (INIS)

Al-Hassanieh, O.

2009-06-01

Isotope ratio enhancement factor and isotope selectivity of 235 U in five excitation schemes (I: 0→10069 cm - 1 →IP, II: 0 →10081 cm - 1 →IP, III: 0 →25349 cm - 1→ IP, IV: 0→28650 cm - 1 →IP, V: 0→16900 cm - 1 →34659 cm - 1 →IP), were computed by a spectral simulation approach. The effect of laser bandwidth and Doppler width on the isotope ratio enhancement factor and isotope selectivity of 235 U has been studied. The photoionization scheme V gives the highest isotope ratio enhancement factor. The main factors which effect the separation possibility are the isotope shift and the relative intensity of the transitions between hyperfine levels. The isotope ratio enhancement factor decreases exponentially by increasing the Doppler width and the laser bandwidth, where the effect of Doppler width is much greater than the effect of the laser bandwidth. (author)

Temperature-dependent transitions between normal and inverse isotope effects pertaining to the interaction of H-H and C-H bonds with transition metal centers.

Science.gov (United States)

Parkin, Gerard

2009-02-17

Deuterium kinetic isotope effects (KIEs) serve as versatile tools to infer details about reaction mechanisms and the nature of transition states, while equilibrium isotope effects (EIEs) associated with the site preferences of hydrogen and deuterium enable researchers to study aspects of molecular structure. Researchers typically interpret primary deuterium isotope effects based on two simple guidelines: (i) the KIE for an elementary reaction is normal (k(H)/k(D) > 1) and (ii) the EIE is dictated by deuterium preferring to be located in the site corresponding to the highest frequency oscillator. In this Account, we evaluate the applicability of these rules to the interactions of H-H and C-H bonds with a transition metal center. Significantly, experimental and computational studies question the predictability of primary EIEs in these systems based on the notion that deuterium prefers to occupy the highest frequency oscillator. In particular, the EIEs for (i) formation of sigma-complexes by coordination of H-H and C-H bonds and (ii) oxidative addition of dihydrogen exhibit unusual temperature dependencies, such that the same system may demonstrate both normal (i.e., K(H)/K(D) > 1) and inverse (i.e., K(H)/K(D) ZPE (where SYM is the symmetry factor, MMI is the mass-moment of inertia term, EXC is the excitation term, and ZPE is the zero-point energy term), and the distinctive temperature profile results from the inverse ZPE (enthalpy) and normal [SYM x MMI x EXC] (entropy) components opposing each other and having different temperature dependencies. At low temperatures, the ZPE component dominates and the EIE is inverse, while at high temperatures, the [SYM x MMI x EXC] component dominates and the EIE is normal. The inverse nature of the ZPE term is a consequence of the rotational and translational degrees of freedom of RH (R = H, CH(3)) becoming low-energy isotopically sensitive vibrations in the product, while the normal nature of the [SYM x MMI x EXC] component

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

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.)

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.

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.)

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

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

Diet and diversity at later medieval Fishergate: the isotopic evidence.

Science.gov (United States)

Müldner, Gundula; Richards, Michael P

2007-10-01

We present the results of stable carbon and nitrogen isotope analysis of bone collagen for 155 individuals buried at the Later Medieval (13th to early 16th century AD) Gilbertine priory of St. Andrew, Fishergate in the city of York (UK). The data show significant variation in the consumption of marine foods between males and females as well as between individuals buried in different areas of the priory. Specifically, individuals from the crossing of the church and the cloister garth had consumed significantly less marine protein than those from other locations. Isotope data for four individuals diagnosed with diffuse idiopathic skeletal hyperostosis (DISH) are consistent with a diet rich in animal protein. We also observe that isotopic signals of individuals with perimortem sharp force trauma are unusual in the context of the Fishergate dataset. We discuss possible explanations for these patterns and suggest that there may have been a specialist hospital or a local tradition of burying victims of violent conflict at the priory. The results demonstrate how the integration of archaeological, osteological, and isotopic data can provide novel information about Medieval burial and society. (c) 2007 Wiley-Liss, Inc.

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.

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.

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.

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.

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.)

CAN GALACTIC CHEMICAL EVOLUTION EXPLAIN THE OXYGEN ISOTOPIC VARIATIONS IN THE SOLAR SYSTEM?

International Nuclear Information System (INIS)

Lugaro, Maria; Liffman, Kurt; Ireland, Trevor R.; Maddison, Sarah T.

2012-01-01

A number of objects in primitive meteorites have oxygen isotopic compositions that place them on a distinct, mass-independent fractionation line with a slope of one on a three-isotope plot. The most popular model for describing how this fractionation arose assumes that CO self-shielding produced 16 O-rich CO and 16 O-poor H 2 O, where the H 2 O subsequently combined with interstellar dust to form relatively 16 O-poor solids within the solar nebula. Another model for creating the different reservoirs of 16 O-rich gas and 16 O-poor solids suggests that these reservoirs were produced by Galactic chemical evolution (GCE) if the solar system dust component was somewhat younger than the gas component and both components were lying on the line of slope one in the O three-isotope plot. We argue that GCE is not the cause of mass-independent fractionation of the oxygen isotopes in the solar system. The GCE scenario is in contradiction with observations of the 18 O/ 17 O ratios in nearby molecular clouds and young stellar objects. It is very unlikely for GCE to produce a line of slope one when considering the effect of incomplete mixing of stellar ejecta in the interstellar medium. Furthermore, the assumption that the solar system dust was younger than the gas requires unusual timescales or the existence of an important stardust component that is not theoretically expected to occur nor has been identified to date.

ISOTOPE METHODS IN HOMOGENEOUS CATALYSIS.

Energy Technology Data Exchange (ETDEWEB)

BULLOCK,R.M.; BENDER,B.R.

2000-12-01

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

An experimental study of odd mass promethium isotopes using proton stripping and pickup reactions

International Nuclear Information System (INIS)

Straume, O.

1979-11-01

Odd Pm isotopes have been studied by one proton pick-up and stripping reactions. Spin assignment and spectroscopic factors have been obtained for a number of energy levels. In the stripping reactions, the relative cross-sections have been measured with an unusually high precision by the use of a target of natural neodymium. The spectroscopic strengths have been extracted using standard distorted wave methods. The nuclear structures of these promethium isotopes fall into three categories. The spherical approach seems valid for 143 Pm and 145 Pm and the deformed regime covers 151 Pm and 153 Pm, while 147 Pm and 149 Pm remain as transitional nuclei. (Auth.)

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.

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

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.

Radiation safety aspects in application of isotopes for industrial radiography in Bangladesh

Energy Technology Data Exchange (ETDEWEB)

Bakht, D. [Titas Gas Transmission and Distribution Company, Dhaka (Bangladesh)

1997-10-01

Industrial Radiography arose out of the widespread applications of X-rays pioneered by Roentgen about 100 years back. It is routinely used in studying the integrity of structural materials and like most countries in the world, its use in Bangladesh is increasing at a faster rate. This is because Bangladesh is a developing country of 3rd world and in the backdrop of agrarian poverty ridden economy, its population may exceed 125 millions by 2000 AD, leaving some 12 millions people unemployed. To support them, therefore, immense activities are activated in different sectors. Accordingly, increasing importance on NDT is given and in most cases particular application of Gamma radiography is preferred using Iridium Isotope Ir-192. Consequently the points of implications of isotopes are in Open Field and Inservice Inspection Radiography, Handling of Radiation Emergencies, Safe Transport of Radioactive Materials and Hazardous Effects and Risk of Ionizing Radiation, etc. Accordingly over exposure of Ir-192 Radionuclides, Accidents and Unusual Occurrences: Case Studies, Training Courses on Safety and Regulation of Sealed Sources, Licenses for Radiography Operation including Safe Disposal of Isotopes are the salient issues to be viewed in appropriate perspectives. The role played by Bangladesh Atomic Energy Commission and Bangladesh Society for NDT in collaboration with other members of the international committee for NDT are furthering the safe industrialization process

Radiation safety aspects in application of isotopes for industrial radiography in Bangladesh

International Nuclear Information System (INIS)

Bakht, D.

1997-01-01

Industrial Radiography arose out of the widespread applications of X-rays pioneered by Roentgen about 100 years back. It is routinely used in studying the integrity of structural materials and like most countries in the world, its use in Bangladesh is increasing at a faster rate. This is because Bangladesh is a developing country of 3rd world and in the backdrop of agrarian poverty ridden economy, its population may exceed 125 millions by 2000 AD, leaving some 12 millions people unemployed. To support them, therefore, immense activities are activated in different sectors. Accordingly, increasing importance on NDT is given and in most cases particular application of Gamma radiography is preferred using Iridium Isotope Ir-192. Consequently the points of implications of isotopes are in Open Field and Inservice Inspection Radiography, Handling of Radiation Emergencies, Safe Transport of Radioactive Materials and Hazardous Effects and Risk of Ionizing Radiation, etc. Accordingly over exposure of Ir-192 Radionuclides, Accidents and Unusual Occurrences: Case Studies, Training Courses on Safety and Regulation of Sealed Sources, Licenses for Radiography Operation including Safe Disposal of Isotopes are the salient issues to be viewed in appropriate perspectives. The role played by Bangladesh Atomic Energy Commission and Bangladesh Society for NDT in collaboration with other members of the international committee for NDT are furthering the safe industrialization process

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

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)

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.

Variation in the isotopic content of precipitation with altitude

International Nuclear Information System (INIS)

Stowhas, L.; Silva, C.; Moser, H.; Stichler, W.

1975-03-01

Monthly precipitation and single storms have been collected during three years at 12 stations along a W-E profile in Chile, going from Juan Fernandez Islands to Valparaiso, Santiago and Infiernillo in the Andes, and analysed for their deuterium content. The deltaD values are correlated with the altitude of the station, the mean temperature - which also largely depends on the altitude - and the distance from the sea. The correlation parameters show however important variations from year to year and even more from month to month. For instance, in the stretch Santiago (520 m a.s.l.) - La Parva (2680 m) the mean isotopic gradient with altitude were: -1.84 deltaD per mil/100 m in 1970, -1.09 in 1971 and -2.0 in 1972. The low value observed in 1971 could be a consequence of the peculiar weather characteristics of this unusually dry year. In the stretch from the coast to Santiago the trend of the isotopic composition of precipitation is more complicated, because the so-called continental effect is superimposed to the altitude effect. The deuterium content variations have been also determined in snowpack profiles at La Parva station. The results show that snow melting occurs slowly at the bottom during the whole winter, at the expenses of the heat stored during summer in the soil. The melting of the surface snow layers only starts at the end of the winter and then proceeds very fast

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)

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

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

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

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.

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

Unusual manifestations of secondary urothelial carcinoma

Directory of Open Access Journals (Sweden)

Chaohui Lisa Zhao

2016-03-01

Full Text Available High-grade papillary urothelial carcinoma regularly invades the bladder wall, adjacent prostate, seminal vesicles, ureters, vagina, rectum, retroperitoneum, and regional lymph nodes. In advanced stages, it may disseminate to the liver, lungs, and bone marrow. On rare occasions, unusual metastatic foci like skin have been reported. The incidence of urothelial carcinoma has increased with associated rise in variants of urothelial carcinoma and unusual metastatic foci. It is imperative that urologists and pathologists are aware of the unusual variants and unusual metastatic locations to expedite the diagnostic process. Hereby we report an unusual case of secondary involvement of spinal nerve by conventional urothelial carcinoma. Also a second case of rhabdoid variant of urothelial carcinoma showing synchronous involvement of bladder and subcutaneous tissue of upper extremity is presented.

Unusual headache syndromes.

Science.gov (United States)

Queiroz, Luiz P

2013-01-01

Some headache syndromes have few cases reported in the literature. Their clinical characteristics, pathogenesis, and treatment may have not been completely defined. They may not actually be uncommon but rather under-recognized and/or underreported. A literature review of unusual headache syndromes, searching PubMed and ISI Web of Knowledge, was performed. After deciding which disorders to study, relevant publications in scientific journals, including original articles, reviews, meeting abstracts, and letters or correspondences to the editors were searched. This paper reviewed the clinical characteristics, the pathogenesis, the diagnosis, and the treatment of five interesting and unusual headache syndromes: exploding head syndrome, red ear syndrome, neck-tongue syndrome, nummular headache, and cardiac cephalgia. Recognizing some unusual headaches, either primary or secondary, may be a challenge for many non-headache specialist physicians. It is important to study them because the correct diagnosis may result in specific treatments that may improve the quality of life of these patients, and this can even be life saving. © 2013 American Headache Society.

Methane clumped isotopes: Progress and potential for a new isotopic tracer

Energy Technology Data Exchange (ETDEWEB)

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.; Sessions, Alex L.; Lawson, Michael; Shuai, Yanhua; Bishop, Andrew; Podlaha, Olaf G.; Ferreira, Alexandre A.; Santos Neto, Eugenio V.; Niemann, Martin; Steen, Arne S.; Huang, Ling; Chimiak, Laura; Valentine, David L.; Fiebig, Jens; Luhmann, Andrew J.; Seyfried, William E.; Etiope, Giuseppe; Schoell, Martin; Inskeep, William P.; Moran, James J.; Kitchen, Nami

2017-11-01

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.

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)

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.

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)

Subcoulomb fusion of 16O in odd Sm isotopes

International Nuclear Information System (INIS)

Pacheco, A.J.

1989-01-01

Cross sections for the formation of evaporation residues were measured for the reaction of 16 O with the odd 147 Sm and 149 Sm nuclei at near barrier energies. The results are well described by statistical model calculations. Fusion cross sections as a function of energy do not show any unusual behaviour that could be attributed to the presence of unpaired nucleons. An analysis based on a one-dimensional penetration model that includes the effect of permanent quadrupolar deformations shows that the extracted values of the parameter β 2 follow the systematics established by the rest of the even samarium isotopes. The dependence of β 2 on the mass of the target nucleus indicates that the influence exerted by collective aspects upon the subbarrier fusion process increases rapidly as a function of the number of neutrons added to the spherical semimagic 144 Sm nucleus. (Author) [es

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

The isotopic contamination in electromagnetic isotope separators; La contagion isotopique dans les separateurs electromagnetiques d'isotopes

Energy Technology Data Exchange (ETDEWEB)

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

1959-07-01

In the early years of isotope separation, and in particular electromagnetic isotope separation, needs for rapid results have conducted to empiric research. This paper describes fundamental research on the electromagnetic isotope separation to a better understanding of isotope separators as well as improving the performances. Focus has been made on the study of the principle of isotope contamination and the remedial action on the separator to improve the isotope separation ratio. In a first part, the author come back to the functioning of an electromagnetic separator and generalities on isotope contamination. Secondly, it describes the two stages separation method with two dispersive apparatus, an electromagnetic separation stage followed by an electrostatic separation stage, both separated by a diaphragm. The specifications of the electrostatic stage are given and its different settings and their consequences on isotope separation are investigated. In a third part, mechanisms and contamination factors in the isotope separation are discussed: natural isotope contamination, contamination by rebounding on the collector, contamination because of a low resolution, contamination by chromatism and diffusion effect, breakdown of condenser voltage. Analysis of experimental results shows the diffusion as the most important contamination factor in electromagnetic isotope separation. As contamination factors are dependent on geometric parameters, sector angle, radius of curvature in the magnetic field and clearance height are discussed in a fourth part. The better understanding of the mechanism of the different contamination factors and the study of influential parameters as pressure and geometric parameters lead to define a global scheme of isotope contamination and determinate optima separator design and experimental parameters. Finally, the global scheme of isotope contamination and hypothesis on optima specifications and experimental parameters has been checked during a

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

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

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.

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

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.)

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.

Rheological Characterization of Unusual DWPF Slurry Samples

International Nuclear Information System (INIS)

Koopman, D. C.

2005-01-01

A study was undertaken to identify and clarify examples of unusual rheological behavior in Defense Waste Processing Facility (DWPF) simulant slurry samples. Identification was accomplished by reviewing sludge, Sludge Receipt and Adjustment Tank (SRAT) product, and Slurry Mix Evaporator (SME) product simulant rheological results from the prior year. Clarification of unusual rheological behavior was achieved by developing and implementing new measurement techniques. Development of these new methods is covered in a separate report, WSRC-TR-2004-00334. This report includes a review of recent literature on unusual rheological behavior, followed by a summary of the rheological measurement results obtained on a set of unusual simulant samples. Shifts in rheological behavior of slurries as the wt. % total solids changed have been observed in numerous systems. The main finding of the experimental work was that the various unusual DWPF simulant slurry samples exhibit some degree of time dependent behavior. When a given shear rate is applied to a sample, the apparent viscosity of the slurry changes with time rather than remaining constant. These unusual simulant samples are more rheologically complex than Newtonian liquids or more simple slurries, neither of which shows significant time dependence. The study concludes that the unusual rheological behavior that has been observed is being caused by time dependent rheological properties in the slurries being measured. Most of the changes are due to the effect of time under shear, but SB3 SME products were also changing properties while stored in sample bottles. The most likely source of this shear-related time dependence for sludge is in the simulant preparation. More than a single source of time dependence was inferred for the simulant SME product slurries based on the range of phenomena observed. Rheological property changes were observed on the time-scale of a single measurement (minutes) as well as on a time scale of hours

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.

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

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

Uses of stable isotopes

International Nuclear Information System (INIS)

Axente, Damian

1998-01-01

The most important fields of stable isotope use with examples are presented. These are: 1. Isotope dilution analysis: trace analysis, measurements of volumes and masses; 2. Stable isotopes as tracers: transport phenomena, environmental studies, agricultural research, authentication of products and objects, archaeometry, studies of reaction mechanisms, structure and function determination of complex biological entities, studies of metabolism, breath test for diagnostic; 3. Isotope equilibrium effects: measurement of equilibrium effects, investigation of equilibrium conditions, mechanism of drug action, study of natural processes, water cycle, temperature measurements; 4. Stable isotope for advanced nuclear reactors: uranium nitride with 15 N as nuclear fuel, 157 Gd for reactor control. In spite of some difficulties of stable isotope use, particularly related to the analytical techniques, which are slow and expensive, the number of papers reporting on this subject is steadily growing as well as the number of scientific meetings organized by International Isotope Section and IAEA, Gordon Conferences, and regional meeting in Germany, France, etc. Stable isotope application development on large scale is determined by improving their production technologies as well as those of labeled compound and the analytical techniques. (author)

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)

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

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.

48 CFR 32.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Unusual contract financing... CONTRACTING REQUIREMENTS CONTRACT FINANCING Non-Commercial Item Purchase Financing 32.114 Unusual contract financing. Any contract financing arrangement that deviates from this part is unusual contract financing...

The isotopic contamination in electromagnetic isotope separators; La contagion isotopique dans les separateurs electromagnetiques d'isotopes

Energy Technology Data Exchange (ETDEWEB)

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

1959-07-01

In the early years of isotope separation, and in particular electromagnetic isotope separation, needs for rapid results have conducted to empiric research. This paper describes fundamental research on the electromagnetic isotope separation to a better understanding of isotope separators as well as improving the performances. Focus has been made on the study of the principle of isotope contamination and the remedial action on the separator to improve the isotope separation ratio. In a first part, the author come back to the functioning of an electromagnetic separator and generalities on isotope contamination. Secondly, it describes the two stages separation method with two dispersive apparatus, an electromagnetic separation stage followed by an electrostatic separation stage, both separated by a diaphragm. The specifications of the electrostatic stage are given and its different settings and their consequences on isotope separation are investigated. In a third part, mechanisms and contamination factors in the isotope separation are discussed: natural isotope contamination, contamination by rebounding on the collector, contamination because of a low resolution, contamination by chromatism and diffusion effect, breakdown of condenser voltage. Analysis of experimental results shows the diffusion as the most important contamination factor in electromagnetic isotope separation. As contamination factors are dependent on geometric parameters, sector angle, radius of curvature in the magnetic field and clearance height are discussed in a fourth part. The better understanding of the mechanism of the different contamination factors and the study of influential parameters as pressure and geometric parameters lead to define a global scheme of isotope contamination and determinate optima separator design and experimental parameters. Finally, the global scheme of isotope contamination and hypothesis on optima specifications and experimental parameters has been checked during a

Distribution of oxygen isotopes in the water masses of Drake Passage and the South Atlantic

Science.gov (United States)

Meredith, Michael P.; Grose, Katie E.; McDonagh, Elaine L.; Heywood, Karen J.; Frew, Russell D.; Dennis, Paul F.

1999-09-01

Measurements of the ratio of stable isotopes of oxygen (18O and 16O) from samples collected on World Ocean Circulation Experiment sections SR1b (eastern Drake Passage) and A11 (Punta Arenas to Cape Town) are used, together with hydrographic data, to deduce information about the formation and variability of South Atlantic and Southern Ocean water masses. The Drake Passage surface waters south of the Polar Front (PF) are isotopically light (δ18O around -0.4‰) owing to the influence of meteoric waters. The salinity and δ18O of the A11 surface waters yield an apparent freshwater end-member which is much isotopically lighter than the local precipitation, thus advection of these waters from farther south dominates over local effects in determining the surface water properties. The Drake Passage section shows unusual proximity of the two main fronts of the Antarctic Circumpolar Current (the PF and Subantarctic Front (SAF)), and we observe cold, fresh, and isotopically light water derived from the temperature-minimum Winter Water at the SAF. This water is of the correct density to freshen the intermediate water north of the SAF and thus play a role in the formation of the comparatively fresh Antarctic Intermediate Water (AAIW) of the South Atlantic. This confirms the role of Antarctic water in forming the South Atlantic variety of AAIW. Across the A11 section the oxygen isotope and salinity data at the AAIW core show very similar traces, with waters in the Malvinas Current loop showing lowest values of both. At the eastern boundary of the South Atlantic, the input of Red Sea Water from east of South Africa is observed via the presence of anomalously isotopically heavy AAIW. We deduce potentially significant temporal variability in the isotopic composition of Weddell Sea Deep Water (WSDW) by comparing the Drake Passage data to earlier data covering the outflow of the Weddell Sea. The A11 data show WSDW consistent with such variability, indicating that its effects could

Isotope-equipped measuring instruments

International Nuclear Information System (INIS)

Miyagawa, Kazuo; Amano, Hiroshi

1980-01-01

In the steel industry, though the investment in isotope-equipped measuring instruments is small as compared with that in machinery, they play important role in the moisture measurement in sintering and blast furnaces, the thickness measurement in rolling process and others in automatic control systems. The economic aspect of the isotope-equipped measuring instruments is described on the basis of the practices in Kimitsu Works of Nippon Steel Corporation: distribution of such instruments, evaluation of economic effects, usefulness evaluation in view of raising the accuracy, and usefulness evaluation viewed from the failure of the isotope instruments. The evaluation of economic effects was made under the premise that the isotope-equipped measuring instruments are not employed. Then, the effects of raising the accuracy are evaluated for a γ-ray plate thickness gauge and a neutron moisture gauge for coke in a blast furnace. Finally, the usefulness was evaluated, assuming possible failure of the isotope-equipped measuring instruments. (J.P.N.)

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.

48 CFR 432.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false Unusual contract financing... CONTRACTING REQUIREMENTS CONTRACT FINANCING Non-Commercial Item Purchase Financing 432.114 Unusual contract financing. The HCA is authorized to approve unusual contract financing. The signed determination and finding...

48 CFR 1332.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 5 2010-10-01 2010-10-01 false Unusual contract financing... CONTRACTING REQUIREMENTS CONTRACT FINANCING Non-Commercial Item Purchase Financing 1332.114 Unusual contract financing. The designee authorized to approve unusual contract financing arrangements is set forth in CAM...

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.

Unusual motions of a vibrating string

Science.gov (United States)

Hanson, Roger J.

2003-10-01

The actual motions of a sinusoidally driven vibrating string can be very complex due to nonlinear effects resulting from varying tension and longitudinal motion not included in simple linear theory. Commonly observed effects are: generation of motion perpendicular to the driving force, sudden jumps in amplitude, hysteresis, and generation of higher harmonics. In addition, these effects are profoundly influenced by wire asymmetries which in a brass harpsichord wire can cause a small splitting of each natural frequency of free vibration into two closely spaced frequencies (relative separation ~0.2% to 2%), each associated with transverse motion along two orthogonal characteristic wire axes. Some unusual resulting patterns of complex motions of a point on the wire are exhibited on videotape. Examples include: sudden changes of harmonic content, generation of subharmonics, and motion which appears nearly chaotic but which has a pattern period of over 10 s. Another unusual phenomenon due to entirely different causes can occur when a violin string is bowed with a higher than normal force resulting in sounds ranging from about a musical third to a twelfth lower than the sound produced when the string is plucked.

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.

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

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.

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.

Shape coexistence of light, even A mercury isotopes

International Nuclear Information System (INIS)

Cole, J.D.

1978-01-01

The results of the studies of the decay of thallium isotopes establish the coexistence and crossing of two bands in the mercury isotopes. The two bands are built on states of different deformation. The band built upon the ground state has an associated small negative β value (oblate shape) while the second band has a large positive β value (prolate shape). The band heads for the deformed bands in the 184 186 188 Hg isotopes are established as 0 + levels at 375.2, 523.8, and 824.5 keV respectively. A comparison between the experimental results and the predictions of calculations based upon the coexistence of two different nuclear deformations has been made. The presence of two different deformations as described by two minima in the nuclear potential energy curve is termed ''shape coexistence.'' The good agreement of the calculations with the experimental results adds further support to the coexistence interpretation. The coexistence and crossing of two bands of different deformation explains the unusual behavior of the yrast level spacing that is referred to as 'backbending' when discussing moment of inertia versus rotational frequency plots based on the yrast levels. The studies of the 186 188 Pt levels have established the lower members of the ground state band and of a rotation-alignment band. The experimental results confirm the rotation-alignment explanation of backbending in the platinum cases discussed. (Auth.)

A new feature in the internal heavy isotope distribution in ozone

International Nuclear Information System (INIS)

Bhattacharya, S. K.; Liang, Mao-Chang; Savarino, Joel; Michalski, G.

2014-01-01

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ( 18 O/ 16 O and 17 O/ 16 O ratio) which does not follow normal mass fractionation rule: δ 17 O ∼ 0.52 * δ 18 O, expressed as an anomaly Δ 17 O = δ 17 O − 0.52 * δ 18 O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ 18 O (s) or δ 18 O (as) (and similarly for δ 17 O) as well as position dependent isotope anomaly Δ 17 O (s) and Δ 17 O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ 17 O (s) is zero. Consequently, Δ 17 O (as) = 1.5 * Δ 17 O (bulk) (named here simply as the “1.5 rule”) which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure

A new feature in the internal heavy isotope distribution in ozone

Science.gov (United States)

Bhattacharya, S. K.; Savarino, Joel; Michalski, G.; Liang, Mao-Chang

2014-10-01

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition (18O/16O and 17O/16O ratio) which does not follow normal mass fractionation rule: δ17O ˜ 0.52*δ18O, expressed as an anomaly Δ17O = δ17O - 0.52*δ18O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ18O (s) or δ18O (as) (and similarly for δ17O) as well as position dependent isotope anomaly Δ17O (s) and Δ17O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ17O (s) is zero. Consequently, Δ17O (as) = 1.5 * Δ17O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

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.

Experimental study on isotope fractionation of evaporating water of different initial isotopic composition

International Nuclear Information System (INIS)

Pooja Devi; Jain, A.K.; Rao, M.S.; Kumar, B.

2014-01-01

The studies of evaporative isotopic fractionation in controlled conditions are of particular importance for understanding the mechanism of evaporation fractionation in natural conditions. We present the measurements of the average isotopic fractionation factors during the evaporation of water having different initial isotopic compositions at constant temperature. The results show that the isotopic composition of residual water become more enriched over the time and the initial isotopic composition of evaporating water has considerable effect on the average isotopic fractionation factors. The average isotopic fractionation factors in evaporation of Water A and Water B under the present experimental conditions were found to be 0.9817 ± 0.0044 and 0.9887 ± 0.0031 for oxygen and 0.9178 ± 0.0182 and 0.9437 ± 0.0169 for hydrogen, respectively. The findings of this work should lead to a better understanding and use of stable isotope techniques in isotope hydrology by using a simple technique of evaporation pan. (author)

Isotopic methods in hydrogeology and their application to the Underground Research Laboratory, Manitoba

International Nuclear Information System (INIS)

Gascoyne, M.; Kotzer, T.

1995-09-01

This review examines isotopic methods used to determine groundwater sources, residence times and processes of geochemical evolution that have been published in the international literature, with specific reference to AECL's experience in these methods and applications to groundwaters at the Underground Research Laboratory (URL), Manitoba. The program of groundwater sampling and analysis currently being planned for the URL area over the next several years will concentrate on specific isotopic measurements that may assist in understanding the groundwater flow system at the URL site. These results will add to the existing data for the URL area and indicate which isotopes are most useful when applied to the known groundwater flow system of the URL. This program of study is especially important because it not only uses standard geochemical and isotopic measurements (e.g., major ion, trace elements, 2 H/ 18 O, 14 C, 34 S) of groundwaters, but will determine values of more exotic and unusual ratios, such as 6 Li/ 7 Li, and B 11 /B 10 , whose potential for understanding groundwater geochemical evolution is largely unknown at present. In addition, the more established but equally complex methods of isotopic analysis, to determine 3 He/ 4 He, 36 Cl/Cl and 129 I/I, will be used to assess their potential for adding to the hydrogeochemical understanding of flow paths in crystalline rock. (author). 182 refs., 11 tabs., 27 figs

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

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.

Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy

Science.gov (United States)

Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

2013-04-01

Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity

Laser separation of uranium isotopes

International Nuclear Information System (INIS)

Porter, J.T.

1981-01-01

Method and apparatus for separating uranium isotopes are claimed. The method comprises the steps of irradiating a uranyl source material at a wavelength selective to a desired isotope and at an effective temperature for isotope spectral line splitting below about 77 deg.K., further irradiating the source material within the fluorescent lifetime of the source material to selectively photochemically reduce the excited isotopic species, and chemically separating the reduced isotope species from the remaining uranyl salt compound

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.

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

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

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.)

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...

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

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

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)

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.)

An unusual foreign body of esophagus

Directory of Open Access Journals (Sweden)

Surinder K Singhal

2010-07-01

Full Text Available We report a rare case of an unusually long foreign body (Datun impacted in the esophagus of a 56 year-old gentleman. He was literate, without any psychiatric illness and had been using “Neem” (Azadirachta indica stick for cleaning his teeth for the past twenty years. Neem sticks are used for brushing teeth, perhaps one of the earliest and very effective dental care. On closer questioning he revealed his habit of passing the Neem stick into his throat with the aim of cleaning it too while cleaning his teeth. He presented to our emergency early in the morning with this strange long foreign body impacted in his esophagus which was removed successfully using a Jackson’s adult rigid oesophagoscope. We believe this to be the first case of such an unusually long foreign body to be reported in the literature.

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

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.

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)

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.

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

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

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

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

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

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)

Isotope separation using tunable lasers

International Nuclear Information System (INIS)

Snavely, B.B.

1975-01-01

Various processes for laser isotope separation based upon the use of the spectroscopic isotope effect in atomic and molecular vapors are discussed. Emphasis is placed upon processes which are suitable for uranium enrichment. A demonstration process for the separation of uranium isotopes using selective photoionization is described. (U.S.)

Physics with isotopically controlled semiconductors

International Nuclear Information System (INIS)

Haller, E.E.

1994-08-01

Control of the isotopic composition of semiconductors offers a wide range of new scientific opportunities. In this paper a number of recent results obtained with isotopically pure as well as deliberately mixed diamond and Ge bulk single crystals and Ge isotope superlattices will be reviewed. Isotopic composition affects several properties such as phonon energies, bandstructure and lattice constant in subtle but theoretically well understood ways. Large effects are observed for thermal conductivity, local vibrational modes of impurities and after neutron transmutation doping (NTD). Several experiments which could profit greatly from isotope control are proposed

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

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

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....

Isotopic exchange reactions. Kinetics and efficiency of the reactors using them in isotopic separation

International Nuclear Information System (INIS)

Ravoire, Jean

1979-11-01

In the first part, some definitions and the thermodynamic and kinetic isotopic effect concepts are recalled. In the second part the kinetic laws are established, in homogeneous and heterogeneous medium (one component being on occasions present in both phases), without and with isotopic effects. Emphasis is put on application to separation of isotopes, the separation factor α being close to 1, one isotope being in large excess with respect to the other one. Isotopic transfer is then given by: J = Ka (x - y/α) where x and y are the (isotopic) mole fractions in both phases, Ka may be either the rate of exchange or a transfer coefficient which can be considered as the 'same in both ways' if α-1 is small compared to the relative error on the measure of Ka. The third part is devoted to isotopic exchange reactors. Relationships between their efficiency and kinetics are established in some simple cases: plug cocurrent flow reactors, perfectly mixed reactors, countercurrent reactors without axial mixing. We treat only cases where α and the up flow to down flow ratio is close to 1 so that Murphee efficiency approximately overall efficiency (discrete stage contactors). HTU (phase 1) approximately HTU (phase 2) approximately HETP (columns). In a fourth part, an expression of the isotopic separative power of reactors is proposed and discussed [fr

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).

Isotopic methods in hydrogeology and their application to the Underground Research Laboratory, Manitoba

Energy Technology Data Exchange (ETDEWEB)

Gascoyne, M [Atomic Energy of Canada Ltd., Pinawa, MB (Canada). Whiteshell Labs.; Kotzer, T

1995-09-01

This review examines isotopic methods used to determine groundwater sources, residence times and processes of geochemical evolution that have been published in the international literature, with specific reference to AECL`s experience in these methods and applications to groundwaters at the Underground Research Laboratory (URL), Manitoba. The program of groundwater sampling and analysis currently being planned for the URL area over the next several years will concentrate on specific isotopic measurements that may assist in understanding the groundwater flow system at the URL site. These results will add to the existing data for the URL area and indicate which isotopes are most useful when applied to the known groundwater flow system of the URL. This program of study is especially important because it not only uses standard geochemical and isotopic measurements (e.g., major ion, trace elements, {sup 2}H/{sup 18}O, {sup 14}C, {sup 34}S) of groundwaters, but will determine values of more exotic and unusual ratios, such as {sup 6}Li/{sup 7}Li, and B{sup 11}/B{sup 10}, whose potential for understanding groundwater geochemical evolution is largely unknown at present. In addition, the more established but equally complex methods of isotopic analysis, to determine {sup 3}He/{sup 4}He, {sup 36}Cl/Cl and {sup 129}I/I, will be used to assess their potential for adding to the hydrogeochemical understanding of flow paths in crystalline rock. (author). 182 refs., 11 tabs., 27 figs.

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

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

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.

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.

Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon

KAUST Repository

Berke, Heinz

2017-05-11

We report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the -iminodiborane ((--NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.

Ca isotopes in refractory inclusions

International Nuclear Information System (INIS)

Niederer, F.R.; Papanastassiou, D.A.

1984-01-01

We report measurements of the absolute isotope abundance of Ca in Ca-Al-rich inclusions from the Allende and Leoville meteorites. Improved high precision measurements are reported also for 46 Ca. We find that nonlinear isotope effects in Ca are extremely rare in these inclusions. The absence of nonlinear effects in Ca, except for the effects in FUN inclusions, is in sharp contrast to the endemic effects in Ti. One fine-grained inclusion shows an excess of 46 Ca of (7 +- 1) per mille, which is consistent with addition of only 46 Ca or of an exotic (*) component with 46 Ca* approx. 48 Ca*. FUN inclusion EK-1-4-1 shows a small 46 Ca excess of (3.3 +- 1.0) per mille; this confirms that the exotic Ca components in EK-1-4-1 were even more deficient in 46 Ca relative to 48 Ca than is the case for normal Ca. The Ca in the Ca-Al-rich inclusions shows mass dependent isotope fractionation effects which have a range from -3.8 to +6.7 per mille per mass unit difference. This range is a factor of 20 wider than the range previously established for bulk meteorites and for terrestrial and lunar samples. Ca and Mg isotope fractionation effects in the Ca-Al-rich inclusions are common and attributed to kinetic isotope effects. (author)

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)

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

Deduction of kinetic mechanism in multisubstrate enzyme reactions from tritium isotope effects. Application to dopamine beta-hydroxylase

International Nuclear Information System (INIS)

Klinman, J.P.; Humphries, H.; Voet, J.G.

1980-01-01

Primary tritium isotope effects have been measured for the hydroxylation of [2-3H] dopamine catalyzed by dopamine beta-hydroxylase. Experimental values vary from 8.8 +/- 1.4 at 0.02 mM oxygen to 4.1 +/- 0.6 at 1.0 mM oxygen. It is shown that the observed dependence of the isotope effect on oxygen concentration provides unequivocal evidence for a kinetically significant dissociation of both dopamine and oxygen from enzyme, ternary complex. This approach, which is applicable to any multisubstrate enzyme characterized by detectable kinetic isotope effects, provides an alternate to classical methods for the elucidation of kinetic order in enzyme-catalyzed reactions

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

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.)

Isotope effect studies of chicken liver NADP malic enzyme: role of the metal ion and viscosity dependence

International Nuclear Information System (INIS)

Grissom, C.B.; Cleland, W.W.

1988-01-01

The role of the metal ion in the oxidative decarboxylation of malate by chicken liver NADP malic enzyme and details of the reaction mechanism have been investigated by 13 C isotope effects. With saturating NADP and the indicated metal ion at a total concentration 10-fold higher than its K/sub m/, the following primary 13 C kinetic isotope effects at C 4 of malate [ 13 (VK/sub mal/)] were observed at pH 8.0: Mg 2+ , 1.0336; Mn 2+ , 1.0365; Cd 2+ , 1.0366; Zn 2+ , 1.0337; Co 2+ , 1.0283; Ni 2+ , 1.025. Knowing the partitioning of the intermediate oxalacetate between decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation to pyuvate and reduction to malate allows calculation of the intrinsic carbon isotope effect for decarboxylation. For Mg 2+ as activator, this was 1.049 with NADP and 1.046 with 3-acetylpyridine adenine dinucleotide phosphate, although the intrinsic primary deuterium isotope effects on dehydrogenation were 5.6 and 4.2, and the partition ratios of the oxalacetate intermediate for decarboxylation as opposed to hydride transfer were 0.11 and 3.96. It was not possible to calculate reasonable intrinsic carbon isotope effects with the other metal ions by use of the partitioning ratio of oxalacetate because of decarboxylation by another mechanism. The variation of 13 (VK/sub mal/) with pH was used to dissect the total forward and external components. When the authors attempted to use the variation of 13 (VK/sub mal/) with solution viscosity to determine the internal and external commitments, incorrect values were obtained because of a specific effect of the viscosogen in decreasing the K/sub m/ for malate, so that VK/sub mal/ actually increased with viscosity instead of decreasing, as theory predicts

Stabilization of actinides and lanthanides in unusually high oxidation states

International Nuclear Information System (INIS)

Eller, P.G.; Penneman, R.A.

1986-01-01

Chemical environments can be chosen which stabilize actinides and lanthanides in unusually high or low oxidation states and in unusual coordination. In many cases, one can rationalize the observed species as resulting from strong charge/size influences provided by specific sites in host lattices (e.g., Tb(IV) in BaTbO 3 or Am(IV) in polytungstate anions). In other cases, the unusual species can be considered from an acid-base viewpoint (e.g., U(III) in AsF 5 /HF solution or Pu(VII) in Li 5 PuO 6 ). In still other cases, an interplay of steric and redox effects can lead to interesting comparisons (e.g., instability of double fluoride salts of Pu(V) and Pu(VI) relative to U, Np, and Am analogues). Generalized ways to rationalize compounds containing actinides and lanthanides in unusual valences (particularly high valences), including the above and numerous other examples, will form the focus of this paper. Recently developed methods for synthesizing high valent f-element fluorides using superoxidizers and superacids at low temperatures will also be described. 65 refs., 8 figs., 9 tabs

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)

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

Isotopically controlled semiconductors

Energy Technology Data Exchange (ETDEWEB)

Haller, Eugene E.

2006-06-19

The following article is an edited transcript based on the Turnbull Lecture given by Eugene E. Haller at the 2005 Materials Research Society Fall Meeting in Boston on November 29, 2005. The David Turnbull Lectureship is awarded to recognize the career of a scientist who has made outstanding contributions to understanding materials phenomena and properties through research, writing, and lecturing, as exemplified by the life work of David Turnbull. Haller was named the 2005 David Turnbull Lecturer for his 'pioneering achievements and leadership in establishing the field of isotopically engineered semiconductors; for outstanding contributions to materials growth, doping and diffusion; and for excellence in lecturing, writing, and fostering international collaborations'. The scientific interest, increased availability, and technological promise of highly enriched isotopes have led to a sharp rise in the number of experimental and theoretical studies with isotopically controlled semiconductor crystals. This article reviews results obtained with isotopically controlled semiconductor bulk and thin-film heterostructures. Isotopic composition affects several properties such as phonon energies, band structure, and lattice constant in subtle, but, for their physical understanding, significant ways. Large isotope-related effects are observed for thermal conductivity in local vibrational modes of impurities and after neutron transmutation doping. Spectacularly sharp photoluminescence lines have been observed in ultrapure, isotopically enriched silicon crystals. Isotope multilayer structures are especially well suited for simultaneous self- and dopant-diffusion studies. The absence of any chemical, mechanical, or electrical driving forces makes possible the study of an ideal random-walk problem. Isotopically controlled semiconductors may find applications in quantum computing, nanoscience, and spintronics.

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.

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.

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

Fractionation of lithium isotopes in cation-exchange chromatography

International Nuclear Information System (INIS)

Oi, Takao; Kawada, Kazuhiko; Kakihana, Hidetake; Hosoe, Morikazu

1991-01-01

Various methods for lithium isotope separation have been developed, and their applicability to large-scale enriched lithium isotope production has been assessed. Ion-exchange chromatography is one such method. Cation-exchange chromatography of lithium was carried out to investigate the lithium isotope effect in aqueous ion-exchange systems. The heavier isotope. 7 Li, was preferentially fractionated into the resin phase in every experiment conducted, and this result is consistent with the results of previous work. The value of the separation factor was 1.00089-1.00171 at 25C. A comparison of lithium isotope effect with those of potassium and rubidium indicated that the isotope effect originating from hydration is larger than the effect due to phase change for lithium, while the opposite is the case with potassium and rubidium

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

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

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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

Intra-event isotope and raindrop size data of tropical rain reveal effects concealed by event averaged data

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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.

A prodigious lichen planus pigmentosus: The Wolf’s isotopic response

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Yugandar I, Shiva Kumar, Sai Prasad, Srilakshmi P, Akshaya N, Abhiram R, Sujalalitha K, Meghana GB

2014-07-01

Full Text Available Lichen planus is a pruritic, benign, papulosquamous, inflammatory dermatosis of unknown etiology that affects either or all of the skin, mucous membrane, hair and nail. In its classic form, it presents with violaceous, scaly, flat-topped, polygonal papules. A female patient aged 43 years with a history of pruritic eruptions for a period of one month over the right armpit and back of the right chest (C8, T1, T2, T3 Dermatomes. She had a history of herpes zoster in the same localization, which had been treated with topical and oral acyclovir two months prior to this visit. This variant may represent as an example of the Wolf’s isotopic response. We presented our case because of its rarity as a Dermatomal distribution of lichen planus pigmentosus (LPP and its appearance in the area of healed herpes zoster as an isotopic response. The case well highlights this unusual condition and represents the first case reported in Indian dermatology literature to our best of knowledge. The clinical and histological features of this case are described here.

Isotope and fast ions turbulence suppression effects: Consequences for high-β ITER plasmas

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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.

Freezing and fractionation: effects of preservation on carbon and nitrogen stable isotope ratios of some limnetic organisms.

Science.gov (United States)

Wolf, J Marshall; Johnson, Brett; Silver, Douglas; Pate, William; Christianson, Kyle

2016-03-15

Stable isotopes of carbon and nitrogen have become important natural tracers for studying food-web structure and function. Considerable research has demonstrated that chemical preservatives and fixatives shift the isotopic ratios of aquatic organisms. Much less is known about the effects of freezing as a preservation method although this technique is commonly used. We conducted a controlled experiment to test the effects of freezing (-10 °C) and flash freezing (–79 °C) on the carbon and nitrogen isotope ratios of zooplankton (Cladocera), Mysis diluviana and Rainbow Trout (Oncorhynchus mykiss). Subsamples (~0.5 mg) of dried material were analyzed for percentage carbon, percentage nitrogen, and the relative abundance of stable carbon and nitrogen isotopes (δ13C and δ15N values) using a Carlo Erba NC2500 elemental analyzer interfaced to a ThermoFinnigan MAT Delta Plus isotope ratio mass spectrometer. The effects of freezing were taxon-dependent. Freezing had no effect on the isotopic or elemental values of Rainbow Trout muscle. Effects on the δ13C and δ15N values of zooplankton and Mysis were statistically significant but small relative to typical values of trophic fractionation. The treatment-control offsets had larger absolute values for Mysis (δ13C: ≤0.76 ± 0.41‰, δ15N: ≤0.37 ± 0.16‰) than for zooplankton (δ13C: ≤0.12 ± 0.06‰, δ15N: ≤0.30 ± 0.27‰). The effects of freezing were more variable for the δ13C values of Mysis, and more variable for the δ15N values of zooplankton. Generally, both freezing methods reduced the carbon content of zooplankton and Mysis, but freezing had a negative effect on the %N of zooplankton and a positive effect on the %N of Mysis. The species-dependencies and variability of freezing effects on aquatic organisms suggest that more research is needed to understand the mechanisms responsible for freezing-related fractionation before standardized protocols for freezing as a preservation method can be adopted.

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)

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

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.

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

Science.gov (United States)

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

2005-01-01

The Pierina high-sulfidation Au-Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO42--H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (??34S=8.5??? to 31.7???; ??18 OSO4=4.9??? to 16.5???; ??18 OOH=2.2??? to 14.4???; ??D=-97??? to -39???), sulfides (??34 S=-3.0??? to 4.3???), sulfur (??34S=-1.0??? to 1.1???), and clay minerals (??18O=4.3??? to 12.5???; ??D=-126??? to -81???) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration-mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4???6) highly acidic condensate that mixed with meteoric water but retained a magmatic ??34S???S signature of ???1???, (3) SO2 disproportionation to HSO4- and H2S between 320 and 180 ??C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz???alunite-quartz??clay???intermediate argillic???propylitic alteration zoning. Magmatic-steam alunite has higher ??34S (8.5??? to 23.2???) and generally lower ??18OSO4 (1.0 to 11.5???), ??18OOH (-3.4 to 5.9???), and ??D (-93 to -77???) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this

Isotopes in oxidation reactions

International Nuclear Information System (INIS)

Stewart, R.

1976-01-01

The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

Unusual Fears in Children with Autism

Science.gov (United States)

Mayes, Susan Dickerson; Calhoun, Susan L.; Aggarwal, Richa; Baker, Courtney; Mathapati, Santosh; Molitoris, Sarah; Mayes, Rebecca D.

2013-01-01

Unusual fears have long been recognized as common in autism, but little research exists. In our sample of 1033 children with autism, unusual fears were reported by parents of 421 (41%) of the children, representing 92 different fears. Many additional children had common childhood fears (e.g., dogs, bugs, and the dark). More than half of children…

Sulfur and selenium isotope separation by distillation

International Nuclear Information System (INIS)

Mills, T. R.; McInteer, B. B.; Montoya, J. G.

1988-01-01

Sulfur and selenium isotopes are used for labeled compounds and as precursors for radioisotope production; however, both limited availability and high costs are problems. A new method is needed for large-scale separation of these isotopes. Experimental distillation columns were used to measure isotopic separations for sulfur and selenium compounds. The maximum total isotope separation of 32 S vs. 34 S were 1.127 for H 2 S, 1.048 for COS, 0.838 for SF 4 , and 1.058 for CH 3 SH. Relative volatilities of 32 S vs. 34 S are 1.0006 for COS and 0.9976 for SF 4 . There is a reverse isotope effect for carbon in COS. No isotopic separation was observed for dimethyl selenide. The lower mass selenium isotopes in H 2 Se are more volatile. Distillation is a promising method for separating sulfur isotopes on a production scale. Existing distillation technology produced separated isotopes with an effect similar to that found for sulfur in SF 4 . 8 refs., 2 tabs

Sulfur and selenium isotope separation by distillation

International Nuclear Information System (INIS)

Mills, T.R.; McInteer, B.B.; Montoya, J.G.

1989-01-01

Sulfur and selenium isotopes are used for labeled compounds and as precursors for radioisotope production; however, both limited availability and high costs are problems. A new method is needed for large-scale separation of theses isotopes. Experimental distillation columns were used to measure isotopic separations for sulfur and selenium compounds. The maximum total isotope separations of 32 S vs. 34 S were 1.127 for H 2 S, 1.048 for COS, 0.838 for SF 4 , and 1.058 for CH 3 SH. Relative volatilities of 32 S and 34 S are 1.0006 for COS and 0.9976 for SF 4 . There is a reverse isotope effect for carbon in COS. No isotopic separation was observed for dimethyl selenide. The lower mass selenium isotopes in H 2 Se are more volatile. Distillation is a promising method for separating sulfur isotopes on a production scale. Existing distillation technology produces separated isotopes with an effect similar to that found for sulfur in SF 4 . (author). 8 refs.; 2 tabs

Unusual radiological findings of adult-onset pulmonary tuberculosis

International Nuclear Information System (INIS)

Lee, Yong Chul; Lee, Jong Beum; Kim, Sue Hyun

1987-01-01

Usual chest radiographic findings in pulmonary tuberculosis are well described in radiologic literatures for both primary and postprimary phases of disease. During the last decade, many authors have enumerated the unusual manifestations of pulmonary tuberculosis in adult population. These unusual findings usually have been involved in the frequent failure of both radiologist and clinician to recognize that tuberculosis could be the cause of a abnormal chest radiograph in patients who are finally and surprisingly proven to have tuberculosis. Authors have evaluated 249 patients who were admitted and newly proven to have adult-onset pulmonary tuberculosis at Chung-Ang University Hospital from January, 1985 to December, 1986. Unusual findings were noted in 76 (30.5%) of the 249 patients with adult-onset pulmonary tuberculosis. These unusual findings most frequently could be seen in 3rd decades and showed no sex difference in incidence. A broad spectrum of abnormal findings including usual and unusual abnormalities were procedure by adult-onset pulmonary tuberculosis. The unusual radiographic findings were arbitrarily classified. Pleural effusion without parenchymal disease (10.0%), unusual location of infiltrate (5.6%) and atelectasis (3.2%) were relatively common. Hilar and / or mediastinal lymphnode enlargement (1.6%), cavity without parenchymal infiltrates (1.6%), septic lung-like infiltrates (1.6%), completely clear lungs (1.2%), miliary infiltrates (1.2%), fibrocalcific scar-like infiltrates (1.2%), masslike density (1.2%) and rheumatoid lung-like infiltrates (1.2%) were occasionally noted. Pneumothorax without parenchymal disease (0.4%) and bron chocutaneous fistula (0.4%) are. The recognition of these unusual findings could further improve the detection and diagnosis of adult-onset pulmonary tuberculosis

Theoretical Study of H/D Isotope Effects on Nuclear Magnetic Shieldings Using an ab initio Multi-Component Molecular Orbital Method

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Masanori Tachikawa

2013-05-01

Full Text Available We have theoretically analyzed the nuclear quantum effect on the nuclear magnetic shieldings for the intramolecular hydrogen-bonded systems of σ-hydroxy acyl aromatic species using the gauge-including atomic orbital technique combined with our multi-component density functional theory. The effect of H/D quantum nature for geometry and nuclear magnetic shielding changes are analyzed. Our study clearly demonstrated that the geometrical changes of hydrogen-bonds induced by H/D isotope effect (called geometrical isotope effect: GIE is the dominant factor of deuterium isotope effect on 13C chemical shift.

Myasthenia Gravis: Unusual Presentations and Diagnostic Pitfalls.

Science.gov (United States)

Rodolico, Carmelo; Parisi, Daniela; Portaro, Simona; Biasini, Fiammetta; Sinicropi, Stefano; Ciranni, Annamaria; Toscano, Antonio; Messina, Sonia; Musumeci, Olimpia; Vita, Giuseppe; Girlanda, Paolo

2016-08-30

Myasthenia gravis (MG) is an autoimmune disorder presenting with fluctuating, fatigable muscle weakness. Initial symptoms classically involve ocular and proximal limb muscles. Rarely, MG may onset with unusual features, so it can be misdiagnosed with other neuromuscular diseases. To describe unusual and atypical presentations of MG in a large cohort of patients, considering and discussing diagnostic difficulties and pitfalls. We report on 21 out of 508 MG patients, coming to our department in the last 27 years and presenting with atypical or unusual features. The diagnosis was achieved performing a careful clinical examination, a proper neurophysiological assessment, the neostigmine test, the AChR and MuSK antibodies assay and chest CT-scan. Patients with atypical/unusual MG onset were the 4.4% of all MG patients population. We describe seven different clinical categories: asymmetric distal upper limbs weakness, foot drop, isolated triceps brachii weakness and foot drop, post exertional axial weakness with dropped head, acute facial dyplegia, limb-girdle MG and MG with sudden lower limbs weakness and recurrent falls. Atypical and unusual presentations may increase the risk to misdiagnose or delay MG diagnosis. Isolated limb-girdle presentation is the most frequent atypical form in our series.

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

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)

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)

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.)

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

Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

Science.gov (United States)

Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

2018-05-01

Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of

Response of the Pre-oriented Goal-directed Attention to Usual and Unusual Distractors: A Preliminary Study

Directory of Open Access Journals (Sweden)

Golnaz Baghdadi

2017-03-01

Full Text Available Introduction: In this study, we investigated the distraction power of the unusual and usual images on the attention of 20 healthy primary school children. Methods: Our study was different from previous ones in that the participants were asked to fix the initial position of their attention on a pre-defined location after being presented with unusual images as distractors. The goals were presented in locations, which were far from the attraction basin of distractors. Our expectation was that the pre-orienting of the attention to the position of targets can reduce the attractive effect of unusual images compared to the usual ones. The percentage of correct responses and the reaction time have been measured as behavioral indicators of attention performance. Results: Results showed that using the goal-directed attention, subjects ignored both kinds of distractors nearly the same way. Conclusion: With regard to previous reports about the more attraction towards the unusual images, it is suggested that the dynamics of the visual attention system be sensitive to the initial condition. That is, changing the initial position of the attention can lead to the decrement of the unusual images’ effects. However, several other possibilities such as a probable delay in processing unusual features could explain this observation, too. 

Absolute isotopic abundances of Ti in meteorites

International Nuclear Information System (INIS)

Niederer, F.R.; Papanastassiou, D.A.; Wasserburg, G.J.

1985-01-01

The absolute isotope abundance of Ti has been determined in Ca-Al-rich inclusions from the Allende and Leoville meteorites and in samples of whole meteorites. The absolute Ti isotope abundances differ by a significant mass dependent isotope fractionation transformation from the previously reported abundances, which were normalized for fractionation using 46 Ti/ 48 Ti. Therefore, the absolute compositions define distinct nucleosynthetic components from those previously identified or reflect the existence of significant mass dependent isotope fractionation in nature. We provide a general formalism for determining the possible isotope compositions of the exotic Ti from the measured composition, for different values of isotope fractionation in nature and for different mixing ratios of the exotic and normal components. The absolute Ti and Ca isotopic compositions still support the correlation of 50 Ti and 48 Ca effects in the FUN inclusions and imply contributions from neutron-rich equilibrium or quasi-equilibrium nucleosynthesis. The present identification of endemic effects at 46 Ti, for the absolute composition, implies a shortfall of an explosive-oxygen component or reflects significant isotope fractionation. Additional nucleosynthetic components are required by 47 Ti and 49 Ti effects. Components are also defined in which 48 Ti is enhanced. Results are given and discussed. (author)

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...

2. Workshop 'Isotopes in Nature'. 1

International Nuclear Information System (INIS)

1979-11-01

The workshop was aimed at discussing in detail the following problems: (1) distribution of stable and radioactive isotopes in nature, (2) theoretical and experimental studies of isotopic effects in natural processes, (3) problems of sample preparation and sample measurement in determining the relative abundance of stable isotopes or radioactive isotopes in nature, (4) age estimations of samples from different areas of the geosphere, (5) contributions to the specification of global and regional substance cycles in nature with the aid of isotopic and geochemical studies. 75 summaries are included

Plutonium isotope ratios in polychaete worms

International Nuclear Information System (INIS)

Beasley, T.M.; Fowler, S.W.

1976-01-01

Reference is made to recent reports that suggest that terrestrial and aquatic organisms may preferentially take up 238 Pu compared with sup(239+240)Pu. It is stated that although kinetic isotope effects are known to occur in biological systems for low mass number elements, such as H, C and N, such effects are generally discounted with higher mass numbers, and differences in the biological 'uptake' of isotopes of high mass number elements, such as those of Pu, are normally attributable to differences in the chemical or physical forms of the isotopes or to different quantities of isotopes available to organisms. This has been applied to explain differential Pu isotope behaviour in animals under controlled laboratory conditions, but it is not certain that it can be applied to explain anomalies of Pu isotope behaviour in organisms contaminated by nuclear test debris or by wastes from nuclear fuel reprocessing plants. Geochemical weathering may also have an effect. Described here are experiments in which it was found that deposit feeding marine worms living in sediments contaminated in different ways with Pu isotopes did not show preferential accumulation of 238 Pu. The worms had been exposed to different chemical and physical forms of the isotopes, including exposure to laboratory-labelled sediment, sediment collected from a former weapons test site, and sediment contaminated by wastes from a nuclear fuel reprocessing plant. The worms were allowed to accumulate Pu for times of 5 to 40 days. Isotope ratios were determined by α-spectrometric techniques. It is considered that the results are important for environmental samples where Pu activity levels are low. (U.K.)

48 CFR 632.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false Unusual contract financing. 632.114 Section 632.114 Federal Acquisition Regulations System DEPARTMENT OF STATE GENERAL CONTRACTING REQUIREMENTS CONTRACT FINANCING Non-Commercial Item Purchase Financing 632.114 Unusual contract financing. The...

48 CFR 2432.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true Unusual contract financing... DEVELOPMENT GENERAL CONTRACTING REQUIREMENTS CONTRACT FINANCING Non-Commercial Item Purchase Financing 2432.114 Unusual contract financing. The Senior Procurement Executive is the agency head for the purpose of...

Isotope mixtures of hydrogen in vanadium

International Nuclear Information System (INIS)

Mecking-Schloetensack, P.

1982-03-01

The properties of isotope-mixtures of Protium and Deuterium stored in Vanadium have been studied. Protium and Deuterium are existing as interstitial-atoms on tetrahedral sites as well as on octahedral sites in this system. This feature leads to large isotopic-effects between the two isotopes. The dependence of the thermodynamic functions like heat of solution, nonconfigurational entropy, specific heat and ordering temperatures from the composition of the isotope-mixture has been determined. (orig.)

Deflection of atomic beams with isotope separation by optical resonance radiation using stimulated emission and the ac stark effect

International Nuclear Information System (INIS)

Bjorkholm, J.E.; Liao, P.F.H.

1977-01-01

Improved atomic beam deflection and improved isotope separation, even in vapors, is proposed by substituting the A.C. Stark effect for the baseband chirp of the pushing beam in the prior proposal by I. Nebenzahl et al., Applied Physics Letters, Vol. 25, page 327 (September 1974). The efficiency inherent in re-using the photons as in the Nebenzahl et al proposal is retained; but the external frequency chirpers are avoided. The entire process is performed by two pulses of monochromatic coherent light, thereby avoiding the complication of amplifying frequency-modulated light pulses. The A.C. Stark effect is provided by the second beam of coherent monochromatic light, which is sufficiently intense to chirp the energy levels of the atoms or isotopes of the atomic beam or vapor. Although, in general, the A.C. Stark effect will alter the isotope shift somewhat, it is not eliminated. In fact, the appropriate choice of frequencies of the pushing and chirping beams may even relax the requirements with respect to the isotope absorption line shift for effective separation. That is, it may make the isotope absorption lines more easily resolvable

Carbon isotope ratios and isotopic correlations between components in fruit juices

Science.gov (United States)

Wierzchnicki, Ryszard

2013-04-01

Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

Science.gov (United States)

Chew, Gina; Walczyk, Thomas

2013-04-02

Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

Unusual event report from Oskarshamn

International Nuclear Information System (INIS)

1996-01-01

The title of the report was intended to reflect the cause of the shutdown and the report to be regarded as a summary of the deficiencies that had been revealed and remedied. No single deficiency was regarded as reportable as an unusual event, but taken together the identified deficiencies deviated from the assumed safety level to the extent that it should be reported. The unusual event report refers to two main documents presenting measures taken to return to reported safety level, one concerning technical and one organizational measures

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Science.gov (United States)

Dobson, P.F.; O'Neil, J.R.

1987-01-01

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6-2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6??? in 18O during differentiation is explained by crystallization of 18O-depleted mafic phases. Silicic glasses have elevated ??18O values and relatively low ??D values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary ??D values of -53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere. ?? 1987.

On effeciency of isotopes application in industry

International Nuclear Information System (INIS)

Yankovskij, L.

1979-01-01

The final results of the long term work in the field of research, projecting and pilot production are: the technology; methods and instruments of the isotope technique and their applications in the peoples economy, especially in industry. Effectiveness of isotope technique and especially its economic effectiveness depends on the scale of application of these techniques (instrument, method, technology) in different branches of the peoples economy. Comparing expenses on istope and radiation researches with total economic effectiveness of the isotope techniques application in some countries, the total economic effectiveness of the isotope researches has been determined. The main content of the paper is the analysis of structure and dynamics of the efficiency factor for the isotope technique application in separate countries for long period of time. Determination of the total economic efficiency of the whole branch of researches, conducted according to the methodology developed by the author, on the example of isotope research in some countries, permits to make a conclusion about the state and development tendencies of these researches in the international scale and can be a good base for making decisions in the field of the scientific policy of countries [ru

Isotopic and chemical variation of organic nanoglobules in primitive meteorites

Science.gov (United States)

de Gregorio, Bradley T.; Stroud, Rhonda M.; Nittler, Larry R.; Alexander, Conel M. O'd.; Bassim, Nabil D.; Cody, George D.; Kilcoyne, A. L. David; Sandford, Scott A.; Milam, Stefanie N.; Nuevo, Michel; Zega, Thomas J.

2013-05-01

Organic nanoglobules are microscopic spherical carbon-rich objects present in chondritic meteorites and other astromaterials. We performed a survey of the morphology, organic functional chemistry, and isotopic composition of 184 nanoglobules in insoluble organic matter (IOM) residues from seven primitive carbonaceous chondrites. Hollow and solid nanoglobules occur in each IOM residue, as well as globules with unusual shapes and structures. Most nanoglobules have an organic functional chemistry similar to, but slightly more carboxyl-rich than, the surrounding IOM, while a subset of nanoglobules have a distinct, highly aromatic functionality. The range of nanoglobule N isotopic compositions was similar to that of nonglobular 15N-rich hotspots in each IOM residue, but nanoglobules account for only about one third of the total 15N-rich hotspots in each sample. Furthermore, many nanoglobules in each residue contained no 15N enrichment above that of bulk IOM. No morphological indicators were found to robustly distinguish the highly aromatic nanoglobules from those that have a more IOM-like functional chemistry, or to distinguish 15N-rich nanoglobules from those that are isotopically normal. The relative abundance of aromatic nanoglobules was lower, and nanoglobule diameters were greater, in more altered meteorites, suggesting the creation/modification of IOM-like nanoglobules during parent-body processing. However, 15N-rich nanoglobules, including many with highly aromatic functional chemistry, likely reflect preaccretionary isotopic fractionation in cold molecular cloud or protostellar environments. These data indicate that no single formation mechanism can explain all of the observed characteristics of nanoglobules, and their properties are likely a result of multiple processes occurring in a variety of environments.

48 CFR 2832.114 - Unusual contract financing.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 6 2010-10-01 2010-10-01 true Unusual contract financing... Contracting Requirements CONTRACT FINANCING Non-Commercial Item Purchase Financing 2832.114 Unusual contract financing. The HCA, or designee at a level not lower than the BPC, is the official authorized to approve...

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

Unusual metastatic localizations of differentiated thyroid carcinoma

International Nuclear Information System (INIS)

Ben Rais, N.; Ghfir, I.

2007-01-01

Full text: Introduction: The majority of thyroid cancers have a slow evolution, a more often loco-regional extension, and a good forecast. Remote metastases, when they exist, generally touch the osseous skeleton and/or pulmonary tissue. However, unusual metastatic localizations much more exceptional are possible. The authors report through these work five cases of atypical metastasis of differentiated thyroid carcinoma followed in Nuclear Medicine department of Ibn Sina hospital in Rabat under the directives of Professor N Ben Rais. Materials and methods: Our five patients had initially undergone a total thyroidectomy for differentiated thyroid carcinoma histologically confirmed. They had profited 4 weeks after the surgical gesture from a reference isotopic exploration (131 Iodine whole body scan and thyroglobulin dosage). The paraclinic assessment was supplemented by a computed tomography (CT). Results: Revealing symptomatology in the first 69 year old patient was dominated by blindness associated with an elective up-take of radioactive 131-Iodine on the level of hypophyseal gland extending to the sphenoid bone. The second 55 year old patient reported right basithoracic pains resisting to the usual antalgic treatment with a bulky mass driving back the kidney right to the bottom at CT with and important up-take 131-Iodine at whole body scan; a surrenalectomy was thus carried out with conservation of the kidney. The three other patients presented at the clinical examination dermohypodermic nodular lesions of various localizations whose anatomopathologic study had confirmed their thyroid metastatic origin. In the 5 patients the rate of thyroglobulin was considerably high. An activity of 3,7 GBq 131-Iodine was managed with the 5 patients. The evolution was marked, in the short run, at the first patient by a recovery partial of the sight, the disappearance of pain in the second patient and a remarkable reduction of thyroglobulin level for all our patients. Conclusion

Proceedings of the Conference on Isotopic and Molecular Processes

International Nuclear Information System (INIS)

Pamula, A.

1999-01-01

The proceedings of the Conference on Isotopic and Molecular Processes held on September 23 - 25, 1999 in Cluj - Napoca, Romania contains 8 plenary lectures, 12 oral presentations and 34 posters on isotopic processes (Section A) and 12 oral presentations plus 61 posters on molecular processes (Section B). The main topics treated in plenary lectures were isotope production, separation and enrichment as well as stable isotope applications. Also in this section studies on isotope effects in different fields are reported. In the section A, besides reports on isotope effects, exchange and separation, new methods of preparation and labelling compounds used particularly in nuclear medicine are presented. Also environmental studies by means of stable isotope and radon monitoring are described. In the section B several communications are treating the applications of radiation effects and different nuclear methods in medicine

Unusual Market Activity Announcements: A Study of Price Manipulation on the Indonesian Stock Exchange

Directory of Open Access Journals (Sweden)

Mamduh M. Hanafi

2010-05-01

Full Text Available We investigate stocks involved in the Unusual Market Activity (UMA Announcements. The Indonesian Stock Exchange occasionally issues UMA announcements when it suspects that there are unusual price increases (positive UMAs or price decreases (negative UMAs, as well as unusual increases in trading volumes. We believe that UMA announcements signal a high probability that stocks are being manipulated. We find no differences in fundamentals and trading variables between stocks in the UMA announcements and those not in the UMA announcements. Any stock is vulnerable to market manipulation. Stocks in the UMA announcements do not exhibit reversal patterns, suggesting that price effect is permanent. UMAs seem to convey relevant information, which is most likely in the form of insider type of information. Keywords: emerging market; price manipulation; unusual market activity announcement.

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.

Unusual raptor nests around the world

Science.gov (United States)

Ellis, D.H.; Craig, T.; Craig, E.; Postupalsky, S.; LaRue, C.T.; Nelson, R.W.; Anderson, D.W.; Henny, C.J.; Watson, J.; Millsap, B.A.; Dawson, J.W.; Cole, K.L.; Martin, E.M.; Margalida, A.; Kung, P.

2009-01-01

From surveys in many countries, we report raptors using unusual nesting materials (e.g., paper money, rags, metal, antlers, and large bones) and unusual nesting situations. For example, we documented nests of Steppe Eagles Aquila nipalensis and Upland Buzzards Buteo hemilasius on the ground beside well-traveled roads, Saker Falcon Falco cherrug eyries in attics and a cistern, and Osprey Pandion haliaetus nests on the masts of boats and on a suspended automobile. Other records include a Golden Eagle A. chrysaetos nest 7.0 m in height, believed to be the tallest nest ever described, and, for the same species, we report nesting in rudimentary nests. Some nest sites are within a few meters of known predators or competitors. These unusual observations may be important in revealing the plasticity of a species' behavioral repertoire. ?? 2009 The Raptor Research Foundation, Inc.

Disentangling effects of growth and nutritional status on seabird stable isotope ratios

Science.gov (United States)

Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

2009-01-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

Calcium Isotope Analysis by Mass Spectrometry

Science.gov (United States)

Boulyga, S.; Richter, S.

2010-12-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. This presentation discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. Additionally, the availability of Ca isotope reference materials will be discussed.

The 2-nd Conference on Isotopic and Molecular Processes. Abstracts

International Nuclear Information System (INIS)

Bogdan, Mircea

2001-01-01

The proceedings of the 2-nd Conference on Isotopic and Molecular Processes held on September 27 - 29, 2001 in Cluj - Napoca, Romania, contains contributions presented as: 11 plenary lectures, 24 oral presentations and 103 posters in two sections, namely, isotopic processes and molecular processes. The main topics treated in this conference were isotope production, separation and enrichment as well as stable isotope applications. Also, studies on isotope effects in different fields are reported. Besides reports on isotope effects, exchange and separation, new methods of preparation and labelling compounds used particularly in nuclear medicine are presented. Environmental studies by means of stable isotope and radon monitoring are described. Applications of radiation effects and different nuclear methods in medicine are also addressed

Kinetic coefficients in isotopically disordered crystals

International Nuclear Information System (INIS)

Zhernov, Arkadii P; Inyushkin, Alexander V

2002-01-01

Peculiarities of the behavior of kinetic coefficients, like thermal conductivity, electric conductivity, and thermoelectric power, in isotopically disordered materials are reviewed in detail. New experimental and theoretical results on the isotope effects in the thermal conductivity of diamond, Ge, and Si semiconductors are presented. The suppression effect of phonon-drag thermopower in the isotopically disordered Ge crystals is discussed. The influence of dynamic and static crystal lattice deformations on the electric conductivity of metals as well as on the ordinary phonon spectrum deformations is considered. (reviews of topical problems)

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.

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

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.

Therapeutic use of radioactive isotopes

CERN Document Server

Caroline Duc

2013-01-01

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

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

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

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

Science.gov (United States)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

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

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)

Effects of climatic seasonality on the isotopic composition of evaporating soil waters

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P. Benettin

2018-05-01

Full Text Available Stable water isotopes are widely used in ecohydrology to trace the transport, storage, and mixing of water on its journey through landscapes and ecosystems. Evaporation leaves a characteristic signature on the isotopic composition of the water that is left behind, such that in dual-isotope space, evaporated waters plot below the local meteoric water line (LMWL that characterizes precipitation. Soil and xylem water samples can often plot below the LMWL as well, suggesting that they have also been influenced by evaporation. These soil and xylem water samples frequently plot along linear trends in dual-isotope space. These trend lines are often termed "evaporation lines" and their intersection with the LMWL is often interpreted as the isotopic composition of the precipitation source water. Here we use numerical experiments based on established isotope fractionation theory to show that these trend lines are often by-products of the seasonality in evaporative fractionation and in the isotopic composition of precipitation. Thus, they are often not true evaporation lines, and, if interpreted as such, can yield highly biased estimates of the isotopic composition of the source water.

Cognitive control and unusual decisions about beauty: An fMRI study

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Albert eFlexas

2014-07-01

Full Text Available Studies of visual aesthetic preference have shown that people without art training generally prefer representational paintings to abstract paintings. This, however, is not always the case: preferences can sometimes go against this usual tendency. We aimed to explore this issue, investigating the relationship between ‘unusual responses’ and reaction time in an aesthetic appreciation task. Results of a behavioural experiment confirmed the trend for laypeople to consider as beautiful mostly representational stimuli and as not beautiful mostly abstract ones (‘usual response’. Furthermore, when participants gave unusual responses, they needed longer time, especially when considering abstract stimuli as beautiful. We interpreted this longer time as greater involvement of the cognitive mastering and evaluation stages during the unusual responses. Results of an fMRI experiment indicated that the anterior cingulate, orbitofrontal cortex and insula were the main structures involved in this effect. We discuss the possible role of these areas in an aesthetic appreciation task.

Precipitation regime influence on oxygen triple-isotope distributions in Antarctic precipitation and ice cores

Science.gov (United States)

Miller, Martin F.

2018-01-01

The relative abundance of 17O in meteoric precipitation is usually reported in terms of the 17O-excess parameter. Variations of 17O-excess in Antarctic precipitation and ice cores have hitherto been attributed to normalised relative humidity changes at the moisture source region, or to the influence of a temperature-dependent supersaturation-controlled kinetic isotope effect during in-cloud ice formation below -20 °C. Neither mechanism, however, satisfactorily explains the large range of 17O-excess values reported from measurements. A different approach, based on the regression characteristics of 103 ln (1 +δ17 O) versus 103 ln (1 +δ18 O), is applied here to previously published isotopic data sets. The analysis indicates that clear-sky precipitation ('diamond dust'), which occurs widely in inland Antarctica, is characterised by an unusual relative abundance of 17O, distinct from that associated with cloud-derived, synoptic snowfall. Furthermore, this distinction appears to be largely preserved in the ice core record. The respective mass contributions to snowfall accumulation - on both temporal and spatial scales - provides the basis of a simple, first-order explanation for the observed oxygen triple-isotope ratio variations in Antarctic precipitation, surface snow and ice cores. Using this approach, it is shown that precipitation during the last major deglaciation, both in western Antarctica at the West Antarctic Ice Sheet (WAIS) Divide and at Vostok on the eastern Antarctic plateau, consisted essentially of diamond dust only, despite a large temperature differential (and thus different water vapour supersaturation conditions) at the two locations. In contrast, synoptic snowfall events dominate the accumulation record throughout the Holocene at both sites.

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.)

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)

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

Kinetic isotope effects in the CH4 + H→CH3 + H2 system. Predictions of the LMR six-body potential-energy reaction hypersurface

International Nuclear Information System (INIS)

Marriott, T.D.

1976-01-01

Scope of Study: The purpose of this study was two-fold. First, it served to test, in part, the usefulness of the LMR six-body potential-energy surface (LMR-PES) for transition-state theory predictions of the kinetic isotope effects for both the forward and reverse reactions of CH 4 + H reversible CH 3 + H 2 . In this regard the agreement between experimental and theoretical isotope effects, assuming the former to be accurate, provides information about the accuracy of the curvature of the potential energy surface for motion both parallel and perpendicular to the reaction coordinate. Second, these isotope effects were used to assess the validity of a number of qualitative and semi-quantitative interpretations of kinetic isotope effects developed in physical organic chemistry with regard to this reaction system. The force constants and geometries obtained numerically from the LMR-PES were found to produce reasonable harmonic approximations to the reactant normal mode frequencies. Neglecting tunneling, the LMR-PES reasonably reproduces the experimental k/sub H//k/sub D/ values for the reactions CH 4 + H(D), CH 3 + HD(DH) and CD 2 + HD(DH). Since previous theoretical treatments of primary deuterium kinetic isotope effects have neglected the bending normal mode frequencies, a semi-quantitative study of the effect of neglecting bending frequencies on the VP, EXC, and ZPE elements as well as the transition-state theory kinetic isotope effects was performed. The Swain-Schaad relationship between primary deuterium and tritium kinetic isotope effects was shown to hold to a reasonable degree of accuracy for the LMR-PES reaction system. A relationship between 13-carbon and 14-carbon kinetic isotope effects similar to the Swain-Schaad relationship was derived

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

Early African Diaspora in colonial Campeche, Mexico: strontium isotopic evidence.

Science.gov (United States)

Price, T Douglas; Tiesler, Vera; Burton, James H

2006-08-01

Construction activities around Campeche's central park led to the discovery of an early colonial church and an associated burial ground, in use from the mid-16th century AD to the late 17th century. Remains of some individuals revealed dental mutilations characteristic of West Africa. Analyses of strontium isotopes of dental enamel from these individuals yielded unusually high (87)Sr/(86)Sr ratios, inconsistent with an origin in Mesoamerica, but consistent with an origin in West Africa in terrain underlain by the West Africa Craton, perhaps near the port of Elmina, a principal source of slaves for the New World during the 16th century. These individuals likely represent some of the earliest representatives of the African Diaspora in the Americas.

Crystal-plastic deformation of zircon : effects on microstructures, textures, microchemistry and the retention of radiogenic isotopes

International Nuclear Information System (INIS)

Kovaleva, E.

2015-01-01

Dating of deep-crustal deformation events potentially can be achieved by using plastically-deformed accessory minerals found in high-temperature shear zones. Deformation microstructures, such as dislocations and low-angle boundaries, form due to plastic deformation in the crystal lattice and act as fluid migration pathways and trace element (e.g. Pb, Ti, U, Th, REE) diffusion pathways through so-called “pipe diffusion”. Deformation microstructures can alter the chemical and isotopic composition of certain grain parts and may lead to complete or partial isotopic resetting of certain geochronometers (e.g. U/Th/Pb, K/Ar, Rb/Sr) in the mineral domains. This work aims to better understand the processes of crystal-plastic deformation and associated trace element redistribution and the resetting of isotopic systems in zircon. This study finds that: a) there are three general finite deformation patterns in deformed zircons; b) suggests that it is possible to reconstruct the macroscopic kinematic framework of the shear zone based on the orientation of deformed zircon grains and the operating misorientation axes; c) and demonstrates the effect of deformation microstructures on trace elements and Pb isotopes in zircon. The final goal of this project is to develop a tool for isotopic dating of high-temperature deformation events in the deep crust. In addition to these results, zircon grains with planar deformation bands have been discovered in paleo-seismic zones; these deformation features have been described in detail and a possible mechanism of their origin and formation is suggested. The effect of planar deformation bands on trace element and isotopic behavior has also been investigated. (author) [de

Isotope effects in mass-spectrometry; Les effets isotopiques en spectrometrie de masse

Energy Technology Data Exchange (ETDEWEB)

Leicknam, J P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires. Departement de physico-chimie, service des isotopes stables, section de spectrometrie de masse

1967-05-01

In the first part, a review is made of the work concerning the influence of isotopic substitution on the stabilities of ionised molecules and the bond-breaking probabilities; metastable transitions are also affected by this substitution. A model based on the Franck-Condon principle accounts for the experimentally observed isotopic effects for diatomic molecules; to a certain extent it is possible to generalise the calculation for the case of isotopic molecules of carbon dioxide gas. For deuterated polyatomic molecules there exist a {pi} effect making it possible to compare the relative stabilities of the X-H and X-D bonds, and a {gamma} effect which characterizes the different behaviours of the X-H bond in a normal molecule and in its partially deuterated homologue. Usually there is a very marked {pi} effect (e.g. the C-D bonds are more difficult to break than the homologous C-H bonds) and a {gamma} effect, the partial deuteration of a molecule leading in general to an increase in the probability of breakage of a given bond. An interpretation of {pi} and {gamma} effects based on Rosenstock near-equilibrium theory accounts for the observed phenomena, qualitatively at least, in the case of propane and acetylene. In the second part are gathered together results concerning isotopic effects produced during the formation of rearranged ions. The existence of cyclic transition ions has made it possible for Mc Lafferty to explain the existence of these ions in the mass spectrum; isotopic substitution leads to a modification of the rearrangement mechanism, the bonding forces being no longer the same. (author) [French] Dans une premiere partie, on rassemble les travaux concernant l'influence de la substitution isotopique sur les stabilites des molecules ionisees et les probabilites de rupture des liaisons; les transitions metastables sont egalement modifiees par cette substitution. Un modele base sur le principe de Franck-Condon rend compte des effets isotopiques

An Unusual Bone Loss Around Implants

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Amirreza Rokn

2013-01-01

Full Text Available AbstractPre-implant disease is an inflammatory process, which can affect the surrounding tissues of a functional Osseointegrated implant that is usually as a result of a disequilibrium between the micro-flora and the body defense system.This case reports a 57 years old male with unusual bone loss around dental implants.This was an unusual case of peri-implantitis which occurred only in the implants on one side of the mouth although they all were unloaded implants.

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

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

The calibration of the intramolecular nitrogen isotope distribution in nitrous oxide measured by isotope ratio mass spectrometry.

Science.gov (United States)

Westley, Marian B; Popp, Brian N; Rust, Terri M

2007-01-01

Two alternative approaches for the calibration of the intramolecular nitrogen isotope distribution in nitrous oxide using isotope ratio mass spectrometry have yielded a difference in the 15N site preference (defined as the difference between the delta15N of the central and end position nitrogen in NNO) of tropospheric N2O of almost 30 per thousand. One approach is based on adding small amounts of labeled 15N2O to the N2O reference gas and tracking the subsequent changes in m/z 30, 31, 44, 45 and 46, and this yields a 15N site preference of 46.3 +/- 1.4 per thousand for tropospheric N2O. The other involves the synthesis of N2O by thermal decomposition of isotopically characterized ammonium nitrate and yields a 15N site preference of 18.7 +/- 2.2 per thousand for tropospheric N2O. Both approaches neglect to fully account for isotope effects associated with the formation of NO+ fragment ions from the different isotopic species of N2O in the ion source of a mass spectrometer. These effects vary with conditions in the ion source and make it impossible to reproduce a calibration based on the addition of isotopically enriched N2O on mass spectrometers with different ion source configurations. These effects have a much smaller impact on the comparison of a laboratory reference gas with N2O synthesized from isotopically characterized ammonium nitrate. This second approach was successfully replicated and leads us to advocate the acceptance of the site preference value 18.7 +/- 2.2 per thousand for tropospheric N2O as the provisional community standard until further independent calibrations are developed and validated. We present a technique for evaluating the isotope effects associated with fragment ion formation and revised equations for converting ion signal ratios into isotopomer ratios. Copyright 2007 John Wiley & Sons, Ltd.

Estimation of the specific mass effect in the isotope shifts of energy levels in the optical spectrum of Ba I and Ba II

International Nuclear Information System (INIS)

Pendrill, L.R.

1984-01-01

A graphical method for separating mass and volume effects from purely optical isotope shift data is presented and compared with King's ''bunching'' method. Recent experimental data on isotope shifts for a wide range of spectral lines in the naturally abundant isotopes of Ba I and Ba II are analysed. Some agreement is found with muonic X-ray data concerning the nuclear size for the isotopes 136, 137 and 138, but there is disagreement (over 20%) for the other isotopes. The level isotope shifts are further parameterised in terms of a linear model, and the specific mass effect is decomposed into sums of one-electron and two-electron shift parameters with respect to the inert-gas like ground state of Ba III. (orig.)

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%.

SIMS analysis of isotopic impurities in ion implants

International Nuclear Information System (INIS)

Sykes, D.E.; Blunt, R.T.

1986-01-01

The n-type dopant species Si and Se used for ion implantation in GaAs are multi-isotopic with the most abundant isotope not chosen because of potential interferences with residual gases. SIMS analysis of a range of 29 Si implants produced by several designs of ion implanter all showed significant 28 Si impurity with a different depth distribution from that of the deliberately implanted 29 Si isotope. This effect was observed to varying degrees with all fifteen implanters examined and in every 29 Si implant analysed to date 29 Si + , 29 Si ++ and 30 Si implants all show the same effect. In the case of Se implantation, poor mass resolution results in the implantation of all isotopes with the same implant distribution (i.e. energy), whilst implants carried out with good mass resolution show the implantation of all isotopes with the characteristic lower depth distribution of the impurity isotopes as found in the Si implants. This effect has also been observed in p-type implants into GaAs (Mg) and for Ga implanted in Si. A tentative explanation of the effect is proposed. (author)

Cutaneous sporotrichosis: Unusual clinical presentations

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Mahajan Vikram

2010-01-01

Full Text Available Three unusual clinical forms of sporotrichosis described in this paper will be a primer for the clinicians for an early diagnosis and treatment, especially in its unusual presentations. Case 1, a 52-year-old man, developed sporotrichosis over pre-existing facial nodulo-ulcerative basal cell carcinoma of seven-year duration, due to its contamination perhaps from topical herbal pastes and lymphocutaneous sporotrichosis over right hand/forearm from facial lesion/herbal paste. Case 2, a 25-year-old woman, presented with disseminated systemic-cutaneous, osteoarticular and possibly pleural (effusion sporotrichosis. There was no laboratory evidence of tuberculosis and treatment with anti-tuberculosis drugs (ATT did not benefit. Both these cases were diagnosed by histopathology/culture of S. schenckii from tissue specimens. Case 3, a 20-year-old girl, had multiple intensely pruritic, nodular lesions over/around left knee of two-year duration. She was diagnosed clinically as a case of prurigo nodularis and histologically as cutaneous tuberculosis, albeit, other laboratory investigations and treatment with ATT did not support the diagnosis. All the three patients responded well to saturated solution of potassium iodide (SSKI therapy. A high clinical suspicion is important in early diagnosis and treatment to prevent chronicity and morbidity in these patients. SSKI is fairly safe and effective when itraconazole is not affordable/ available.

Boron geochemistry from some typical Tibetan hydrothermal systems: Origin and isotopic fractionation

International Nuclear Information System (INIS)

Zhang, Wenjie; Tan, Hongbing; Zhang, Yanfei; Wei, Haizhen; Dong, Tao

2015-01-01

The Tibetan plateau is characterized by intense hydrothermal activity and abnormal enrichment of trace elements in geothermal waters. Hydrochemistry and B isotope samples from geothermal waters in Tibet were systematically measured to describe the fractionation mechanisms and provide constraints on potential B reservoirs. B concentrations range from 0.35 to 171.90 mg/L, and isotopic values vary between −16.57 ‰ and +0.52 ‰. Geothermal fields along the Indus-Yarlung Zangbo suture zone and N–S rifts are observed with high B concentrations and temperatures. The similar hydrochemical compositions of high-B geothermal waters with magmatic fluid and consistent modeling of B isotopic compositions with present δ"1"1B values imply that the B in high-B geothermal waters is mainly contributed by magmatic sources, probably through magma degassing. In contrast, geothermal fields in other regions of the Lhasa block have relatively low B concentrations and temperatures. After considering the small fractionation factor and representative indicators of Na/Ca, Cl/HCO_3, Na + K and Si, the conformity between modeling results and the isotopic compositions of host rocks suggests that the B in low-temperature geothermal fields is mainly sourced from host rocks. According to simulated results, the B in some shallow geothermal waters not only originated from mixing of cold groundwater with deep thermal waters, but it was also contributed by equilibration with marine sedimentary rocks with an estimated proportion of 10%. It was anticipated that this study would provide useful insight into the sources and fractionation of B as well as further understanding of the relationships between B-rich salt lakes and geothermal activities in the Tibetan plateau. - Highlights: • Chemical and boron isotopic data of geothermal waters in Tibetan plateau were introduced. • Unusual enrichment of boron in Tibetan geothermal waters is related to magmatic and host rocks. • Boron

Thermophysical properties of solid lithium hydride and its isotopic modifications

International Nuclear Information System (INIS)

Mel'nikova, T.N.

1981-01-01

The theory of the anharmonic lattice is used to calculate the thermophysical properties (thermal expansivity, lattice constant, compressibility, and elastic moduli) of all the isotopic modifications of solid lithium hydride sup(6,7)Li(H,D,T) at temperatures up to the melting point. A general analysis of isotopic effects is carried out; in particular the reverse isotopic effect in the lattice constant is explained and the isotopic effect in melting is discussed. The results of the calculations agree with available experimental data and can be used for those isotopic modifications of lithium hydride for which there exist no experimental results. (author)

Influence of Three-square-well Interaction Potential on Isotope Effect Coefficient of High-TC Superconductors

International Nuclear Information System (INIS)

Udomsamuthirun, P.; Dokkaemklang, S.; Kumvongsa, C.; Maneeratanakul, S.

2005-10-01

In this research, the exact formula of the isotope effect coefficient of s wave and d-wave superconductor in weak-coupling limit are derived by using a three square- well interaction potential that pairing interaction consists of 3 parts : an attractive electron-phonon interaction, an attractive non-electron-phonon interaction , and a repulsive Coulomb interaction . op ac , w w and c w is the characteristic energy cutoff of the Debye phonon , non-phonon ,and Coulomb respectively and 2 / 1 ac M- a w , and c op , w w do not depend on isotope mass(M). We find that, in all case of consideration, the isotope coefficient converges to 0.5 at lower value of Coulomb coupling constant and larger values of phonon and non-phonon coupling constant

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

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

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.

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

Isotopes and Radiation in Entomology. Proceedings of a Symposium on the Use of Isotopes and Radiation in Entomology

Energy Technology Data Exchange (ETDEWEB)

NONE

1968-06-15

Proceedings of a Symposium jointly organized by the IAEA and the Food and Agriculture Organization of the United Nations and held in Vienna, 4-8 December 1967. The meeting was attended by 82 participants from 29 countries and six international organizations. Contents: Isotope applications - ecology (7 papers); Radiation effect studies - non-genetic (8 papers); Isotope applications - physiology and biochemistry (2 papers); Isotope applications - chemosterilants (2 papers); Sterile-male technique (9 papers); Radiation effect studies - genetic (5 papers); Isotope applications - genetic (1 paper). Each paper is in its original language (21 English, 11 French, 1 Russian and 1 Spanish) and is preceded by an abstract in English with a second one in the original language if this is not English. Discussions are in English. (author)

Use of Isotopes for Studying Reaction Mechanisms -RE ...

Indian Academy of Sciences (India)

can give even greater details of chemical processes. Isotopic substitution ... isotope effect (KIE) would depend on the location of the isotope with respect to ... magnitude of KIE is given by kH/ko. ... How can one explain these variations? Theory.

Application of the isotopic index in isotope geochemical investigation

International Nuclear Information System (INIS)

Schuetze, H.

1982-06-01

A method is described which allows to calculate approximately isotope exchange equilibria between different crystalline silicates. The algorithm uses a newly introduced isotopic index. It is defined using isotopic increments of the variant types of silicatic bonds. This isotopic index gives a quantitative measure of the ability to enrich 18 O or 30 Si, respectively. The dependence of isotopic fractionations on temperature can be calculated approximately by means of the isotopic index, too. On this theoretical base some problems of magmatism and two varieties of an isotope geochemical model of the evolution of the Earth's crust are treated. Finally, the possibility is demonstrated to give prognostic statements about the likelihood of ore bearing of different granites. (author)

Isotopic meteoric line for Colombia

International Nuclear Information System (INIS)

Rodriguez N, Cesar O

2004-01-01

Isotope analyses from representative rainfall samples taken from different areas in Colombia were processed to yield the meteoric line. Stable isotope composition in precipitation reflects the effects of temperature, altitude and of the continental site, being affected by different sources of atmospheric humidity over the Colombian territory. There is a seasonal variation in isotopic composition of precipitation with grater σ deviation during the rainy season and lower values in the dry season. In coastal areas the variation is smaller and is more pronounced than at continental stations. Correlation between altitude and isotope content led to equations, which indicate, on a regional level, a change in isotopic composition with altitude, of about 0.5 σ units per 200 m, for O 18 and 4 σ units per 200 m for H 2 . Such equations may be used to identify the original altitude of precipitation water, in hydrological surface and groundwater studies. Meteoric line and the concepts derived from the resulting equations presented in this paper may be applied to the interpretation of isotope analysis in future hydrological studies, particularly in areas without available data

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

Shielding container for radioactive isotopes

International Nuclear Information System (INIS)

Sumi, Tetsuo; Tosa, Masayoshi; Hatogai, Tatsuaki.

1975-01-01

Object: To effect opening and closing bidirectional radiation used particularly for a gamma densimeter or the like by one operation. Structure: This device comprises a rotatable shielding body for receiving radioactive isotope in the central portion thereof and having at least two radiation openings through which radiation is taken out of the isotope, and a shielding container having openings corresponding to the first mentioned radiation openings, respectively. The radioactive isotope is secured to a rotational shaft of the shielding body, and the shielding body is rotated to register the openings of the shielding container with the openings of the shielding body or to shield the openings, thereby effecting radiation and cut off of gamma ray in the bidirection by one operation. (Kamimura, M.)

The isotope systematics of a juvenile intraplate volcano: Pb, Nd, and Srisotope ratios of basalts from Loihi Seamount, Hawaii

International Nuclear Information System (INIS)

Staudigel, H.; Zindler, A.; Leslie, T.

1984-01-01

Sr, Nd, and Pb isotope ratios for a representative suite of 15 basanites, alkali basalts, transitional basalts and tholeiites from Loihi Seamount, Hawaii, display unusually large variations for a single volcano, but lie within known ranges for Hawaiian basalts. Nd isotope ratios in alkali basalts show the largest relative variation (0.51291 - 0.51305), and include the nearly constant tholeiite value (approx.= 0.51297). Pb isotope ratios show similarly large ranges for tholeiites and alkali basalts and continue Tatsumoto's [31] 'Loa' trend towards higher 206 Pb/ 204 Pb, ratios, resulting in a substantial overlap with the 'Kea' trend. 206 Pb/ 204 Pb ratios for Loihi and other volcanoes along the Loa and Kea trends [31] are observed to correlate with the age of the underlying lithosphere suggesting lithosphere involvement in the formation of Hawaiian tholeiites. Loihi lavas display no correlation of Nd, Sr, or Pb isotope ratios with major element compositions or eruptive age, in contrast with observations of some other Hawaiian volcanoes. Isotope data for Loihi, as well as average values for Hawaiian volcanoes, are not adequately explained by previously proposed two-end-member models; new models for the origin and the development of Hawaiian volcanoes must include mixing of at least three geochemically distinct source regions and allow for the involvement of heterogeneous oceanic lithosphere. (orig.)

Use of Isotopes for Studying Reaction Mechanisms

Indian Academy of Sciences (India)

In the first part of this series, we discussed how isotopes can be used as markers to determine the nature of intermediates in chemical reactions. The second part covered the effect of isotopes on equilibria and reactions, in processes where the bond to the isotopic a tom is broken. We showed with specific examples how.

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)

Isotopically modified compounds

International Nuclear Information System (INIS)

Kuruc, J.

2009-01-01

In this chapter the nomenclature of isotopically modified compounds in Slovak language is described. This chapter consists of following parts: (1) Isotopically substituted compounds; (2) Specifically isotopically labelled compounds; (3) Selectively isotopically labelled compounds; (4) Non-selectively isotopically labelled compounds; (5) Isotopically deficient compounds.

Unusual magnetoresistance in cubic B20 Fe0.85Co0.15Si chiral magnets

Science.gov (United States)

Huang, S. X.; Chen, Fei; Kang, Jian; Zang, Jiadong; Shu, G. J.; Chou, F. C.; Chien, C. L.

2016-06-01

The B20 chiral magnets with broken inversion symmetry and C4 rotation symmetry have attracted much attention. The broken inversion symmetry leads to the Dzyaloshinskii-Moriya that gives rise to the helical and Skyrmion states. We report the unusual magnetoresistance (MR) of B20 chiral magnet Fe0.85Co0.15Si that directly reveals the broken C4 rotation symmetry and shows the anisotropic scattering by Skyrmions with respect to the current directions. The intimacy between unusual MR and broken symmetry is well confirmed by theoretically studying an effective Hamiltonian with spin-orbit coupling. The unusual MR serves as a transport signature for the Skyrmion phase.

Unusual magnetoresistance in cubic B20 Fe0.85Co0.15Si chiral magnets

International Nuclear Information System (INIS)

Huang, S X; Chen, Fei; Zang, Jiadong; Chien, C L; Kang, Jian; Shu, G J; Chou, F C

2016-01-01

The B20 chiral magnets with broken inversion symmetry and C 4 rotation symmetry have attracted much attention. The broken inversion symmetry leads to the Dzyaloshinskii–Moriya that gives rise to the helical and Skyrmion states. We report the unusual magnetoresistance (MR) of B20 chiral magnet Fe 0.85 Co 0.15 Si that directly reveals the broken C 4 rotation symmetry and shows the anisotropic scattering by Skyrmions with respect to the current directions. The intimacy between unusual MR and broken symmetry is well confirmed by theoretically studying an effective Hamiltonian with spin–orbit coupling. The unusual MR serves as a transport signature for the Skyrmion phase. (paper)

Broadband non-selective excitation of plutonium isotopes for isotope ratio measurements in resonance ionization mass spectrometry: a theoretical study.

Science.gov (United States)

Sankari, M

2012-10-15

Making isotope ratio measurements with minimum isotope bias has always been a challenging task to mass spectrometrists, especially for the specific case of plutonium, owing to the strategic importance of the element. In order to use resonance ionization mass spectrometry (RIMS) as a tool for isotope ratio measurements, optimization of the various laser parameters and other atomic and system parameters is critical to minimize isotopic biases. Broadband simultaneous non-selective excitation of the isotopes of plutonium in the triple resonance excitation scheme with λ(1) = 420.77 nm, λ(2) = 847.28 nm, and λ(3) = 767.53 nm based on density matrix formalism has been theoretically computed for the determination of isotope ratios. The effects of the various laser parameters and other factors such as the atomization temperature and the dimensions of the atomic beam on the estimation of isotope ratios were studied. The effects of Doppler broadening, and time-dependent excitation parameters such as Rabi frequencies, ionization rate and the effect of non-Lorenztian lineshape have all been incorporated. The average laser powers and bandwidths for the three-excitation steps were evaluated for non-selective excitation. The laser intensity required to saturate the three-excitation steps were studied. The two-dimensional lineshape contour and its features were investigated, while the reversal of peak asymmetry of two-step and two-photon excitation peaks under these conditions is discussed. Optimized powers for the non-selective ionization of the three transitions were calculated as 545 mW, 150 mW and 545 mW and the laser bandwidth for all the three steps was ~20 GHz. The isotopic bias between the resonant and off-resonant isotope under the optimized conditions was no more than 9%, which is better than an earlier reported value. These optimized laser power and bandwidth conditions are better than in the earlier experimental work since these comprehensive calculations yield

Synthesis of [methine-3H]DDT and its nitro-analog, and isotope effects in their enzyme-catalyzed dehydrochlorination

International Nuclear Information System (INIS)

Kurihara, N.; Ikemoto, Y.; Okutani, S.; Clark, A.G.

1989-01-01

[methine- 3 H]1,1-Di-(4-chlorophenyl)-2,2,2-trichloroethane ([methine- 3 H]DDT) and its di-(4-nitrophenyl) analog, both of high purity with a moderately high specific activity were prepared. Chloro-benzene was condensed with [1- 3 H]1-(4-chlorophenyl)-2,2,2-trichloro-ethanol, which has been synthesized by sodium boro[ 3 H]hydride reduction of 4-chlorophenyl trichloromethyl ketone. The purified [ 3 H]DDT had a specific activity of 0.77 Ci/mmol (28.49 GBq/mmol). [methine- 3 H]1,1-Diphenyl-2,2,2-trichloroethane was similarly synthesized and was nitrated to give [methine- 3 H]1,1-di-(4-nitrophenyl)-2,2,2-trichloro-ethane of 1.63 Ci/mmol (60.31 GBq/mmol). Dehydrochlorination with housefly enzyme (glutathione-dependent DDT dehydrochlorinase) showed a remarkable isotope effect. For DDT, the observed tritium isotope effect on V max /K m was 11.51±0.52. For the nitro-analog, the value was 11.3±1.2. We measured deuterium isotope effect on V max /K m for DDT in a competitive mode and obtained the value 4.19±0.34. Based on these values, the magnitude of intrinsic isotope effect values on DDT-dehydrochlorination reaction was discussed. (author)

Iodine isotopes and radiation safety

International Nuclear Information System (INIS)

Styro, B.; Nedvekajte, T.; Filistovich, V.

1992-01-01

Methods of concentration determination of stable and radioactive iodine isotopes in the Earth's different geospheres are described. Iodine isotopes concentration data, chemical forms and transformations as well as their exchange among separate geospheres of their global biochemical circulation (ocean, atmosphere, lithosphere and biosphere) are presented. Information on iodine isotopes as after-effects of nuclear installations accident (in particular, the Chernobyl accident) is generalized. The book is intended for scientists and practical workers in ecology and radioactivity protection and for a students of physics. 442 refs.; 82 figs.; 36 tabs

The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

Science.gov (United States)

von Sperber, Christian; Kries, Hajo; Tamburini, Federica; Bernasconi, Stefano M.; Frossard, Emmanuel

2014-01-01

Plants and microorganisms under phosphorus (P) stress release extracellular phosphatases as a strategy to acquire inorganic phosphate (Pi). These enzymes catalyze the hydrolysis of phosphoesters leading to a release of Pi. During the enzymatic hydrolysis an isotopic fractionation (ε) occurs leaving an imprint on the oxygen isotope composition of the released Pi which might be used to trace phosphorus in the environment. Therefore, enzymatic assays with acid phosphatases from wheat germ and potato tuber and alkaline phosphatase from Escherichia coli were prepared in order to determine the oxygen isotope fractionation caused by these enzymes. Adenosine 5‧ monophosphate and glycerol phosphate were used as substrates. The oxygen isotope fractionation caused by acid phosphatases is 20-30‰ smaller than for alkaline phosphatases, resulting in a difference of 5-7.5‰ in δ18O of Pi depending on the enzyme. We attribute the enzyme dependence of the isotopic fractionation to distinct reaction mechanisms of the two types of phosphatases. The observed difference is large enough to distinguish between the two enzymatic processes in environmental samples. These findings show that the oxygen isotope composition of Pi can be used to trace different enzymatic processes, offering an analytical tool that might contribute to a better understanding of the P-cycle in the environment.

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.

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)

Recent development in isotope ratio mass spectrometry

International Nuclear Information System (INIS)

Platzner, I.

1992-01-01

Within the limited of this review the following topics will be briefly discussed: a) Accuracy, precision, internal relative standard deviation (RISD) and external relative standard deviation (RESD) of isotope ratio measurements. With advanced instrumentation and use of standard reference materials, high accuracy and RESD = 0.002% (or better) may be achieved; b) The advantages of modern automatic isotope ratio mass spectrometer are briefly described. Computer controlled operation and data acquisition, and multiple ion collection are the recent important improvement; c) The isotopic fractionation during the course of isotope ratio measurement is considered as a major source of errors in thermal ionization of metallic elements. The phenomenon in strontium, neodymium, uranium, lead and calcium and methods to correct the measured data are discussed; d) Applications of isotope ratio mass spectrometry in atomic weight determinations, the isotope dilution technique, isotope geology, and isotope effects in biological systems are described together with specific applications in various research and technology area. (author)

alfa-Deuterium kinetic isotope effects in reactions of methyllithium. Is better aggregation the cause of lower reactivity?

DEFF Research Database (Denmark)

Holm, Torkil

1996-01-01

The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium......The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium...

Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2

Science.gov (United States)

Rhee, Young Min; Kim, Myung Soo

1998-10-01

The deuterium isotope effect on the product energy partitioning in the title reaction was investigated both experimentally and theoretically. The measured kinetic energy release (KER) showed a significant dependence on the position of deuteration. A reliable potential energy surface of the reaction was constructed from ab initio results using the recently developed interpolation algorithm. The classical trajectory calculation on this surface well reproduced the experimental finding. Close inspection of the potential energy surface revealed that the isotope effect on KER and the product rotations arose from the alteration of the symmetry of the reaction path near the transition state induced by the mass change upon isotopic substitution. The product vibrations were found to be affected by the change in the coupling constants which also arose from the mass-dependent change in the reaction path. Possibility of the quantum mechanical tunneling was also considered. Tunneling-corrected classical trajectory results were in excellent agreement with the experimental ones, indicating that the reaction proceeds via barrier penetration below the threshold.

Geothermal investigations with isotope and geochemical techniques in Latin America

International Nuclear Information System (INIS)

1992-03-01

The IAEA Co-ordinated Research Programme (CRP) for Latin America on the Use of Isotope and Geochemical Techniques in Geothermal Exploration started in 1984. The first activity carried out was a Seminar on isotope and geochemical techniques in geothermal exploration, which took place in June 1984 in Morelia, Mexico. During the seminar, which was attended by representatives of the institutions which later took part in the programme, the objectives, main research lines, and geothermal fields to be studied during the CRP were discussed. The first research contracts were awarded towards the end of 1984. The field work started in 1985 and continued through 1990. During the implementation of the CRP a considerable number of geothermal fields were studied in the nine participating countries. The investigations carried out were geochemically quite comprehensive in most cases, but in some others they were still in a reconnaissance stage when the CRP ended: the latter studies are not reported in these proceedings, but the data obtained are in principle available from the relevant national institutions. While investigations with conventional geochemical techniques had already started in several fields before 1985, isotope methods were applied for the first time in all cases during this CRP. Due to the remoteness and high elevation of many of the fields studied and the adverse meteorological conditions during long periods of the year, the investigations could not proceed rapidly: this is the main reason for the unusually long duration of the CRP, which could be concluded only after more than five years after its inception

Deciphering the iron isotope message of the human body

Science.gov (United States)

Walczyk, Thomas; von Blanckenburg, Friedhelm

2005-04-01

Mass-dependent variations in isotopic composition are known since decades for the light elements such as hydrogen, carbon or oxygen. Multicollector-inductively coupled plasma mass spectrometry (MC-ICP-MS) and double-spike thermal ionization mass spectrometry (TIMS) permit us now to resolve small variations in isotopic composition even for the heavier elements such as iron. Recent studies on the iron isotopic composition of human blood and dietary iron sources have shown that lighter iron isotopes are enriched along the food chain and that each individual bears a certain iron isotopic signature in blood. To make use of this finding in biomedical research, underlying mechanisms of isotope fractionation by the human body need to be understood. In this paper available iron isotope data for biological samples are discussed within the context of isotope fractionation concepts and fundamental aspects of human iron metabolism. This includes evaluation of new data for body tissues which show that blood and muscle tissue have a similar iron isotopic composition while heavier iron isotopes are concentrated in the liver. This new observation is in agreement with our earlier hypothesis of a preferential absorption of lighter iron isotopes by the human body. Possible mechanisms for inducing an iron isotope effect at the cellular and molecular level during iron uptake are presented and the potential of iron isotope effects in human blood as a long-term measure of dietary iron absorption is discussed.

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

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

Uranium isotope separation using styrene cation exchangers

International Nuclear Information System (INIS)

Kahovec, J.

1980-01-01

The separation of 235 U and 238 U isotopes is carried out either by simple isotope exchange in the system uranium-cation exchanger (sulphonated styrene divinylbenzene resin), or by combination of isotope exchange in a uranium-cation exchanger (Dowex 50, Amberlite IR-120) system and a chemical reaction. A review is presented of elution agents used, the degree of cation exchanger cross-linking, columns length, and 235 U enrichment. The results are described of the isotope effect study in a U(IV)-U(VI)-cation exchanger system conducted by Japanese and Romanian authors (isotope exchange kinetics, frontal analysis, reverse (indirect) frontal analysis). (H.S.)

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.).

Unusual radiological characteristics of teratoid/rhabdoid brain tumor ...

African Journals Online (AJOL)

We report a case of atypical teratoid rhabdoid brain tumor for 4 months old male child, who presented with unusual radiological findings, that can be confused with other brain tumors ,so we high light these unusual imaging features to aid in making correct diagnosis. Keywords: atypical teratoid–rhabdoid tumor, brain tumor, ...

The testis: the unusual, the rare and the bizarre

International Nuclear Information System (INIS)

Stewart, V.R.; Sidhu, P.S.

2007-01-01

Ultrasound is the preferred technique when imaging the scrotal contents. Although appearances of many of the more common abnormalities present the examiner with no diagnostic difficulty, the more unusual conditions may present a considerable challenge. Many normal variants, unusual and rare abnormalities may be instantly recognized once seen. The current review highlights the more unusual and rare conditions affecting the scrotal contents in order to allow the reader the opportunity to gain knowledge of their existence and to aid future interpretation of the difficult examination

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.)

Pyroxene Homogenization and the Isotopic Systematics of Eucrites

Science.gov (United States)

Nyquist, L. E.; Bogard, D. D.

1996-01-01

The original Mg-Fe zoning of eucritic pyroxenes has in nearly all cases been partly homogenized, an observation that has been combined with other petrographic and compositional criteria to establish a scale of thermal "metamorphism" for eucrites. To evaluate hypotheses explaining development of conditions on the HED parent body (Vesta?) leading to pyroxene homogenization against their chronological implications, it is necessary to know whether pyroxene metamorphism was recorded in the isotopic systems. However, identifying the effects of the thermal metamorphism with specific effects in the isotopic systems has been difficult, due in part to a lack of correlated isotopic and mineralogical studies of the same eucrites. Furthermore, isotopic studies often place high demands on analytical capabilities, resulting in slow growth of the isotopic database. Additionally, some isotopic systems would not respond in a direct and sensitive way to pyroxene homogenization. Nevertheless, sufficient data exist to generalize some observations, and to identify directions of potentially fruitful investigations.

Chemical and isotopic composition of precipitations in Syria

International Nuclear Information System (INIS)

Abou Zakhem, B.; Hafez, R.

2007-05-01

The objective of this study is to determine isotopic characteristics of precipitation, the climatic and geographical conditions affecting isotopic composition in order to obtain the input function of groundwater to evaluate the water resources.13 meteoric stations were selected in Syria for cumulative monthly rainfall sampling during two hydrological cycles; 1991-1992 and 1992-1993. The chemical and isotopic compositions of monthly precipitation were studied. The winter and spring rainfall isotopic characteristics were determined, in addition to the Syrian meteoric line (SMWL) was estimated with a slope of 6.62 and that of both Syria and Jordan of 6.73. The effect of climatic factors as temperature and relative air humidity on oxygen-18, deuterium and d-excess were studied and it was found that the relationship between temperature and oxygen-18 and deuterium is a positive linear correlation; however, it is a negative correlation with d-excess. The mean seasonal variation amplitude of 18 O was about 6%, and the amount effect on isotopic content of precipitation was studied. The geographic factors and its affect on isotopic contents of precipitation such as altitude were considered, furthermore, the isotopic gradient with altitude was determined for both oxygen-18 and deuterium (-0.14 % and -0.84% /100m respectively). The spatial distribution of oxygen-18, deuterium, tritium and d-excess indicted the effect of mountain chains and gaps between mountains on the isotopic content, the continental effect on tritium build-up by about 33% per 100 Km from the coast. The increase of d-excess values towards the south west proves the eastern Mediterranean climate type over this region.(author)

Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi

Directory of Open Access Journals (Sweden)

G. M. Weiss

2017-12-01

Full Text Available Over the last decade, hydrogen isotopes of long-chain alkenones have been shown to be a promising proxy for reconstructing paleo sea surface salinity due to a strong hydrogen isotope fractionation response to salinity across different environmental conditions. However, to date, the decoupling of the effects of alkalinity and salinity, parameters that co-vary in the surface ocean, on hydrogen isotope fractionation of alkenones has not been assessed. Furthermore, as the alkenone-producing haptophyte, Emiliania huxleyi, is known to grow in large blooms under high light intensities, the effect of salinity on hydrogen isotope fractionation under these high irradiances is important to constrain before using δDC37 to reconstruct paleosalinity. Batch cultures of the marine haptophyte E. huxleyi strain CCMP 1516 were grown to investigate the hydrogen isotope fractionation response to salinity at high light intensity and independently assess the effects of salinity and alkalinity under low-light conditions. Our results suggest that alkalinity does not significantly influence hydrogen isotope fractionation of alkenones, but salinity does have a strong effect. Additionally, no significant difference was observed between the fractionation responses to salinity recorded in alkenones grown under both high- and low-light conditions. Comparison with previous studies suggests that the fractionation response to salinity in culture is similar under different environmental conditions, strengthening the use of hydrogen isotope fractionation as a paleosalinity proxy.

Effects of alkalinity and salinity at low and high light intensity on hydrogen isotope fractionation of long-chain alkenones produced by Emiliania huxleyi

Science.gov (United States)

Weiss, Gabriella M.; Pfannerstill, Eva Y.; Schouten, Stefan; Sinninghe Damsté, Jaap S.; van der Meer, Marcel T. J.

2017-12-01

Over the last decade, hydrogen isotopes of long-chain alkenones have been shown to be a promising proxy for reconstructing paleo sea surface salinity due to a strong hydrogen isotope fractionation response to salinity across different environmental conditions. However, to date, the decoupling of the effects of alkalinity and salinity, parameters that co-vary in the surface ocean, on hydrogen isotope fractionation of alkenones has not been assessed. Furthermore, as the alkenone-producing haptophyte, Emiliania huxleyi, is known to grow in large blooms under high light intensities, the effect of salinity on hydrogen isotope fractionation under these high irradiances is important to constrain before using δDC37 to reconstruct paleosalinity. Batch cultures of the marine haptophyte E. huxleyi strain CCMP 1516 were grown to investigate the hydrogen isotope fractionation response to salinity at high light intensity and independently assess the effects of salinity and alkalinity under low-light conditions. Our results suggest that alkalinity does not significantly influence hydrogen isotope fractionation of alkenones, but salinity does have a strong effect. Additionally, no significant difference was observed between the fractionation responses to salinity recorded in alkenones grown under both high- and low-light conditions. Comparison with previous studies suggests that the fractionation response to salinity in culture is similar under different environmental conditions, strengthening the use of hydrogen isotope fractionation as a paleosalinity proxy.

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

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

48 CFR 235.070 - Indemnification against unusually hazardous risks.

Science.gov (United States)

2010-10-01

... 48 Federal Acquisition Regulations System 3 2010-10-01 2010-10-01 false Indemnification against unusually hazardous risks. 235.070 Section 235.070 Federal Acquisition Regulations System DEFENSE... DEVELOPMENT CONTRACTING 235.070 Indemnification against unusually hazardous risks. ...

Calcium isotopic anomalies in the Allende meteorite

International Nuclear Information System (INIS)

Lee, T.; Papanastassiou, D.A.; Wasserburg, G.J.

1978-01-01

We report isotopic anomalies in Ca which were found in two Ca-Al-rich inclusions of the Allende meteorite. These inclusions previously had been shown to contain special anomalies for Mg and O which were attributed to fractionation and unknown nuclear effects. The Ca data, when corrected for mass fractionation by using 40 Ca/ 44 Ca as a standard, show nonlinear isotopic effects in 48 Ca of +13.5 per mil and in 42 Ca of +1.7 per mil for one sample. The second sample shows a 48 Ca depletion of -2.9 per mil, but all other isotopes are normal. Samples with large excesses in 26 Mg show no Ca anomalies. The effects demonstrate that isotopic anomalies exist for higher-atomic-number refractory elements in solar-system materials and do not appear to be readily explainable by a simple model. The correlation of O, Mg, and Ca results on the same inclusions requires the addition and preservation in the solar system of components from idverse nucleosynthetic sources. Observed anomalous Mg and Ca compositions for coexisting mineral phases are uniform within each inclusion, and require initial isotopic homogeneity within an inclusion but the preservation of wide variations between inclusions. Assuming formation of these inclusions by condensation from a gaseous part of the solar nebula, this implies isotopic heterogeneity on a scale of 10-10 2 km within the nebula

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.

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.

Unusual computed tomography findings and complications in acute appendicitis

International Nuclear Information System (INIS)

Palacio, Glaucia Andrade e Silva; D'Ippolito, Giuseppe

2003-01-01

The objective of this article is to describe and illustrate unusual computed tomography (CT) findings in patients with acute appendicitis. We reviewed the charts of 200 patients with clinical suspicion of acute appendicitis who were submitted to abdominal CT before surgery. Patients with unusual presentation or complications were selected for illustrating the main CT findings. Unusual complications of acute appendicitis were related to anomalous position of the appendix, contiguity to intraperitoneal organs such as the liver, gall bladder, annexes and the bladder and continuous use of anti inflammatory or antibiotics during the diagnostic process. We concluded that CT is a useful diagnostic tool in patients with complicated or unusual presentation acute appendicitis. The first step towards diagnosis in these cases i to have in mind the hypothesis of appendicitis in patients with acute abdominal pain. (author)

Production Situation and Technology Prospect of Medical Isotopes

Directory of Open Access Journals (Sweden)

GAO Feng;LIN Li;LIU Yu-hao;MA Xing-jun

2016-10-01

Full Text Available The isotope production technology was overviewed, including traditional and newest technology. The current situation of medical isotope production was introduced. The problems faced by isotope supply and demand were analyzed. The future development trend of medical isotopes and technology prospect were put forward. As the most populous country, nuclear medicine develops rapidly, however, domestic isotope mainly relies on imports. The highly productive and relatively safe MIPR is expected to be an effective way to breakthrough the bottleneck of the development of nuclear medicine. Traditional isotope production technologies with reactor can be improved. It's urgent to research and promote new isotope production technologies with reactor. Those technologies which do not depend on reactor will have a bright market prospects.

Isotope effects and their implications for the covalent binding of inhaled [3H]- and [14C]formaldehyde in the rat nasal mucosa

International Nuclear Information System (INIS)

Heck Hd'; Casanova, M.

1987-01-01

DNA-protein crosslinks were formed in the nasal respiratory mucosa of Fischer-344 rats exposed for 3 hr to selected concentrations of [ 3 H]- and [ 14 C]formaldehyde ( 3 HCHO and H 14 CHO). In rats depleted of glutathione (GSH) and exposed to 10 ppm of 3 HCHO and H 14 CHO, the 3 H/ 14 C ratio of the fraction of the DNA that was crosslinked to proteins was significantly (39 +/- 6%) higher than that of the inhaled gas. This suggests an isotope effect, either on the formation of DNA-protein crosslinks by labeled HCHO or on the oxidation of labeled HCHO catalyzed by formaldehyde (FDH) or aldehyde dehydrogenase (AldDH). The possibility of an isotope effect on the formation of crosslinks was investigated using rat hepatic nuclei incubated with [ 3 H]- and [ 14 C]formaldehyde (0.1 mM, 37 degrees C). A small (3.4 +/- 0.9%) isotope effect was detected on this reaction, which slightly favored 3 HCHO over H 14 CHO in binding to DNA. The magnitude of this isotope effect cannot account for the high isotope ratio observed in the crosslinked DNA in vivo. The possibility of an isotope effect on the oxidation of 3 HCHO and H 14 CHO catalyzed by FDH was investigated using homogenates of the rat nasal mucosa incubated with [ 3 H]- and [ 14 C]formaldehyde at total formaldehyde concentrations ranging from 0.1 to 11 microM, NAD+ (1 mM), GSH (15 mM), and pyrazole (1 mM). The experiments showed that 3 HCHO is oxidized significantly more slowly than H 14 CHO under these conditions (Vmax/Km (H 14 CHO) divided by Vmax/Km ( 3 HCHO) = 1.82 +/- 0.11). A similar isotope effect was observed in the absence of GSH, presumably due to the oxidation of 3 HCHO and H 14 CHO catalyzed by AldDH

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

On the odd-even effect in the charge radii of isotopes

International Nuclear Information System (INIS)

Talmi, I.

1984-01-01

Core polarization by valence neutrons is suggested as a possible mechanism for producing odd-even variation in the charge radii of isotopes. The nuclei considered have closed proton shells and neutrons in states with lowest seniority or generalized seniority. Simple expressions are derived for jsup(n) neutron configurations and various multipole terms of the pn interaction. The resulting expressions give a good fit to the radii of calcium isotopes and also of lead isotopes for which these expressions are only approximate. (orig.)

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

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)

Stable isotope analysis in primatology: a critical review.

Science.gov (United States)

Sandberg, Paul A; Loudon, James E; Sponheimer, Matt

2012-11-01

Stable isotope analysis has become an important tool in ecology over the last 25 years. A wealth of ecological information is stored in animal tissues in the relative abundances of the stable isotopes of several elements, particularly carbon and nitrogen, because these isotopes navigate through ecological processes in predictable ways. Stable carbon and nitrogen isotopes have been measured in most primate taxonomic groups and have yielded information about dietary content, dietary variability, and habitat use. Stable isotopes have recently proven useful for addressing more fine-grained questions about niche dynamics and anthropogenic effects on feeding ecology. Here, we discuss stable carbon and nitrogen isotope systematics and critically review the published stable carbon and nitrogen isotope data for modern primates with a focus on the problems and prospects for future stable isotope applications in primatology. © 2012 Wiley Periodicals, Inc.

Anomalous isotope effects in the U(IV)-U(VI) exchange system

International Nuclear Information System (INIS)

Fujii, Yasuhiko; Nomura, Masao; Okamoto, Makoto; Onitsuka, Hatsuki; Nakanishi, Takashi.

1992-01-01

In previous papers, the enrichment of 236 U in the U(IV) - U(VI) chemical exchange system was found to be significantly smaller than the value estimated by the normal mass dependence enrichment of 235 U. Further experiments have been carried out in the present work to confirm the strange phenomenon of the isotopic anomaly in uranium enrichment. The results have indicated that the separation coefficient of 236 U is the same value as one previously reported. To confirm the anomaly of uranium isotope separation, α-ray spectrometry was implemented to check the enrichment behavior of 234 U. Although no theoretical explanation is given for the isotopic anomaly, this is favorable phenomenon for the re-enrichment of recycled uranium which contains isotopes 232 U and 236 U. (author)

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