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Sample records for isotopically enhanced molecular

  1. Isotope separation using molecular gases and molecular lasers

    International Nuclear Information System (INIS)

    Jetter, H.

    1975-01-01

    Isotope separation using molecular gas and molecular lasers offers several advantages over the alternative method which uses dye lasers and atomic vapour. These advantages are the easy handling of the raw material, the big isotopic shift in the IR, the good efficiency of the laser and the chemical extraction of the excited isotopes. In the case of uranium difficulties arise from the great number of superimposed lines in the absorption band of the UF 6 molecule. Several of these absorption bands were measured using laser spectrometers with ultra-high resolution. The conditions for selective excitation were estimated. (orig.) [de

  2. The role and future of in-vitro isotopic techniques in molecular biology

    International Nuclear Information System (INIS)

    Dar, L.; Khan, B.K.

    2004-01-01

    In this review we discuss isotopic in-vitro molecular biology techniques, and their advantages and applications. Isotopic methods have helped to shape molecular biology since its early days. Despite the availability of non-isotopic alternatives, isotopic methods continue to be used in molecular biology due to certain advantages, especially related to sensitivity and cost-effectiveness. Numerous techniques involving the use of isotopes help in the characterization of genes, including the detection of single nucleotide polymorphisms (SNPs) or mutations. Other isotopic molecular methods are utilized to study the phenotypic expression of gene sequences and their mutation. Emerging branches of molecular biology like functional genomics and proteomics are extremely important for exploiting the rapidly growing data derived from whole genomic sequencing of human and microbial genomes. Recent molecular biology applications like the high-throughput array techniques are relevant in the context of both structural and functional genomics. In proteomics, stable isotope based technology has found applications in the analysis of protein structure and interactions. (author)

  3. Molecular Isotopic Distribution Analysis (MIDAs) with adjustable mass accuracy.

    Science.gov (United States)

    Alves, Gelio; Ogurtsov, Aleksey Y; Yu, Yi-Kuo

    2014-01-01

    In this paper, we present Molecular Isotopic Distribution Analysis (MIDAs), a new software tool designed to compute molecular isotopic distributions with adjustable accuracies. MIDAs offers two algorithms, one polynomial-based and one Fourier-transform-based, both of which compute molecular isotopic distributions accurately and efficiently. The polynomial-based algorithm contains few novel aspects, whereas the Fourier-transform-based algorithm consists mainly of improvements to other existing Fourier-transform-based algorithms. We have benchmarked the performance of the two algorithms implemented in MIDAs with that of eight software packages (BRAIN, Emass, Mercury, Mercury5, NeutronCluster, Qmass, JFC, IC) using a consensus set of benchmark molecules. Under the proposed evaluation criteria, MIDAs's algorithms, JFC, and Emass compute with comparable accuracy the coarse-grained (low-resolution) isotopic distributions and are more accurate than the other software packages. For fine-grained isotopic distributions, we compared IC, MIDAs's polynomial algorithm, and MIDAs's Fourier transform algorithm. Among the three, IC and MIDAs's polynomial algorithm compute isotopic distributions that better resemble their corresponding exact fine-grained (high-resolution) isotopic distributions. MIDAs can be accessed freely through a user-friendly web-interface at http://www.ncbi.nlm.nih.gov/CBBresearch/Yu/midas/index.html.

  4. 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

  5. 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

  6. Carbon Isotope Chemistry in Molecular Clouds

    Science.gov (United States)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  7. Covalently bound molecular states in beryllium and carbon isotopes

    International Nuclear Information System (INIS)

    Wolfram von, Oertzen; Hans-Gerhard, Bohlen; Wolfram von, Oertzen

    2003-01-01

    Nuclear clustering in N=Z nuclei has been studied since many decades. States close to the decay thresholds, as described by the Ikeda diagram, are of particular interest. Recent studies in loosely bound systems, as observed with neutron-rich nuclei has revived the interest in cluster structures in nuclei, with additional valence neutrons, which give rise to pronounced covalent molecular structures. The Beryllium isotopes represent the first example of such unique states in nuclear physics with extreme deformations. In the deformed shell model these are referred to as super- and hyper-deformation. These states can be described explicitly by molecular concepts, with neutrons in covalent binding orbits. Examples of recent experiments performed at the HMI-Berlin demonstrating the molecular structure of the rotational bands in Beryllium isotopes are presented. Further work on chain states (nuclear polymers) in the carbon isotopes is in progress, these are the first examples of deformed structures in nuclei with an axis ratio of 3:1. A threshold diagram with clusters bound via neutrons in covalent molecular configurations can be established, which can serve as a guideline for future work. (authors)

  8. Low energy methods of molecular laser isotope separation

    International Nuclear Information System (INIS)

    Makarov, G N

    2015-01-01

    Of the many proposals to date for laser-assisted isotope separation methods, isotope-selective infrared (IR) multiphoton dissociation (MPD) of molecules has been the most fully developed. This concept served as the basis for the development and operation of the carbon isotope separation facility in Kaliningrad, Russia. The extension of this method to heavy elements, including uranium, is hindered by, among other factors, the high power consumption and the lack of high-efficiency high-power laser systems. In this connection, research and development covering low energy methods for the laser separation of isotopes (including those of heavy atoms) is currently in high demand. This paper reviews approaches to the realization of IR-laser-induced isotope-selective processes, some of which are potentially the basis on which low-energy methods for molecular laser isotope separation can be developed. The basic physics and chemistry, application potential, and strengths and weaknesses of these approaches are discussed. Potentially promising alternatives to the title methods are examined. (reviews of topical problems)

  9. Isotopic and molecular fractionation in combustion; three routes to molecular marker validation, including direct molecular 'dating' (GC/AMS)

    Science.gov (United States)

    Currie, L. A.; Klouda, G. A.; Benner, B. A.; Garrity, K.; Eglinton, T. I.

    The identification of unique isotopic, elemental, and molecular markers for sources of combustion aerosol has growing practical importance because of the potential effects of fine particle aerosol on health, visibility and global climate. It is urgent, therefore, that substantial efforts be directed toward the validation of assumptions involving the use of such tracers for source apportionment. We describe here three independent routes toward carbonaceous aerosol molecular marker identification and validation: (1) tracer regression and multivariate statistical techniques applied to field measurements of mixed source, carbonaceous aerosols; (2) a new development in aerosol 14C metrology: direct, pure compound accelerator mass spectrometry (AMS) by off-line GC/AMS ('molecular dating'); and (3) direct observation of isotopic and molecular source emissions during controlled laboratory combustion of specific fuels. Findings from the combined studies include: independent support for benzo( ghi)perylene as a motor vehicle tracer from the first (statistical) and second (direct 'dating') studies; a new indication, from the third (controlled combustion) study, of a relation between 13C isotopic fractionation and PAH molecular fractionation, also linked with fuel and stage of combustion; and quantitative data showing the influence of both fuel type and combustion conditions on the yields of such species as elemental carbon and PAH, reinforcing the importance of exercising caution when applying presumed conservative elemental or organic tracers to fossil or biomass burning field data as in the first study.

  10. 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

  11. 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.

  12. Molecular laser isotope separation programme at BARC

    International Nuclear Information System (INIS)

    Sarkar, Sisir K.; Parthasarathy, Venkatachari

    2007-09-01

    Little over thirty years ago, BARC ventured into a new frontier of scientific research: Molecular Laser Isotope Separation (MLIS) programme based on the interaction of lasers with molecules. The initial project was a scheme to produce enriched uranium. The idea was to use the intense, monochromatic light of lasers to break the chemical bonds of only those molecules containing the fissionable isotope uranium-235. At present the programme is evolving around separation of low and middle mass isotopes, namely sulphur 34/33/32, oxygen 17/18, carbon 13/12, hydrogen T/D/H to be followed by an advanced engineering programme designed to lead to a demonstration plant. The latest results have come very close to the design parameters specified for a full-scale separation of carbon isotopes. All these expertise provide an infra structure for future front line R and D activities in the general area of Laser Photochemical Technology which would include i) LIS of other useful elements ii) Material processing and iii) Fuel reprocessing/ waste management (author)

  13. Oxygen isotopic fractionation of O₂ during adsorption and desorption processes using molecular sieve at low temperatures.

    Science.gov (United States)

    Ahn, Insu; Kusakabe, Minoru; Lee, Jong Ik

    2014-06-15

    Cryogenic trapping using molecular sieves is commonly used to collect O2 extracted from silicates for (17)O/(16)O and (18)O/(16)O analyses. However, gases which interfere with (17)O/(16)O analysis, notably NF3, are also trapped and their removal is essential for accurate direct measurement of the (17)O/(16)O ratio. It is also necessary to identify and quantify any isotopic fractionation associated with the use of cryogenic trapping using molecular sieves. The oxygen isotopic compositions of O2 before and after desorption from, and adsorption onto, 13X and 5A molecular sieves (MS13X and MS5A) at 0°C, -78°C, -114°C, and -130°C were measured in order to determine the oxygen isotopic fractionation at these temperatures. We also investigated whether isotopic fractionation occurred when O2 gas was transferred sequentially into a second cold finger, also containing molecular sieve. It was confirmed that significant oxygen isotopic fractionation occurs between the gaseous O2 and that adsorbed onto molecular sieve, if desorption and adsorption are incomplete. As the fraction of released or untrapped O2 becomes smaller with decreasing trapping temperature (from 0 to -130°C), the isotopic fractionation becomes larger. Approximately half of the total adsorbed O2 is released from the molecular sieve during desorption at -114°C, which is the temperature recommended for separation from NF3 (retained on the molecular sieve), and this will interfere with (17)O/(16)O measurements. The use of a single cold finger should be avoided, because partial desorption is accompanied by oxygen isotopic fractionation, thereby resulting in inaccurate isotopic data. The use of a dual cold finger arrangement is recommended because, as we have confirmed, the transfer of O2 from the first trap to the second is almost 100%. However, even under these conditions, a small isotopic fractionation (0.18 ± 0.05‰ in δ(17)O values and 0.26 ± 0.06‰ in δ(18)O values) occurred, with O2 in

  14. Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

    Science.gov (United States)

    Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

    2018-06-01

    Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

  15. Molecular dynamics simulation of hydrogen isotope injection into graphene

    International Nuclear Information System (INIS)

    Nakamura, Hiroaki; Takayama, Arimichi; Ito, Atsushi

    2007-07-01

    We reveal the hydrogen isotope effect of three chemical reactions, i.e., the reflection, the absorption and the penetration ratios, by classical molecular dynamics simulation with a modified Brenner's reactive empirical bond order (REBO) potential. We find that the reflection by π-electron does not depend on the mass of the incident isotope, but the peak of the reflection by nuclear moves to higher side of incident energy. In addition to the reflection, we also find that the absorption ratio in the positive z side of the graphene becomes larger, as the mass of the incident isotope becomes larger. On the other hand, the absorption ratio in the negative z side of the graphene becomes smaller. Last, it is found that the penetration ratio does not depend on the mass of the incident isotope because the graphene potential is not affected by the mass. (author)

  16. Modified molecular sieves: stationary phase for the gas chromatographic separation of hydrogen isotopes

    International Nuclear Information System (INIS)

    Pushpa, K.K.; Annaji Rao, K.; Iyer, R.M.

    1993-01-01

    Gas chromatographic separation of hydrogen isotopes on different molecular sieves at liquid nitrogen temperature has been investigated. Normal molecular sieves 5A, 13X and AW500 are not satisfactory for the purpose both in the partially dehydrated as well as totally dehydrated state. Molecular sieve 4A in partially dehydrated state separated H 2 and D 2 while H 2 and HD are not well resolved. Iron exchanged or coated molecular sieves 4A, 5A, 13X and AW500 in the partially dehydrated state separated the isotopic mixtures H 2 , HD, D 2 and H 2 , HT, T 2 . The resolution varied depending on the amount of iron content and the residual moisture in the molecular sieves. Good separations were obtained on 15% Fe coated molecular sieve 5A and 5% Fe coated molecular sieve 4A. (author). 18 refs., 6 figs., 3 tabs

  17. 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

  18. The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

    Science.gov (United States)

    Wasylenki, L.E.; Weeks, C.L.; Bargar, J.R.; Spiro, T.G.; Hein, J.R.; Anbar, A.D.

    2011-01-01

    Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect ??97/95Modissolved-??97/95Moadsorbed=1.8??? have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces. ?? 2011 Elsevier Ltd.

  19. Molecular modeling study of lithium isotopic separation by crown-ethers in ethanol

    International Nuclear Information System (INIS)

    Dehez, F.

    2002-01-01

    The isotopic separation of lithium ion isotopes is studied at the CEA in Pierrelatte using a liquid chromatography technique. Exchange systems are composed by crown-ethers grafted on silica (12C4, 15C5, B15C5, DB15C5, 18C6, B18C6). Lithium is introduced as a salt melted in ethanol. This work concerns the theoretical study of lithium isotopic exchange reactions with those systems. After a brief presentation of isotope separation techniques and isotopic effects (Chap.I), we describe the methods of theoretical chemistry used in this work (Chap. II). In chapter III, we test AM1 and PM3 semi-empirical methods for the treatment of Li + /crown-ether species. Then, we calculate isotopic separation factors via ab initio and semi-empirical calculations for the exchange reactions in vacuum. The different crown-ethers are considered with and without graftings arms. Studies of exchange reactions in ethanol are presented in chapter IV. First, each species of the reaction are solvated by a few ethanol molecules. Isotopic separation factors calculated show a large effect of the solvent on the exchange reaction. The effect of the grafting arm has been investigated using hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics for species with the 12C4. Trajectories have been generated successively with 7 Li and 6 Li. Atomic velocity autocorrelation functions have allowed the access to vibrational frequencies necessary to calculate isotopic separation factors. The last chapter is devoted to methodological developments made during this Ph.D. We propose an approach to treat long range electrostatic interactions in hybrid QM/MM method, relying on a lattice summation technique. (author) [fr

  20. Diverging effects of isotopic fractionation upon molecular diffusion of noble gases in water: mechanistic insights through ab initio molecular dynamics simulations.

    Science.gov (United States)

    Pinto de Magalhães, Halua; Brennwald, Matthias S; Kipfer, Rolf

    2017-03-22

    Atmospheric noble gases are routinely used as natural tracers to analyze gas transfer processes in aquatic systems. Their isotopic ratios can be employed to discriminate between different physical transport mechanisms by comparison to the unfractionated atmospheric isotope composition. In many applications of aquatic systems molecular diffusion was thought to cause a mass dependent fractionation of noble gases and their isotopes according to the square root ratio of their masses. However, recent experiments focusing on isotopic fractionation within a single element challenged this broadly accepted assumption. The determined fractionation factors of Ne, Ar, Kr and Xe isotopes revealed that only Ar follows the prediction of the so-called square root relation, whereas within the Ne, Kr and Xe elements no mass-dependence was found. The reason for this unexpected divergence of Ar is not yet understood. The aim of our computational exercise is to establish the molecular-resolved mechanisms behind molecular diffusion of noble gases in water. We make the hypothesis that weak intermolecular interactions are relevant for the dynamical properties of noble gases dissolved in water. Therefore, we used ab initio molecular dynamics to explicitly account for the electronic degrees of freedom. Depending on the size and polarizability of the hydrophobic particles such as noble gases, their motion in dense and polar liquids like water is subject to different diffusive regimes: the inter-cavity hopping mechanism of small particles (He, Ne) breaks down if a critical particle size achieved. For the case of large particles (Kr, Xe), the motion through the water solvent is governed by mass-independent viscous friction leading to hydrodynamical diffusion. Finally, Ar falls in between the two diffusive regimes, where particle dispersion is propagated at the molecular collision time scale of the surrounding water molecules.

  1. 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

  2. Molecular selectivity of graphene-enhanced Raman scattering.

    Science.gov (United States)

    Huang, Shengxi; Ling, Xi; Liang, Liangbo; Song, Yi; Fang, Wenjing; Zhang, Jin; Kong, Jing; Meunier, Vincent; Dresselhaus, Mildred S

    2015-05-13

    Graphene-enhanced Raman scattering (GERS) is a recently discovered Raman enhancement phenomenon that uses graphene as the substrate for Raman enhancement and can produce clean and reproducible Raman signals of molecules with increased signal intensity. Compared to conventional Raman enhancement techniques, such as surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS), in which the Raman enhancement is essentially due to the electromagnetic mechanism, GERS mainly relies on a chemical mechanism and therefore shows unique molecular selectivity. In this paper, we report graphene-enhanced Raman scattering of a variety of different molecules with different molecular properties. We report a strong molecular selectivity for the GERS effect with enhancement factors varying by as much as 2 orders of magnitude for different molecules. Selection rules are discussed with reference to two main features of the molecule, namely its molecular energy levels and molecular structures. In particular, the enhancement factor involving molecular energy levels requires the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies to be within a suitable range with respect to graphene's Fermi level, and this enhancement effect can be explained by the time-dependent perturbation theory of Raman scattering. The enhancement factor involving the choice of molecular structures indicates that molecular symmetry and substituents similar to that of the graphene structure are found to be favorable for GERS enhancement. The effectiveness of these factors can be explained by group theory and the charge-transfer interaction between molecules and graphene. Both factors, involving the molecular energy levels and structural symmetry of the molecules, suggest that a remarkable GERS enhancement requires strong molecule-graphene coupling and thus effective charge transfer between the molecules and graphene. These conclusions are further

  3. Structure of Li, Be And B isotopes studied with quantum molecular dynamic model

    International Nuclear Information System (INIS)

    Abdel-Hafiez, A.; Saleh, Z.A.

    2000-01-01

    Quantum molecular dynamics (QMD) is applied to study the ground state properties of Li, Be and B isotopes. The model Hamiltonian includes both two-and three-body density dependent interactions, a Coulomb term, and a momentum dependent Pauli potential. With parameters which guarantee the infinite nuclear matter properties, the QMD model can only reproduce the binding energies for Be and B isotopes. The experimental root mean square radii of the Li, Be and B isotopes are not sufficiently reproduced by these parameters. It is shown, however, that the binding energies and root mean square radii of these isotopes can simultaneously be reproduced in the lower density limit of the potential parameters

  4. Atomic and molecular isotope separation

    International Nuclear Information System (INIS)

    Melamed, N.T.

    1979-01-01

    A method for differentially exciting a selected isotopic species in a mixture of isotopic species is described characterized in that almost the entire isotopic mixture is placed in an excited gaseous state; and a preselected isotopic species is then selectively de-excited through stimulated emission

  5. Practical-scale tests of cryogenic molecular sieve for separating low-concentration hydrogen isotopes from helium

    International Nuclear Information System (INIS)

    Willms, R.S.; Taylor, D.J.; Enoeda, Mikio; Okuno, Kenji

    1994-01-01

    Earlier bench-scale work at the Tritium Systems Test Assembly (TSTA) at Los Alamos National Laboratory examined a number of adsorbents for their suitability for separating low-concentration hydrogen (no tritium) from helium. One of the effective adsorbents was Linde 5A molecular sieve. Recently, experiments including tritium were conducted using practical-scale adsorbers. These tests used existing cryogenic molecular sieve beds (CMSB's) which each contain about 1.6 kg of Linde 5A molecular sieve. They are part of the TSTA integrated tritium processing system. Gas was fed to each CMSB at about 13 SLPM with a nominal composition of 99% He, 0.98% H 2 and 0.02% HT. In all cases, for an extended period of time, the beds allowed no detectable (via Raman spectroscopy) hydrogen isotopes to escape in the bed effluent. Thereafter, the hydrogen isotopes appeared in the bed exit with a relatively sharp breakthrough curve. This work concludes that cryogenic molecular sieve adsorption is an practical and effective means of separating low-concentration hydrogen isotopes from a helium carrier

  6. Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

    Science.gov (United States)

    Keedakkadan, Habeeb Rahman; Abe, Osamu

    2015-04-30

    The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic

  7. Mass spectrometric investigation of the isotopes of ozone in the laboratory and the stratosphere

    International Nuclear Information System (INIS)

    Mauersberger, K.; Morton, J.; Schueler, B.

    1991-01-01

    During the last few years information on the isotope anomalies of ozone has substantially increased. Whenever ozone is formed in a gas phase reaction, an enhancement in its heavy isotopes is found of magnitude 12-14% ( 50 O 3 ) above the statistically expected values. The mass-independent enhancement decreases toward higher pressures and also shows a pronounced temperature dependence. Toward lower temperatures the enhancement becomes less. Studies of all possible ozone isotopes have shown that molecular symmetry plays a major role. Even large enhancements, above the laboratory results, have been occasionally measured in the stratosphere using a number of different experimental techniques. A correlation between very high heavy ozone enhancement (> 30%) and high solar activity may exist. The behavior of ozone isotopes will provide information about the ozone formation process

  8. Thermal transport across solid-solid interfaces enhanced by pre-interface isotope-phonon scattering

    Science.gov (United States)

    Lee, Eungkyu; Luo, Tengfei

    2018-01-01

    Thermal transport across solid interfaces can play critical roles in the thermal management of electronics. In this letter, we use non-equilibrium molecular dynamics simulations to investigate the isotope effect on the thermal transport across SiC/GaN interfaces. It is found that engineered isotopes (e.g., 10% 15N or 71Ga) in the GaN layer can increase the interfacial thermal conductance compared to the isotopically pure case by as much as 23%. Different isotope doping features, such as the isotope concentration, skin depth of the isotope region, and its distance from the interface, are investigated, and all of them lead to increases in thermal conductance. Studies of spectral temperatures of phonon modes indicate that interfacial thermal transport due to low-frequency phonons (transport. This work may provide insights into interfacial thermal transport and useful guidance to practical material design.

  9. Enhancement of isotope exchange reactions over ceramic breeder material by deposition of catalyst metal

    International Nuclear Information System (INIS)

    Narisato, Y.; Munakata, K.; Koga, A.; Yokoyama, Y.; Takata, T.; Okabe, H.

    2004-01-01

    The deposition of catalyst metals in ceramic breeders could enhance the release rate of tritium due to the promotion of isotope exchange reactions taking place at the interface of the breeder surface and the sweep gas. In this work, the authors examined the effects of catalytic active metal deposited on lithium titanate on the isotope exchange reactions. With respect to the virgin lithium titanate, it was found that the rate of the isotope exchange reactions taking place on the surface is quite low. However, the deposition of palladium greatly increased the exchange reaction rate. The effect of the amounts of deposited palladium on the isotope exchange reaction rate was also investigated. The results indicate that the exchange reactions are still enhanced even if the amounts of deposited palladium are as low as 0.04%

  10. 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.

  11. Integrated modelling of enhanced in situ biodenitrification in a fractured aquifer: biogeochemistry and isotope geochemistry

    Science.gov (United States)

    Rodríguez-Escales, Paula; Folch, Albert; van Breukelen, Boris M.; Vidal-Gavilan, Georgina; Soler, Albert

    2014-05-01

    Enhanced in-situ biodenitrification is a feasible technology to recovery groundwater polluted by nitrates and achieves drinking water standards. Under optimum conditions, nitrate is reduced by autochthonous bacteria trough different reactions until arrive to harmless dinitrogen gas. Isotopic fractionation monitoring in field applications allows knowing the exact degree and the real scope of this technology. Using the Rayleigh equation the change in the isotope ratio of the nitrate molecule (δ15N-NO3-, δ18O-NO3-) is related to the fraction of molecules remaining as a result of biodenitrification. However, Rayleigh application at field scale is sometimes limited due to other processes involved during groundwater flow such as dispersion or adsorption and geological media heterogeneities that interferes in concentration values. Then, include isotope fractionation processes in reactive transport models is a useful tool to interpret and predict data from in-situ biodenitrification. We developed a reactive transport model of enhanced in situ application at field scale in a fractured aquifer that considers biogeochemical processes as well as isotope fractionation to enable better monitoring and management of this technology. Processes considered were: microbiological- exogenous and endogenous nitrate and sulfate respiration coupled with microbial growth and decay, geochemical reactions (precipitation of calcite) and isotopic fractionation (δ15N-NO3-; δ18O- NO3- and carbon isotope network). The 2-D simulations at field scale were developed using PHAST code. Modeling of nitrate isotope geochemistry has allowed determining the extent of biodenitrification in model domain. We have quantified which is the importance in decreasing of nitrate concentrations due to biodegradation (percentage of biodegradation, 'B%') and due to dilution process (percentage of dilution, 'D%'). On the other hand, the stable carbon isotope geochemistry has been modeled. We have considered the

  12. Lipid Biomarkers and Molecular Carbon Isotopes for Elucidating Carbon Cycling Pathways in Hydrothermal Vents

    Science.gov (United States)

    Zhang, C. L.; Dai, J.; Campbell, B.; Cary, C.; Sun, M.

    2003-12-01

    Increasing molecular evidence suggests that hydrothermal vents in mid-ocean ridges harbor large populations of free-living bacteria, particularly the epsilon Proteobacteria. However, pathways for carbon metabolism by these bacteria are poorly known. We are addressing this question by analyzing the lipid biomarkers and their isotope signatures in environments where the epsilon Proteobacteria are likely predominant. Solid materials were collected from hydrothermal vents in the East Pacific Rise and at the Guaymas Basin in the Gulf of California. Fatty acids extracted from these samples are dominated by 16:0 (27-41%), 18:0 (16-48%), 18:1 (11-42%), 16:1 (7-12%), and 14:0 (5-28%). In addition, 15:0 and anteiso-15:0 are significantly present (2-3%) in samples from the Guaymas Basin. The isotopic compositions of these fatty acids range from -15.0\\permil to -33.1\\permil with the most positive values occurring only in monounsaturated fatty acids (16:1 and 18:1). We are currently unable to assign these biomarkers to any of the epsilon Proteobacteria because biomarkers are poorly known for these organisms isolated from the vents. However, no polyunsaturated fatty acids were detected in these samples, which are consistent with the absence of vent animals at the sampling sites. Signature biomarkers of 20:1 and cy21:0, which are characteristic of the thermophilic chemolithoautotrophs such as Aquificales, are also absent in these samples. These results imply that the deeply branched Aquificales species do not constitute the major microbial community in these vent environments. The large range of molecular isotopic compositions suggests that these lipids are synthesized from various carbon sources with different isotopic compositions or through different biosynthetic pathways, or both. We are currently measuring the isotopic compositions of the total organic carbon in the bulk samples and will determine the fractionations between lipid biomarkers and the total organic carbon

  13. Isotopic separation

    International Nuclear Information System (INIS)

    Castle, P.M.

    1979-01-01

    This invention relates to molecular and atomic isotope separation and is particularly applicable to the separation of 235 U from other uranium isotopes including 238 U. In the method described a desired isotope is separated mechanically from an atomic or molecular beam formed from an isotope mixture utilising the isotropic recoil momenta resulting from selective excitation of the desired isotope species by radiation, followed by ionization or dissociation by radiation or electron attachment. By forming a matrix of UF 6 molecules in HBr molecules so as to collapse the V 3 vibrational mode of the UF 6 molecule the 235 UF 6 molecules are selectively excited to promote reduction of UF 6 molecules containing 235 U and facilitate separation. (UK)

  14. 16O + 16O molecular structures of superdeformed states in S isotopes

    Science.gov (United States)

    Taniguchi, Y.

    2017-06-01

    Structures of excited states in S isotopes are investigated by using the antisymmetrized molecular dynamics and generator coordinate method (GCM). The GCM basis wave functions are calculated via energy variation with a constraint on the quadrupole deformation parameter β. By applying the GCM after parity and angular momentum projections, the coexistence of positive- and negative-parity superdeformed (SD) bands are predicted in 33-36S except for negative-parity states in 36S. The SD bands have structures of 16O + 16O + valence neutron(s) in molecular orbitals around the two 16O cores in a cluster picture. The configurations of the valence neutron(s) in the SD states are δ and/or π molecular orbitals.

  15. Molecular and stable carbon isotopic characterization of PAH contaminants at McMurdo Station, Antarctica

    International Nuclear Information System (INIS)

    Kim, Moonkoo . E-mail moonkoo.kim@wmich.edu; Kennicutt, Mahlon C.; Qian Yaorong

    2006-01-01

    The molecular and stable carbon isotopic compositions of contaminant polycyclic aromatic hydrocarbons (PAHs) at McMurdo Station, Antarctica were analyzed in samples collected from land and sub-tidal area. PAHs in the study areas were characterized by high amounts of naphthalene and alkylated naphthalenes from petroleum products introduced by human activities in the area. Principal component analysis (PCA) of PAH composition data identified multiple sources of PAH contamination in the study area. Compositional assignments of origins were confirmed using compound specific stable carbon isotopic analysis

  16. 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)

  17. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    NARCIS (Netherlands)

    Haumann, F.A.; Batenburg, A.M.; Pieterse, G.; Gerbig, C.; Krol, M.C.; Rockmann, T.

    2013-01-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H-2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H-2 and several other species as well as the H-2 isotopic composition in air samples that were collected in the BARCA

  18. Unconventional isotope systems applied to enhancing the petrogenesis of uranium deposits

    International Nuclear Information System (INIS)

    Voignot, A.; Chipley, D.; Kyser, K.; Uvarova, Y.

    2014-01-01

    Among the new techniques applied to the petrogenesis and evolution of uranium deposits from their formation to later alteration is isotope tracing. The isotope systems being used include Li, C, N, Fe, Mo, Tl, Pb and U, all of which reflect different, but overlapping, processes. Although Pb isotopes have been used to understand the temporal evolution and migration of radiogenic Pb from the deposits, Li, C, N, Mo, Tl and U isotope systems are new ways to analyze deposits and barren areas and to reveal their precise redox mechanisms. Geochemical technologies for exploration include "2"3"8U/"2"3"5U ratios of uranium minerals, which vary as a function of the type of uranium deposit and the efficiency of the redox processes. Lithium isotope ratios in muscovite and chlorite associated with mineralizing events are distinct from background ratios, with the lowest values reflecting the beginning of hydrothermal alteration systems and the highest values indicative of the terminal flow of hydrothermal fluids. Carbon and N reflect the influence of biospheric processes on the deposits and dispersion of elements that can be used for exploration. Iron, Mo and Tl are common elements in many uranium deposits and are among the most redox active elements. Their isotopes separate among phases having different oxidation potentials. They reflect the efficiency of the redox systems associated with fixing the uranium and the subsequent processes involved in mobilizing elements from the deposits. Isotopes add benefits to refining genetic models for uranium deposits, thereby enhancing our exploration models as well. An additional goal of applying isotope geochemistry to uranium deposits is to be able to use them to reflect a definitive process that occurs in the deposit and not in barren systems, and then to relate these to something that is easier to measure, namely elemental concentrations. (author)

  19. Molecular sieve isolation technique for use in stable carbon isotope analysis of individual long-chain n-alkanes in crude oil

    International Nuclear Information System (INIS)

    Yamada, Keita; Kon, Makoto; Naraoka, Hiroshi; Ishiwatari, Ryoshi; Uzaki, Minoru.

    1994-01-01

    An isolation procedure of microgram amounts of long-chain n-alkanes from crude oil using molecular sieve was examined for its applicability to stable carbon isotope analysis by gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The procedure examined is as follows: molecular sieve (type 5A, 200 mg) in 1 ml of isooctane solvent are mixed with a saturated hydrocarbon fraction extracted from an appropriate amount (approx. 20 mg) of crude oil and stayed at room temperatures for more than 3 hours. Long-chain n-alkanes are isolated by extraction with n-hexane after dissolution of the resulting molecular sieve with 47% hydrofluoric acid solution. The recoveries were 90±6% for C 15 -C 34 n-alkanes when their total amounts applied do not exceed 1.4 mg. No effect of the isolation procedure on carbon isotope ratios of n-alkanes was observed. (author)

  20. Oxygen isotope evidence for sorption of molecular oxygen to pyrite surface sites and incorporation into sulfate in oxidation experiments

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela

    2009-01-01

    Experiments were conducted to investigate (i) the rate of O-isotope exchange between SO 4 and water molecules at low pH and surface temperatures typical for conditions of acid mine drainage (AMD) and (ii) the O- and S-isotope composition of sulfates produced by pyrite oxidation under closed and open conditions (limited and free access of atmospheric O 2 ) to identify the O source/s in sulfide oxidation (water or atmospheric molecular O 2 ) and to better understand the pyrite oxidation pathway. An O-isotope exchange between SO 4 and water was observed over a pH range of 0-2 only at 50 deg. C, whereas no exchange occurred at lower temperatures over a period of 8 a. The calculated half-time of the exchange rate for 50 deg. C (pH = 0 and 1) is in good agreement with former experimental data for higher and lower temperatures and excludes the possibility of isotope exchange for typical AMD conditions (T ≤ 25 deg. C, pH ≥ 3) for decades. Pyrite oxidation experiments revealed two dependencies of the O-isotope composition of dissolved sulfates: O-isotope values decreased with longer duration of experiments and increasing grain size of pyrite. Both changes are interpreted as evidence for chemisorption of molecular O 2 to pyrite surface sites. The sorption of molecular O 2 is important at initial oxidation stages and more abundant in finer grained pyrite fractions and leads to its incorporation in the produced SO 4 . The calculated bulk contribution of atmospheric O 2 in the dissolved SO 4 reached up to 50% during initial oxidation stages (first 5 days, pH 2, fine-grained pyrite fraction) and decreased to less than 20% after about 100 days. Based on the direct incorporation of molecular O 2 in the early-formed sulfates, chemisorption and electron transfer of molecular O 2 on S sites of the pyrite surface are proposed, in addition to chemisorption on Fe sites. After about 10 days, the O of all newly-formed sulfates originates only from water, indicating direct interaction

  1. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    NARCIS (Netherlands)

    Haumann, F.A.; Batenburg, A.M.; Pieterse, G.; Gerbig, C; Krol, M.C.; Röckmann, T.

    2013-01-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço

  2. Molecular isotopic tracing of carbon flow and trophic relationships in a methane supported microbial community

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Werne, J.; Baas, B.

    2002-01-01

    A molecular isotopic study in cold-seep sediments from Kazan mud volcano in the eastern Mediterranean Sea indicates that a significant proportion of methane released in this environment is incorporated into biomass in methane-supported chemosynthetic microbial communities. Furthermore, extremely

  3. Laser ablation molecular isotopic spectrometry of water for {sub 1}D{sup 2}/{sub 1}H{sup 1} ratio analysis

    Energy Technology Data Exchange (ETDEWEB)

    Sarkar, Arnab [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Mao, Xianglei; Chan, George C.-Y. [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Russo, Richard E., E-mail: rerusso@lbl.gov [Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States)

    2013-10-01

    Laser Ablation Molecular Isotopic Spectrometry (LAMIS) has been investigated for optical isotopic analysis of the deuterium to protium ratio in enriched water samples in ambient air at atmospheric pressure. Multivariate PLSR (Partial Least Squares Regression) based calibrations were carried out and validated using multiple statistical parameters. Comparisons of results are reported using two spectrometers having two orders of magnitude difference in spectral resolution. The accuracy and precision of isotopic analysis depends on the spectral resolution and the inherent isotope shift of the elements. The requirements for spectral resolution of the measurement system can be significantly relaxed when the isotopic abundance ratio is determined using chemometric processing of the spectra. Large isotopic shifts in the individual rotational branches of OH/OD molecular emission spectra were measured. Optimized temporal conditions for LAMIS measurements were established. Several sub-regions of spectra were used for PLSR calibration and the results demonstrate that both the emission intensity and degree of spectral differentiation affect the quality of the PLSR calibration. LAMIS results also were compared with traditional LIBS results obtained using PLSR and a spectral deconvolution method, demonstrating the advantages of LAMIS over LIBS with respect to isotopic composition determination. - Highlights: • D/H isotopic ratio in water over a large dynamic range was measured by LAMIS. • PLSR based multivariate calibration was used for construction of calibrations. • Region of interest significantly affects the analytical results of isotopic ratio. • LAMIS has improved results over LIBS irrespective of the spectrometer resolution. • The superiority is more prominent in the case using low resolution spectrometer.

  4. The molecular physics of photolytic fractionation of sulfur and oxygen isotopes in planetary atmospheres (Invited)

    Science.gov (United States)

    Johnson, M. S.; Schmidt, J. A.; Hattori, S.; Danielache, S.; Meusinger, C.; Schinke, R.; Ueno, Y.; Nanbu, S.; Kjaergaard, H. G.; Yoshida, N.

    2013-12-01

    Atmospheric photochemistry is able to produce large mass independent anomalies in atmospheric trace gases that can be found in geological and cryospheric records. This talk will present theoretical and experimental investigations of the molecular mechanisms producing photolytic fractionation of isotopes with special attention to sulfur and oxygen. The zero point vibrational energy (ZPE) shift and reflection principle theories are starting points for estimating isotopic fractionation, but these models ignore effects arising from isotope-dependent changes in couplings between surfaces, excited state dynamics, line densities and hot band populations. The isotope-dependent absorption spectra of the isotopologues of HCl, N2O, OCS, CO2 and SO2 have been examined in a series of papers and these results are compared with experiment and ZPE/reflection principle models. Isotopic fractionation in planetary atmospheres has many interesting applications. The UV absorption of CO2 is the basis of photochemistry in the CO2-rich atmospheres of the ancient Earth, and of Mars and Venus. For the first time we present accurate temperature and isotope dependent CO2 absorption cross sections with important implications for photolysis rates of SO2 and H2O, and the production of a mass independent anomaly in the Ox reservoir. Experimental and theoretical results for OCS have implications for the modern stratospheric sulfur budget. The absorption bands of SO2 are complex with rich structure producing isotopic fractionation in photolysis and photoexcitation.

  5. Enhancing atom densities in solid hydrogen by isotopic substitution

    International Nuclear Information System (INIS)

    Collins, G.W.; Souers, P.C.; Mapoles, E.R.; Magnotta, F.

    1991-01-01

    Atomic hydrogen inside solid H 2 increases the energy density by 200 MegaJoules/m 3 , for each percent mole fraction stored. How many atoms can be stored in solid hydrogen? To answer this, we need to know: (1) how to produce and trap hydrogen atoms in solid hydrogen, (2) how to keep the atoms from recombining into the ground molecular state, and (3) how to measure the atom density in solid hydrogen. Each of these topics will be addressed in this paper. Hydrogen atoms can be trapped in solid hydrogen by co-condensing atoms and molecules, external irradiation of solid H 2 , or introducing a radioactive impurity inside the hydrogen lattice. Tritium, a heavy isotope of hydrogen, is easily condensed as a radioactive isotopic impurity in solid H 2 . Although tritium will probably not be used in future rockets, it provides a way of applying a large, homogenious dose to solid hydrogen. In all of the data presented here, the atoms are produced by the decay of tritium and thus knowing how many atoms are produced from the tritium decay in the solid phase is important. 6 refs., 6 figs

  6. Determination of boron isotope ratios by high-resolution continuum source molecular absorption spectrometry using graphite furnace vaporizers

    Science.gov (United States)

    Abad, Carlos; Florek, Stefan; Becker-Ross, Helmut; Huang, Mao-Dong; Heinrich, Hans-Joachim; Recknagel, Sebastian; Vogl, Jochen; Jakubowski, Norbert; Panne, Ulrich

    2017-10-01

    Boron isotope amount ratios n(10B)/n(11B) have been determined by monitoring the absorption spectrum of boron monohydride (BH) in a graphite furnace using high-resolution continuum source molecular absorption spectrometry (HR-CS-MAS). Bands (0 → 0) and (1 → 1) for the electronic transition X1Σ+ → A1Π were evaluated around wavelengths 433.1 nm and 437.1 nm respectively. Clean and free of memory effect molecular spectra of BH were recorded. In order to eliminate the memory effect of boron, a combination of 2% (v/v) hydrogen gas in argon and 1% trifluoromethane in argon, an acid solution of calcium chloride and mannitol as chemical modifiers was used. Partial least square regression (PLS) for analysis of samples and reference materials were applied. For this, a spectral library with different isotopes ratios for PLS regression was built. Results obtained around the 433.1 nm and 437.1 nm spectral regions are metrologically compatible with those reported by mass spectrometric methods. Moreover, for the evaluated region of 437 nm, an accuracy of 0.15‰ is obtained as the average deviation from the isotope reference materials. Expanded uncertainties with a coverage factor of k = 2 range between 0.15 and 0.44‰. This accuracy and precision are compatible with those obtained by mass spectrometry for boron isotope ratio measurements.

  7. Isotope separation apparatus and method

    International Nuclear Information System (INIS)

    Cotter, T.P.

    1982-01-01

    The invention relates to a method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferable substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. The laser beam comprises pi-pulses of a selected wavelength which excite unexcited molecules, or cause stimulated emission of excited molecules of one of the isotopes. Excitation caused by first direction pi-pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning pi-pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement is accomplished by a large number of pi-pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam

  8. Isotope separation apparatus and method

    International Nuclear Information System (INIS)

    Feldman, B. J.

    1985-01-01

    The invention relates to an improved method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferably substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. Because the molecules in the beam occupy various degenerate energy levels, if the laser beam comprises chirped pulses comprising selected wavelengths, the laser beam will very efficiently excite substantially all unexcited molecules and will cause stimulated emission of substantially all excited molecules of a selected one of the isotopes in the beam which such pulses encounter. Excitation caused by first direction chirped pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning chirped pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement of essentially all the molecules containing the one isotope is accomplished by a large number of chirped pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam

  9. Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes

    Science.gov (United States)

    Mazzuca, James W.; Haut, Nathaniel K.

    2018-06-01

    It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

  10. Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes.

    Science.gov (United States)

    Mazzuca, James W; Haut, Nathaniel K

    2018-06-14

    It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

  11. Surface-Enhanced Raman Scattering in Molecular Junctions.

    Science.gov (United States)

    Iwane, Madoka; Fujii, Shintaro; Kiguchi, Manabu

    2017-08-18

    Surface-enhanced Raman scattering (SERS) is a surface-sensitive vibrational spectroscopy that allows Raman spectroscopy on a single molecular scale. Here, we present a review of SERS from molecular junctions, in which a single molecule or molecules are made to have contact from the top to the bottom of metal surfaces. The molecular junctions are nice platforms for SERS as well as transport measurement. Electronic characterization based on the transport measurements of molecular junctions has been extensively studied for the development of miniaturized electronic devices. Simultaneous SERS and transport measurement of the molecular junctions allow both structural (geometrical) and electronic information on the single molecule scale. The improvement of SERS measurement on molecular junctions open the door toward new nanoscience and nanotechnology in molecular electronics.

  12. Rapid enhancement of chemical weathering recorded by extremely light seawater lithium isotopes at the Permian-Triassic boundary

    Science.gov (United States)

    Sun, He; Xiao, Yilin; Gao, Yongjun; Zhang, Guijie; Casey, John F.; Shen, Yanan

    2018-04-01

    Lithium (Li) isotope analyses of sedimentary rocks from the Meishan section in South China reveal extremely light seawater Li isotopic signatures at the Permian–Triassic boundary (PTB), which coincide with the most severe mass extinction in the history of animal life. Using a dynamic seawater lithium box model, we show that the light seawater Li isotopic signatures can be best explained by a significant influx of riverine [Li] with light δ7Li to the ocean realm. The seawater Li isotope excursion started ≥300 Ky before and persisted up to the main extinction event, which is consistent with the eruption time of the Siberian Traps. The eruption of the Siberian Traps exposed an enormous amount of fresh basalt and triggered CO2 release, rapid global warming, and acid rains, which in turn led to a rapid enhancement of continental weathering. The enhanced continental weathering delivered excessive nutrients to the oceans that could lead to marine eutrophication, anoxia, acidification, and ecological perturbation, ultimately resulting in the end-Permian mass extinction.

  13. Environmental controls on stable isotopes of precipitation in Lanzhou, China: An enhanced network at city scale.

    Science.gov (United States)

    Chen, Fenli; Zhang, Mingjun; Wang, Shengjie; Qiu, Xue; Du, Mingxia

    2017-12-31

    Stable hydrogen and oxygen isotopes in precipitation are very sensitive to environmental changes, and can record evolution of water cycle. The Lanzhou city in northwestern China is jointly influenced by the monsoon and westerlies, which is considered as a vital platform to investigate the moisture regime for this region. Since 2011, an observation network of stable isotopes in precipitation was established across the city, and four stations were included in the network. In 2013, six more sampling stations were added, and the enhanced network might provide more meaningful information on spatial incoherence and synoptic process. This study focused on the variations of stable isotopes (δ 18 O and δD) in precipitation and the environmental controls based on the 1432 samples in this enhanced network from April 2011 to October 2014. The results showed that the precipitation isotopes had great spatial diversity, and the neighboring stations may present large difference in δD and δ 18 O. Based on the observation at ten sampling sites, an isoscape in precipitation was calculated, and the method is useful to produce isoscape for small domains. The temperature effect and amount effect was reconsidered based on the dataset. Taking meteorological parameters (temperature, precipitation amount, relative humidity, water vapor pressure and dew point temperature) as variables in a multi-linear regression, the result of coefficients for these meteorological parameters were calculated. Some cases were also involved in this study, and the isotopic characteristics during one event or continuous days were used to understand the environmental controls on precipitation isotopes. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Isotopic evidence for enhanced fossil fuel sources of aerosol ammonium in the urban atmosphere.

    Science.gov (United States)

    Pan, Yuepeng; Tian, Shili; Liu, Dongwei; Fang, Yunting; Zhu, Xiaying; Gao, Meng; Gao, Jian; Michalski, Greg; Wang, Yuesi

    2018-04-20

    The sources of aerosol ammonium (NH 4 + ) are of interest because of the potential of NH 4 + to impact the Earth's radiative balance, as well as human health and biological diversity. Isotopic source apportionment of aerosol NH 4 + is challenging in the urban atmosphere, which has excess ammonia (NH 3 ) and where nitrogen isotopic fractionation commonly occurs. Based on year-round isotopic measurements in urban Beijing, we show the source dependence of the isotopic abundance of aerosol NH 4 + , with isotopically light (-33.8‰) and heavy (0 to +12.0‰) NH 4 + associated with strong northerly winds and sustained southerly winds, respectively. On an annual basis, 37-52% of the initial NH 3 concentrations in urban Beijing arises from fossil fuel emissions, which are episodically enhanced by air mass stagnation preceding the passage of cold fronts. These results provide strong evidence for the contribution of non-agricultural sources to NH 3 in urban regions and suggest that priority should be given to controlling these emissions for haze regulation. This study presents a carefully executed application of existing stable nitrogen isotope measurement and mass-balance techniques to a very important problem: understanding source contributions to atmospheric NH 3 in Beijing. This question is crucial to informing environmental policy on reducing particulate matter concentrations, which are some of the highest in the world. However, the isotopic source attribution results presented here still involve a number of uncertain assumptions and they are limited by the incomplete set of chemical and isotopic measurements of gas NH 3 and aerosol NH 4 + . Further field work and lab experiments are required to adequately characterize endmember isotopic signatures and the subsequent isotopic fractionation process under different air pollution and meteorological conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Observation of silicon self-diffusion enhanced by the strain originated from end-of-range defects using isotope multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Isoda, Taiga; Uematsu, Masashi; Itoh, Kohei M., E-mail: kitoh@appi.keio.ac.jp [School of Fundamental Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2015-09-21

    Si self-diffusion in the presence of end-of-range (EOR) defects is investigated using {sup nat}Si/{sup 28}Si isotope multilayers. The isotope multilayers were amorphized by Ge ion implantation, and then annealed at 800–950 °C. The behavior of Si self-interstitials is investigated through the {sup 30}Si self-diffusion. The experimental {sup 30}Si profiles show further enhancement of Si self-diffusion at the EOR defect region, in addition to the transient enhanced diffusion via excess Si self-interstitials by EOR defects. To explain this additional enhanced diffusion, we propose a model which takes into account enhanced diffusion by tensile strain originated from EOR defects. The calculation results based on this model have well reproduced the experimental {sup 30}Si profiles.

  16. Antisymmetrized molecular dynamics studies for exotic clustering phenomena in neutron-rich nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, M. [Hokkaido University, Department of Physics, Sapporo (Japan); Hokkaido University, Nuclear Reaction Data Centre, Faculty of Science, Sapporo (Japan); Suhara, T. [Matsue College of Technology, Matsue (Japan); Kanada-En' yo, Y. [Kyoto University, Department of Physics, Kyoto (Japan)

    2016-12-15

    We present a review of recent works on clustering phenomena in unstable nuclei studied by antisymmetrized molecular dynamics (AMD). The AMD studies in these decades have uncovered novel types of clustering phenomena brought about by the excess neutrons. Among them, this review focuses on the molecule-like structure of unstable nuclei. One of the earliest discussions on the clustering in unstable nuclei was made for neutron-rich Be and B isotopes. AMD calculations predicted that the ground state clustering is enhanced or reduced depending on the number of excess neutrons. Today, the experiments are confirming this prediction as the change of the proton radii. Behind this enhancement and reduction of the clustering, there are underlying shell effects called molecular and atomic orbits. These orbits form covalent and ionic bonding of the clusters analogous to the atomic molecules. It was found that this ''molecular-orbit picture'' reasonably explains the low-lying spectra of Be isotopes. The molecular-orbit picture is extended to other systems having parity asymmetric cluster cores and to the three cluster systems. O and Ne isotopes are the candidates of the former, while the 3α linear chains in C isotopes are the latter. For both subjects, many intensive studies are now in progress. We also pay a special attention to the observables which are the fingerprint of the clustering. In particular, we focus on the monopole and dipole transitions which are recently regarded as good probe for the clustering. We discuss how they have and will reveal the exotic clustering. (orig.)

  17. Enhanced Continental Weathering on Antarctica During the Mid Miocene Climatic Optima Based on Pb Isotopes

    Science.gov (United States)

    Martin, E. E.; Fenn, C.; Basak, C.

    2012-12-01

    Feedbacks between climate and continental weathering can be monitored over geologic time scales using Pb isotopes preserved in marine sediments. During chemical weathering, radiogenic Pb is preferentially released to the dissolved phase, producing weathering solutions with more radiogenic isotopic values than the parent rock. The offset between the composition of the solution and rock tend to increase with the intensity of incongruent weathering (von Blanckenburg and Nägler, 2001; Harlavan and Erel, 2002). The seawater isotopic signal extracted from Fe-Mn oxides on bulk marine sediments is interpreted to represent the composition of local dissolved weathering inputs. For example, increasing seawater Pb isotopes observed during the most recent deglaciation are believed to reflect enhanced weathering of newly exposed glacial rock flour under warm conditions (Foster and Vance, 2006; Kurzweil et al., 2010). For this study we evaluated Nd and Pb isotopes from both the seawater fraction (extracted from Fe-Mn oxides) and parent rock (the detrital fraction of marine sediment) during the Mid-Miocene Climatic Optimum (MMCO) and subsequent cooling and East Antarctic Ice Sheet (EAIS) expansion (18 to 8 Ma) from Ocean Drilling Program site 744 on Kerguelen Plateau (2300 m; Indian sector) and sites 689 and 690 on Maud Rise (2080 m and 2914 m; Atlantic sector). The absolute value of seawater 206Pb/204Pb and separation between values for seawater and detrital fractions increased during the MMCO, suggesting enhanced weathering in proglacial and deglaciated areas exposed by ice sheet meltback during the warm interval. During the ensuing cooling, seawater values and the offset between the two archives decreased. Similar trends are displayed by 207Pb/204Pb and 208Pb/204Pb, although 207Pb/204Pb detrital values tend to be higher than seawater values. Reconstructions of atmospheric pCO2 in the Miocene have suggested both 1) decoupling between pCO2 and climate with consistently low

  18. Optimal laser control of molecular wave packet dynamics under the influence of dissipation: possibility of isotope separation

    International Nuclear Information System (INIS)

    Ohtsuki, Yukiyoshi

    2004-01-01

    Possibility of fs-laser-pulse isotope separation is numerically investigated using optimal control theory. Optimal pulses that separate the 1:1 mixture of 79 Br 2 and 28 1 Br 2 are calculated. Quantum interferences induced by the optimally designed fs pulse efficiently enhance the isotope shifts through multiple electronic transitions, which results in a high enrichment factor. When utilizing vibrational multi-photon transitions (a virtual model), an optimal pulse can transfer the two isotopes to specified different vibrational states with almost 100% probability. In the presence of colored noises, the optimal pulse achieves the control with minimum loss of product yields within the bath correlation time. (author)

  19. 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.)

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  1. Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning

    Science.gov (United States)

    Haumann, F. A.; Batenburg, A. M.; Pieterse, G.; Gerbig, C.; Krol, M. C.; Röckmann, T.

    2013-09-01

    In this study, we identify a biomass-burning signal in molecular hydrogen (H2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H2 and several other species as well as the H2 isotopic composition in air samples that were collected in the BARCA (Balanço Atmosférico Regional de Carbono na Amazônia) aircraft campaign during the dry season. We derive a relative H2 emission ratio with respect to carbon monoxide (CO) of 0.31 ± 0.04 ppb ppb-1 and an isotopic source signature of -280 ± 41‰ in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The ΔH2 / ΔCO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

  2. 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

  3. Molecular and carbon isotopic variability of hydrocarbon gases from mud volcanos in the Gulf of Cadiz, NE Atlantic.

    NARCIS (Netherlands)

    Stadnitskaia, A.; Ivanov, M.K.; Blinova, V.; Kreulen, R.; van Weering, T.C.E.

    2006-01-01

    Investigations of molecular and carbon isotopic variability of hydrocarbon gases from methane through butanes (pentanes) have been performed on six mud volcanoes from two fluid venting provinces located in the Gulf of Cadiz, NE Atlantic. The main aims were to define the basic gas types, to describe

  4. Level densities of iron isotopes and lower-energy enhancement of y-strength function

    International Nuclear Information System (INIS)

    Voinov, A V; Grimes, S M; Agvaanluvsan, U; Algin, E; Belgya, T; Brune, C R; Guttormsen, M; Hornish, M J; Massey, T N; Mitchell, G; Rekstad, J; Schiller, A; Siem, S

    2005-01-01

    The neutron spectrum from the 55 Mn(d,n) 56 Fe reaction has been measured at E d = 7 MeV. The level density of 56 Fe obtained from neutron evaporation spectrum has been compared to the level density from Oslo-type 57 Fe( 3 He, aγ) 56 Fe experiment [1]. The good agreement supports the recent results [1, 8] including an availability of a low-energy enhancement in the γ-strength function for iron isotopes. The new level density function allowed us to investigate an excitation energy dependence of this enhancement, which is shown to increase with increasing excitation energy

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-05-01

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

  6. Molecular cavity optomechanics as a theory of plasmon-enhanced Raman scattering.

    Science.gov (United States)

    Roelli, Philippe; Galland, Christophe; Piro, Nicolas; Kippenberg, Tobias J

    2016-02-01

    The exceptional enhancement of Raman scattering by localized plasmonic resonances in the near field of metallic nanoparticles, surfaces or tips (SERS, TERS) has enabled spectroscopic fingerprinting down to the single molecule level. The conventional explanation attributes the enhancement to the subwavelength confinement of the electromagnetic field near nanoantennas. Here, we introduce a new model that also accounts for the dynamical nature of the plasmon-molecule interaction. We thereby reveal an enhancement mechanism not considered before: dynamical backaction amplification of molecular vibrations. We first map the system onto the canonical Hamiltonian of cavity optomechanics, in which the molecular vibration and the plasmon are parametrically coupled. We express the vacuum optomechanical coupling rate for individual molecules in plasmonic 'hot-spots' in terms of the vibrational mode's Raman activity and find it to be orders of magnitude larger than for microfabricated optomechanical systems. Remarkably, the frequency of commonly studied molecular vibrations can be comparable to or larger than the plasmon's decay rate. Together, these considerations predict that an excitation laser blue-detuned from the plasmon resonance can parametrically amplify the molecular vibration, leading to a nonlinear enhancement of Raman emission that is not predicted by the conventional theory. Our optomechanical approach recovers known results, provides a quantitative framework for the calculation of cross-sections, and enables the design of novel systems that leverage dynamical backaction to achieve additional, mode-selective enhancements. It also provides a quantum mechanical framework to analyse plasmon-vibrational interactions in terms of molecular quantum optomechanics.

  7. Deproteinization assessment using isotopically enriched compounds to trace the coprecipitation of low-molecular-weight selenium species with proteins.

    Science.gov (United States)

    Godin, Simon; Bouzas-Ramos, Diego; Fontagné-Dicharry, Stéphanie; Bouyssière, Brice; Bueno, Maïté

    2017-08-01

    Studies have shown that information related to the presence of low-molecular-weight metabolites is frequently lost after deproteinization of complex matrices, such as blood and plasma, during sample preparation. Therefore, the effect of several deproteinization reagents on low-molecular-weight selenium species has been compared by species-specific isotope labeling. Two isotopically enriched selenium tracers were used to mimic models of small inorganic anionic ( 77 Se-selenite) and organic zwitterionic ( 76 Se-selenomethionine) species. The results presented here show that the use of a methanol-acetonitrile-acetone (1:1:1 v/v/v) mixture provided approximately two times less tracer loss from plasma samples in comparison with the classic procedure using acetonitrile, which may not be optimal as it leads to important losses of low-molecular-weight selenium species. In addition, the possible interactions between selenium tracers and proteins were investigated, revealing that both coprecipitation phenomena and association with proteins were potentially responsible for selenite tracer losses during protein precipitation in blood samples. However, coprecipitation phenomena were found to be fully responsible for losses of both tracers observed in plasma samples and of the selenomethionine tracer in blood samples. This successfully applied strategy is anticipated to be useful for more extensive future studies in selenometabolomics. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. 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

  9. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    International Nuclear Information System (INIS)

    Minoshima, Yusuke; Seki, Yusuke; Takayanagi, Toshiyuki; Shiga, Motoyuki

    2016-01-01

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  10. Effects of temperature and isotopic substitution on electron attachment dynamics of guanine–cytosine base pair: Ring-polymer and classical molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Minoshima, Yusuke; Seki, Yusuke [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Takayanagi, Toshiyuki, E-mail: tako@mail.saitama-u.ac.jp [Department of Chemistry, Saitama University, 255 Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan); Shiga, Motoyuki [Center for Computational Science and E-Systems, Japan Atomic Energy Agency, 148-4, Kashiwanoha Campus, 178-4 Wakashiba, Kashiwa, Chiba 277-0871 (Japan)

    2016-06-15

    Highlights: • Dynamics of excess electron attachment to guanine–cytosine base pair. • Ring-polymer and classical molecular dynamics simulations are performed. • Temperature and isotope substitution effects are investigated. - Abstract: The dynamical process of electron attachment to a guanine–cytosine pair in the normal (h-GC) and deuterated (d-GC) forms has been studied theoretically by semiclassical ring-polymer molecular dynamics (RPMD) simulations using the empirical valence bond model. The initially formed dipole-bound anion is converted rapidly to the valence-bound anion within about 0.1 ps in both h-GC and d-GC. However, the subsequent proton transfer in h-GC occurs with a rate five times greater than the deuteron transfer in d-GC. The change of rates with isotopic substitution and temperature variation in the RPMD simulations are quantitatively and qualitatively different from those in the classical molecular dynamics (MD) simulations, demonstrating the importance of nuclear quantum effects on the dynamics of this system.

  11. Isotope separation by photodissociation of Van der Wall's molecules

    International Nuclear Information System (INIS)

    Lee, Y.T.

    1977-01-01

    A method of separating isotopes based on the dissociation of a Van der Waal's complex is described. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam

  12. Apparatus for extraction and separation of a preferentially photo-dissociated molecular isotope into positive and negative ions by means of an electric field

    International Nuclear Information System (INIS)

    Fletcher, J.C.

    1978-01-01

    Apparatus for the separation and extraction of molecular isotopes is claimed. Molecules of one and the same isotope are preferentially photo-dissociated by a laser and an ultraviolet source, or by multi-photon absorption of laser radiation. The resultant ions are confined with a magnetic field, moved in opposite directions by an electric field, extracted from the photo-dissociation region by means of screening and accelerating grids, and collected in ducts

  13. Resonant-enhanced spectroscopy of molecular rotations with a scanning tunneling microscope.

    Science.gov (United States)

    Natterer, Fabian Donat; Patthey, François; Brune, Harald

    2014-07-22

    We use rotational excitation spectroscopy with a scanning tunneling microscope to investigate the rotational properties of molecular hydrogen and its isotopes physisorbed on the surfaces of graphene and hexagonal boron nitride (h-BN), grown on Ni(111), Ru(0001), and Rh(111). The rotational excitation energies are in good agreement with ΔJ = 2 transitions of freely spinning p-H2 and o-D2 molecules. The variations of the spectral line shapes for H2 among the different surfaces can be traced back to a molecular resonance-mediated tunneling mechanism. Our data for H2/h-BN/Rh(111) suggest a local intrinsic gating on this surface due to lateral static dipoles. Spectra on a mixed monolayer of H2, HD, and D2 display all three J = 0 → 2 rotational transitions, irrespective of tip position, thus pointing to a multimolecule excitation, or molecular mobility in the physisorbed close-packed layer.

  14. Following Carbon Isotopes from Methane to Molecules

    Science.gov (United States)

    Freeman, K. H.

    2017-12-01

    Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

  15. 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

  16. Multiple-isotope separation in gas centrifuge

    International Nuclear Information System (INIS)

    Wood, Houston G.; Mason, T.C.; Soubbaramayer

    1996-01-01

    In previous works, the Onsager's pancake equation was used to provide solution to the internal counter-current flow field, which is necessary to calculate solutions to the isotope transport equation. The diffusion coefficient was assumed to be constant which is a good approximation for gases with large molecular weights, and small differences in the molecular weights of the various isotopes. A new optimization strategy was presented for determining the operating parameters of a gas centrifuge to be used for multiple-component isotope separation. Scoop drag, linear wall temperature gradient, the feed rate ant the cut have been chosen as operating parameters for the optimization. The investigation was restricted to a single centrifuge, and the problem of cascading for multiple-isotope separation was not addressed. The model describing the flow and separation phenomena in centrifuge includes a set of equations describing the fluid dynamics of the counter-current flow and the diffusion equations written for each isotope of the mixture. In this paper, an optimization algorithm is described and applied to an example for the re enrichment of spent reactor uranium

  17. Chemical separation of boron isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Palko, A.A.

    1978-06-01

    This is the final report of the research performed at ORNL on the chemical fractionation of boron isotopes between BF/sub 3/ gas and the liquid molecular addition compounds of BF/sub 3/. Thirty compounds were studied, ten of them in detail. Graphs and equations are given for variation of isotopic equilibrium constant, vapor pressure, and BF/sub 3/ solubility as a function of temperature. Rate of isotopic exchange and melting points were determined. Several of the compounds are likely candidates for use in a gas-liquid countercurrent exchange system for large-scale separation of boron isotopes. 23 figs, 53 tables, 39 references.

  18. Chemical separation of boron isotopes

    International Nuclear Information System (INIS)

    Palko, A.A.

    1978-06-01

    This is the final report of the research performed at ORNL on the chemical fractionation of boron isotopes between BF 3 gas and the liquid molecular addition compounds of BF 3 . Thirty compounds were studied, ten of them in detail. Graphs and equations are given for variation of isotopic equilibrium constant, vapor pressure, and BF 3 solubility as a function of temperature. Rate of isotopic exchange and melting points were determined. Several of the compounds are likely candidates for use in a gas-liquid countercurrent exchange system for large-scale separation of boron isotopes. 23 figs, 53 tables, 39 references

  19. Organic and Isotopic Signatures of Life: Lessons from the Early Earth

    Science.gov (United States)

    Freeman, K. H.; Eigenbrode, J. L.; House, C. H.

    2002-12-01

    In the study of life on earth, isotopic analyses of organic biomarkers provide essential insight to their biological and environmental provenance. Isotopic analyses of organic materials on other planets present a number of challenges, both analytical and interpretive. Prebiotic planetary organic materials can derive from condensation reactions and by delivery through meteorites or interplanetary dust, with the relative importance of each influenced by the oxidation state of the atmosphere. Material delivered to planets can have an interstellar origin, although it is dominated by compounds influenced by the formation of the solar system. Each of these processes impact molecular isotopic signatures and must be considered in life-detection strategies. Pronounced effects are observed for hydrogen isotopes, with smaller fractionations observed for other elements. Theoretical, laboratory and observational studies of non-terrean materials are essential to further understand molecular isotopic heterogeneity associated with these exclusively abiotic processes. Studies of Archean-aged samples provide an important resource for interpreting molecular isotopic patterns as signatures of life processes. Carbon assimilation and biomass synthesis from simple precursor compounds typically discriminate against 13C. This generality, however, is complicated by the observations of a wide range of fractionation factors associated with important microbial carbon-uptake processes. Metabolic processes further distribute isotopic signatures, such that wide isotopic heterogeneity is observed among cellular biochemical constituents. In addition, preservation/contamination concerns dominate studies of very ancient organic matter, as they likely will in life-detection studies. However, both biochemical heterogeneity and sample integrity can be addressed by considering patterns from different paleoenvironments. Molecular results demonstrate that Late Archean microbial life on this planet was

  20. Trends in the use of stable isotopes in biochemistry and pharmacology

    International Nuclear Information System (INIS)

    Matwiyoff, N.A.; Walker, T.E.

    1977-01-01

    Recent trends in the use of the stable isotopes 13 C, 15 N and 18 O in biochemistry and pharmacology are reviewed with emphasis on the studies that have employed nuclear magnetic resonance (nmr) spectroscopy and mass spectrometry as analytical techniques. Pharmacological studies with drugs and other compounds labelled with stable isotopes have developed in parallel with the rapid progress in the enhancement of sensitivity and selectivity of gas chromatography - mass spectrometric analyses, and have been directed largely to an evaluation of pharmako-kinetics and drug metabolic pathways. In these studies, illustrated with selected samples, isotopically labelled compounds have been used to advantage as internal standards for the mass spectrometric analyses and as in vivo tracers for metabolites. In the broader discipline of biochemistry, stable isotopes and isotopically labelled compounds have been used increasingly in conjuction with both nmr spectroscopy and mass spectrometry in tracer and structural studies. The more recent trends in the use of stable isotopes in these biochemical studies are discussed in the context of the improvements in analytical techniques. Specific examples will be drawn from investigations of the biosynthesis of natural products by micro-organisms; the protein, fat and carbohydrate fluxes in humans; and the structure and function of enzymes, membranes and other macro-molecular assemblages. The potential for the future development of stable isotopes in biochemistry and pharmacology are considered briefly, together with some of the problems that must be solved if their considerable potential is to be realized. (author)

  1. Isotope separation using vibrationally excited molecules

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Keck, J.C.

    1977-01-01

    A system for isotope separation or enrichment wherein molecules of a selected isotope type in a flow of molecules of plural isotope types are vibrationally excited and collided with a background gas to provide enhanced diffusivity for the molecules of the selected isotope type permitting their separate collection. The system typically is for the enrichment of uranium using a uranium hexafluoride gas in combination with a noble gas such as argon. The uranium hexafluoride molecules having a specific isotope of uranium are vibrationally excited by laser radiation. The vibrational energy is converted to a translation energy upon collision with a particle of the background gas and the added translation energy enhances the diffusivity of the selected hexafluoride molecules facilitating its condensation on collection surfaces provided for that purpose. This process is periodically interrupted and the cryogenic flow halted to permit evaporation of the collected molecules to provide a distinct, enriched flow

  2. Safeguards implications of laser isotope separation

    International Nuclear Information System (INIS)

    Moriarty, T.F.; Taylor, K.

    1993-10-01

    The purpose of this report is to describe and emphasise the safeguards and relevant features of atomic vapour laser isotope separation (AVLIS) and molecular laser isotope separation (MLIS), and to consider the issues that must be addressed before a safeguards approach at a commercial AVLIS or MLIS facility can be implemented. (Author)

  3. 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

  4. Tritium isotopic exchange in air detritiation dryers

    International Nuclear Information System (INIS)

    Everatt, A.E.; Johnson, R.E.; Senohrabek, J.A.; Shultz, C.M.

    1989-02-01

    Isotopic exchange between tritiated and non-tritiated water species in a molecular sieve bed has been demonstrated. At high humidities (+6 degrees Celsius dew point) the rate of tritium isotopic exchange in a 2.4 L molecular sieve bed has been demonstrated to be at least 50% of published exchange rates. In an industrial-sized air detritiation dryer, utilizing the pretreatment technique of H 2 O steam washing to elute the residual tritium, a DF of 12 600 has been demonstrated when operating at an inlet vapor tritium concentration of 14 Ci/kg and at inlet and outlet dew points of 4.8 and -54 degrees Celsius, respectively. In the NPD dryer bed studied, which was not optimally designed for full benefit from isotopic exchange, at least one order of magnitude in additional detritiation is attributed to isotopic exchange in the unsaturated zone. The technique of eluting the residual tritium from an industrial sized bed by H 2 O washing at high temperature, high humidity and low bed loading has been demonstrated to be a fast and effective way of removing tritium from a molecular sieve bed during regeneration. The isotopic exchange model accurately predicted the exchange between tritiated and non-tritiated water species in a molecular sieve bed where there is no net adsorption or desorption. The model's prediction of the tritium breakthrough trend observed in the NPD tests was poor; however, a forced fit can be achieved if the exchange rates in the MTZ and the unsaturated zone are manipulated. More experiments are needed to determine the relative rates of tritium exchange in the saturated, mass transfer, and unsaturated zones of a dryer bed

  5. Isotope separation by standing waves

    International Nuclear Information System (INIS)

    Altshuler, S.

    1984-01-01

    The separation of isotopes is accomplished by scattering a beam of particles from a standing electromagnetic wave. The particles may consist of either atoms or molecules, the beam having in either case a desired isotope and at least one other. The particle beam is directed so as to impinge on the standing electromagnetic wave, which may be a light wave. The particles, that is, the atomic or molecular quantum-mechanical waves, see basically a diffraction grating corresponding to the troughs and peaks of the electromagnetic wave. The frequency of the standing electromagnetic wave substantially corresponds to an internal energy level-transition of the desired isotope. Accordingly, the desired isotope is spatially separated by being scattered or diffracted. (author)

  6. Dielectrophoretic separation of gaseous isotopes

    International Nuclear Information System (INIS)

    McConnell, D.B.

    1976-01-01

    This invention relates to a process for the separation of gaseous isotopes by electrophoresis assisted by convective countercurrent flow and to an apparatus for use in the process. The invention is especially applicable to heavy water separation from steam; however, it is to be understood that the invention is broadly applicable to the separation of gaseous isotopes having different dipole moments and/or different molecular weights. (author)

  7. Interpreting closed-loop learning control of molecular fragmentation in terms of wave-packet dynamics and enhanced molecular ionization

    International Nuclear Information System (INIS)

    Cardoza, David; Baertschy, Mark; Weinacht, Thomas

    2005-01-01

    We interpret a molecular fragmentation experiment using shaped, ultrafast laser pulses in terms of enhanced molecular ionization during dissociation. A closed-loop learning control experiment was performed to maximize the CF 3 + /CH 3 + production ratio in the dissociative ionization of CH 3 COCF 3 . Using ab inito molecular structure calculations and quasistatic molecular ionization calculations along with data from pump-probe experiments, we identify the primary control mechanism which is quite general and should be applicable to a broad class of molecules

  8. Vibrational energy transfer kinetics in molecular disequilibrium. Final technical report

    International Nuclear Information System (INIS)

    Rich, J.W.

    1982-09-01

    The present Calspan experiments have shown direct evidence of preferential vibrational pumping of two heavy isotopes of CO: 13 C 16 O and 12 C 18 O. The nature of the enhancement is generally consistent with the predictions of theoretical modeling. These are the first direct experimental demonstrations of this isotope selection method. The potential advantages of such a means of isotope separation are inherent in the V-V pumping process itself. Summarizing these: (1) Selectivity actually increases at higher reactant pressures, since the selection mechanism is collisional. Accordingly, rather high throughputs are possible, unlike other techniques in which molecular collisions actually decrease selectivity. (2) A variety of excitation methods can potentially be used - electric discharge, optical excitation by coherent or incoherent sources, or chemical excitation; laser excitation is not critical to the process. (3) The method can be applied to many isotopes of the lighter atoms. It is not inherently species-specific

  9. Ionic molecular films. Applications. 3. Electron beam stimulated enhanced adherence

    Energy Technology Data Exchange (ETDEWEB)

    Baldacchini, G; Montereali, R M; Scavarda do Carmo, L C

    1989-11-01

    This paper reports on the advantages of the use of the technique of electron beam lithography to imprint enhanced sensitive patterns on ionic molecular substrates (bulk crystals or films). With this technique, localized superficial defects are produced which change the chemical properties of surfaces. Sensitized surfaces react with absorbates providing enhanced adherence of such substances. The use of spacially controlled electron beams allows the construction of small (sub-micron) feature chemical and very localized enhanced adherence of absorbates.

  10. Method for separating gaseous mixtures of isotopes

    International Nuclear Information System (INIS)

    Neimann, H.J.; Schuster, E.; Kersting, A.

    1976-01-01

    A gaseous mixture of isotopes is separated by laser excitation of the isotope mixture with a narrow band of wavelengths, molecularly exciting mainly the isotope to be separated and thereby promoting its reaction with its chemical partner which is excited in a separate chamber. The excited isotopes and the chemical partner are mixed, perhaps in a reaction chamber to which the two excited components are conducted by very short conduits. The improvement of this method is the physical separation of the isotope mixture and its partner during excitation. The reaction between HCl and the mixture of 238 UF 6 and 235 UF 6 is discussed

  11. Perfect-absorption graphene metamaterials for surface-enhanced molecular fingerprint spectroscopy

    Science.gov (United States)

    Guo, Xiangdong; Hu, Hai; Liao, Baoxin; Zhu, Xing; Yang, Xiaoxia; Dai, Qing

    2018-05-01

    Graphene plasmon with extremely strong light confinement and tunable resonance frequency represents a promising surface-enhanced infrared absorption (SEIRA) sensing platform. However, plasmonic absorption is relatively weak (approximately 1%-9%) in monolayer graphene nanostructures, which would limit its sensitivity. Here, we theoretically propose a hybrid plasmon-metamaterial structure that can realize perfect absorption in graphene with a low carrier mobility of 1000 cm2 V-1 s-1. This structure combines a gold reflector and a gold grating to the graphene plasmon structures, which introduce interference effect and the lightning-rod effect, respectively, and largely enhance the coupling of light to graphene. The vibration signal of trace molecules can be enhanced up to 2000-fold at the hotspot of the perfect-absorption structure, enabling the SEIRA sensing to reach the molecular level. This hybrid metal-graphene structure provides a novel path to generate high sensitivity in nanoscale molecular recognition for numerous applications.

  12. Apportioning sources of organic matter in streambed sediments: An integrated molecular and compound-specific stable isotope approach

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Richard J., E-mail: Richard.J.Cooper@uea.ac.uk [School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ (United Kingdom); Pedentchouk, Nikolai; Hiscock, Kevin M.; Disdle, Paul [School of Environmental Sciences, University of East Anglia, Norwich Research Park, Norwich NR4 7TJ (United Kingdom); Krueger, Tobias [IRI THESys, Humboldt University, 10099 Berlin (Germany); Rawlins, Barry G. [British Geological Survey, Keyworth, Nottingham NG12 5GG (United Kingdom)

    2015-07-01

    We present a novel application for quantitatively apportioning sources of organic matter in streambed sediments via a coupled molecular and compound-specific isotope analysis (CSIA) of long-chain leaf wax n-alkane biomarkers using a Bayesian mixing model. Leaf wax extracts of 13 plant species were collected from across two environments (aquatic and terrestrial) and four plant functional types (trees, herbaceous perennials, and C{sub 3} and C{sub 4} graminoids) from the agricultural River Wensum catchment, UK. Seven isotopic (δ{sup 13}C{sub 27}, δ{sup 13}C{sub 29}, δ{sup 13}C{sub 31}, δ{sup 13}C{sub 27–31}, δ{sup 2}H{sub 27}, δ{sup 2}H{sub 29}, and δ{sup 2}H{sub 27–29}) and two n-alkane ratio (average chain length (ACL), carbon preference index (CPI)) fingerprints were derived, which successfully differentiated 93% of individual plant specimens by plant functional type. The δ{sup 2}H values were the strongest discriminators of plants originating from different functional groups, with trees (δ{sup 2}H{sub 27–29} = − 208‰ to − 164‰) and C{sub 3} graminoids (δ{sup 2}H{sub 27–29} = − 259‰ to − 221‰) providing the largest contrasts. The δ{sup 13}C values provided strong discrimination between C{sub 3} (δ{sup 13}C{sub 27–31} = − 37.5‰ to − 33.8‰) and C{sub 4} (δ{sup 13}C{sub 27–31} = − 23.5‰ to − 23.1‰) plants, but neither δ{sup 13}C nor δ{sup 2}H values could uniquely differentiate aquatic and terrestrial species, emphasizing a stronger plant physiological/biochemical rather than environmental control over isotopic differences. ACL and CPI complemented isotopic discrimination, with significantly longer chain lengths recorded for trees and terrestrial plants compared with herbaceous perennials and aquatic species, respectively. Application of a comprehensive Bayesian mixing model for 18 streambed sediments collected between September 2013 and March 2014 revealed considerable temporal variability in the

  13. Method of isotope separation by chemi-ionization

    International Nuclear Information System (INIS)

    Wexler, S.; Young, C.E.

    1977-01-01

    A method is disclosed for separating isotopes in an isotopic mixture by aerodynamically accelerating a gaseous compound to form a jet of molecules, and passing the jet through a stream of electron donor atoms whereby an electron transfer takes place, thus forming negative ions of the molecules. The molecular ions are then passed through a radiofrequency quadrupole mass filter to separate the specific isotopes. cThis method may be used for any compounds having a sufficiently high electron affinity to permit negative ion formation, and is especially useful for the separation of plutonium and uranium isotopes. 10 claims, 1 figure

  14. Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

    Science.gov (United States)

    Simon, Justin

    2017-01-01

    Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

  15. Isotope-selective ionization using four-pulse alignment

    International Nuclear Information System (INIS)

    Akagi, Hiroshi; Kasajima, Tatsuya; Kumada, Takayuki; Itakura, Ryuji; Yokoyama, Atsushi; Hasegawa, Hirokazu; Ohshima, Yasuhiro

    2013-01-01

    We have proposed a laser isotope separation method utilizing molecular alignment and non-resonant multiphoton ionization, and demonstrated isotope-selective ionization of 14 N 2 and 15 N 2 isotopomers, using one-pulse alignment. In the present work, we used a train of four identical pulses, instead of one pulse, to obtain the higher selectivity. (author)

  16. On the strong and selective isotope effect in the UV excitation of N2 with implications toward the nebula and Martian atmosphere.

    Science.gov (United States)

    Muskatel, B H; Remacle, F; Thiemens, Mark H; Levine, R D

    2011-04-12

    Isotopic effects associated with molecular absorption are discussed with reference to natural phenomena including early solar system processes, Titan and terrestrial atmospheric chemistry, and Martian atmospheric evolution. Quantification of the physicochemical aspects of the excitation and dissociation processes may lead to enhanced understanding of these environments. Here we examine a physical basis for an additional isotope effect during photolysis of molecular nitrogen due to the coupling of valence and Rydberg excited states. The origin of this isotope effect is shown to be the coupling of diabatic electronic states of different bonding nature that occurs after the excitation of these states. This coupling is characteristic of energy regimes where two or more excited states are nearly crossing or osculating. A signature of the resultant isotope effect is a window of rapid variation in the otherwise smooth distribution of oscillator strengths vs. frequency. The reference for the discussion is the numerical solution of the time dependent Schrödinger equation for both the electronic and nuclear modes with the light field included as part of the Hamiltonian. Pumping is to all extreme UV dipole-allowed, valence and Rydberg, excited states of N(2). The computed absorption spectra are convoluted with the solar spectrum to demonstrate the importance of including this isotope effect in planetary, interstellar molecular cloud, and nebular photochemical models. It is suggested that accidental resonance with strong discrete lines in the solar spectrum such as the CIII line at 97.703 nm can also have a marked effect.

  17. Quasimolecular states in a reaction with carbon isotopes

    Czech Academy of Sciences Publication Activity Database

    Torilov, S. Yu.; Maltsev, N. A.; Goldberg, V. Z.; Gridnev, K. A.; Zherebchevsky, V. I.; Lönnroth, T.; Novatskii, B. G.; Slotte, J. M. K.; Sobolev, Yuri, G.; Trzaska, W. H.; Tyurin, G. P.; Khlebnikov, S. V.

    2015-01-01

    Roč. 102, č. 2 (2015), s. 69-72 ISSN 0021-3640 R&D Projects: GA MŠk LG14004 Institutional support: RVO:61389005 Keywords : rich Be isotope * C isotope * C-14+C-12 Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.172, year: 2015

  18. Molecular diffusion of stable water isotopes in polar firn as a proxy for past temperatures

    Science.gov (United States)

    Holme, Christian; Gkinis, Vasileios; Vinther, Bo M.

    2018-03-01

    Polar precipitation archived in ice caps contains information on past temperature conditions. Such information can be retrieved by measuring the water isotopic signals of δ18O and δD in ice cores. These signals have been attenuated during densification due to molecular diffusion in the firn column, where the magnitude of the diffusion is isotopologue specific and temperature dependent. By utilizing the differential diffusion signal, dual isotope measurements of δ18O and δD enable multiple temperature reconstruction techniques. This study assesses how well six different methods can be used to reconstruct past surface temperatures from the diffusion-based temperature proxies. Two of the methods are based on the single diffusion lengths of δ18O and δD , three of the methods employ the differential diffusion signal, while the last uses the ratio between the single diffusion lengths. All techniques are tested on synthetic data in order to evaluate their accuracy and precision. We perform a benchmark test to thirteen high resolution Holocene data sets from Greenland and Antarctica, which represent a broad range of mean annual surface temperatures and accumulation rates. Based on the benchmark test, we comment on the accuracy and precision of the methods. Both the benchmark test and the synthetic data test demonstrate that the most precise reconstructions are obtained when using the single isotope diffusion lengths, with precisions of approximately 1.0 °C . In the benchmark test, the single isotope diffusion lengths are also found to reconstruct consistent temperatures with a root-mean-square-deviation of 0.7 °C . The techniques employing the differential diffusion signals are more uncertain, where the most precise method has a precision of 1.9 °C . The diffusion length ratio method is the least precise with a precision of 13.7 °C . The absolute temperature estimates from this method are also shown to be highly sensitive to the choice of fractionation factor

  19. Stable-isotope studies. Progress report, March 1, 1980-August 25, 1982

    International Nuclear Information System (INIS)

    Ishida, T.

    1982-01-01

    Investigations during the past two-and-a half year priod have been directed toward the following three areas: (1) studies of vapor pressure isotope effects (fluoroform, methyl fluoride, methylene difluorides, ammonia); (2) studies on the fractionation of nitrogen isotope systems; and (3) theory of isotope effect. Studies on the fractionation of nitrogen isotope fractionaton systems involved two fronts. One is a study of 15 N-production by means of a countercurrent isotope exchange in a packed column between a gas phase, which is a mixture of various NO/sub x/, and a liquid phase, which is mainly N 2 O 3 and N 2 O 4 . The second deals with a concept of closed reflux cycle for the Nitrox and/or the NO/N 2 O 3 -process. In the theoretical field, studies of isotopic reduced partition function ratio has led to revelations of interesting correlations between molecular structures, molecular forces, and the isotope effects. The investigations for this period are summarized and a more thorough discussion is presented for each ongoing research

  20. Isotope separation process

    International Nuclear Information System (INIS)

    Wexler, Sol; Young, C.E.

    1976-01-01

    Description is given of method for separating a specific isotope from a mixture of isotopes of an actinide element present as MF 6 , wherein M is the actinide element. It comprises: preparing a feed gas mixture of MF 6 in a propellant gas; passing the feed gas mixture under pressure through an expansion nozzle while heating the mixture to about 600 0 C; releasing the heated gas mixture from the nozzle into an exhaust chamber having a reduced pressure, whereby a gas jet of MF 6 molecules, MF 6 molecular clusters and propellant gas molecules is formed, the MF 6 molecules having a translational energy of about 3 eV; converting the MF 6 molecules to MF 6 ions by passing the jet through a cross jet of electron donor atoms so that an electron transfer takes place between the MF 6 - molecules and the electron donor atoms whereby the jet is now quasi-neutral, containing negative MF 6 - ions and positive donor ions; passing the quasi-neutral jet through a radiofrequency mass filter tuned to separate the MF 6 ions containing the specific isotope from the MF 6 - ions of the other isotopes and neutralizing and collecting the MF 6 molecules of the specific isotope [fr

  1. Isotopes in molecular biology

    International Nuclear Information System (INIS)

    Goldfarb, P.S.G.

    1988-01-01

    The use of radioisotopes in molecular biology, with particular reference to the structure and functions of DNA, RNA and the cellular synthesis of proteins, is discussed. The use of labelled DNA and RNA in diagnostic techniques is presented. (U.K.)

  2. A distance-dependent metal-enhanced fluorescence sensing platform based on molecular beacon design.

    Science.gov (United States)

    Zhou, Zhenpeng; Huang, Hongduan; Chen, Yang; Liu, Feng; Huang, Cheng Zhi; Li, Na

    2014-02-15

    A new metal-enhanced fluorescence (MEF) based platform was developed on the basis of distance-dependent fluorescence quenching-enhancement effect, which combined the easiness of Ag-thiol chemistry with the MEF property of noble-metal structures as well as the molecular beacon design. For the given sized AgNPs, the fluorescence enhancement factor was found to increase with a d(6) dependency in agreement with fluorescence resonance energy transfer mechanism at shorter distance and decrease with a d(-3) dependency in agreement with plasmonic enhancement mechanism at longer distance between the fluorophore and the AgNP surface. As a proof of concept, the platform was demonstrated by a sensitive detection of mercuric ions, using thymine-containing molecular beacon to tune silver nanoparticle (AgNP)-enhanced fluorescence. Mercuric ions were detected via formation of a thymine-mercuric-thymine structure to open the hairpin, facilitating fluorescence recovery and AgNP enhancement to yield a limit of detection of 1 nM, which is well below the U.S. Environmental Protection Agency regulation of the Maximum Contaminant Level Goal (10nM) in drinking water. Since the AgNP functioned as not only a quencher to reduce the reagent blank signal but also an enhancement substrate to increase fluorescence of the open hairpin when target mercuric ions were present, the quenching-enhancement strategy can greatly improve the detection sensitivity and can in principle be a universal approach for various targets when combined with molecular beacon design. © 2013 Elsevier B.V. All rights reserved.

  3. Isotope separation by photoselective dissociative electron

    International Nuclear Information System (INIS)

    Stevens, C.G.

    1978-01-01

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule is described. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, 235 UF 6 is separated from a UF 6 mixture by selective excitation followed by dissociative electron capture into 235 UF 5 - and F

  4. Beneficial use of isotopes

    International Nuclear Information System (INIS)

    Bertel, E.; Stevens, G.H.

    1998-01-01

    The paper gives an outlook on the main isotopes currently used for beneficial applications, provides an overview on geographic distribution of isotope production capabilities and identifies the main suppliers world-wide. It analyses trends in different countries and regions, including the refurbishment and/or replacement of ageing facilities and the implementation of new capabilities. Issues related to adequate supply of isotopes and potential under or over capacity of production for some key products are discussed. The evolution of the isotope production sector is analysed. Issues such as lowering of governmental support to production facilities, emergence of international co-operation and agreements on production capabilities, and developments in non-OECD/NEA countries are addressed. The paper offers some concluding remarks on the importance of maintaining and enhancing beneficial uses of isotopes, the role of government policies, the need for co-operation between countries and between the private and public sectors. The paper addresses the role of international cooperation in making efficient use of existing isotope production capacity and investigates ways for reducing the need for investment in additional capacity. (author)

  5. Dielectrophoretic separation of gaseous isotopes

    International Nuclear Information System (INIS)

    McConnell, D.B.

    1975-01-01

    Gaseous isotopes are separated from a mixture in a vertically elongated chamber by subjecting the mixture to a nonuniform transverse electric field. Dielectrophoretic separation of the isotopes is effected, producing a transverse temperature gradient in the chamber, thereby enhancing the separation by convective countercurrent flow. In the example given, the process and apparatus are applied to the production of heavy water from steam

  6. Determination of zinc stable isotopes in biological materials using isotope dilution inductively coupled plasma mass spectrometry

    International Nuclear Information System (INIS)

    Patterson, K.Y.; Veillon, Claude

    1992-01-01

    A method is described for using isotope dilution to determine both the amount of natural zinc and enriched isotopes of zinc in biological samples. Isotope dilution inductively coupled plasma mass spectrometry offers a way to quantify not only the natural zinc found in a sample but also the enriched isotope tracers of zinc. Accurate values for the enriched isotopes and natural zinc are obtained by adjusting the mass count rate data for measurable instrumental biases. Analytical interferences from the matrix are avoided by extracting the zinc from the sample matrix using diethylammonium diethyldithiocarbamate. The extraction technique separates the zinc from elements which form interfering molecular ions at the same nominal masses as the zinc isotopes. Accuracy of the method is verified using standard reference materials. The detection limit is 0.06 μg Zn per sample. Precision of the abundance ratios range from 0.3-0.8%. R.S.D. for natural zinc concentrations is about 200-600 μg g -1 . The accuracy and precision of the measurements make it possible to follow enriched isotopic tracers of zinc in biological samples in metabolic tracer studies. (author). 19 refs.; 1 fig., 4 tabs

  7. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    Science.gov (United States)

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

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  8. Facilitation of AMPA receptor synaptic delivery as a molecular mechanism for cognitive enhancement

    DEFF Research Database (Denmark)

    Knafo, Shira; Venero, César; Sánchez-Puelles, Cristina

    2012-01-01

    ) that enhances spatial learning and memory in rats. We have now investigated the cellular and molecular basis of this cognitive enhancement, using biochemical, morphological, electrophysiological, and behavioral analyses. We have found that FGL triggers a long-lasting enhancement of synaptic transmission......MKII activation. These results provide a mechanistic link between facilitation of AMPA receptor synaptic delivery and improved hippocampal-dependent learning, induced by a pharmacological cognitive enhancer....

  9. Isotope separation process

    International Nuclear Information System (INIS)

    Cox, D.M.; Maas, E.T.

    1982-01-01

    Processes are disclosed for the separation of isotopes of an element comprising vaporizing uranyl compounds having the formula (UO2a2)n, where a is a monovalent anion and n in an integer from 2 to 4, the compounds having an isotopically shifted infrared absorption spectrum associated with uranyl ions containing said element which is to be separated, and then irradiating the uranyl compound with infrared radiation which is preferentially absorbed by a molecular vibration of uranyl ions of the compound containing a predetermined isotope of that element so that excited molecules of the compound are provided which are enriched in the molecules of the compound containing that predetermined isotope, thus enabling separation of these excited molecules. The processes disclosed include separation of the excited molecules by irradiating under conditions such that the excited molecules dissociate, and also separating the excited molecules by a discrete separation step. The latter includes irradiating the excited molecules by a second infrared laser in order to convert the excited molecules into a separable product, or also by chemically converting the excited molecules, preferably by reaction with a gaseous reactant

  10. Isotope ratio in stellar atmospheres and nucleosynthesis

    International Nuclear Information System (INIS)

    Barbuy, B.L.S.

    1987-01-01

    The determination of isotopic ratios in stellar atmospheres is studied. The isotopic shift of atomic and molecular lines of different species of a certain element is examined. CH and MgH lines are observed in order to obtain the 12 C: 13 C and 24 Mg: 25 Mg: 26 Mg isotpic ratios. The formation of lines in stellar atmospheres is computed and the resulting synthetic spectra are employed to determine the isotopic abundances. The results obtained for the isotopic ratios are compared to predictions of nucleosynthesis theories. Finally, the concept of primary and secondary element is discussed, and these definitions are applied to the observed variations in the abundance of elements as a function of metallicity. (author) [pt

  11. Molecular hydrogen (H2) combustion emissions and their isotope (D/H) signatures from domestic heaters, diesel vehicle engines, waste incinerator plants, and biomass burning

    NARCIS (Netherlands)

    Vollmer, M.K.; Walter, S.; Mohn, J.; Steinbacher, M.; Bond, S.W.; Röckmann, T.; Reimann, S.

    2012-01-01

    Molecular hydrogen (H2), its stable isotope signature ( D), and the key combustion parameters carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were measured from various combustion processes. H2 in the exhaust of gas and oil-fired heaters and of waste incinerator plants was generally

  12. Isotopic Changes During Digestion: Protein

    Science.gov (United States)

    Tuross, N.

    2013-12-01

    Nutrient and hydrological inputs traverse a complicated route of pH, enzymatic and cellular processes in digestion in higher animals. The end products of digestion are the starting products for biosynthesis that are often used to interpret past life-ways. Using an artificial gut system, the isotopic changes (dD, d18O, d13C and d15N) of protein are documented. Three separate protein sources are subjected to the conditions, chemical and enzymatic, found in the stomach and upper small intestine with only a small shift in the oxygen isotopic composition of the proteins observed. Middle to lower small intestine parameters produced both greater isotopic effects and significantly lower molecular weight products. The role of the gastric enterocyte and the likely involvement of the internal milieu of this cell in the isotopic composition of amino acids that are transported to the liver are reported.

  13. Laser isotope separation using selective inhibition and encouragement of dimer formation

    International Nuclear Information System (INIS)

    Kivel, B.

    1979-01-01

    Method and apparatus for inhibiting dimer formation of molecules of a selected isotope type in a cooled flow of gas to enhance the effectiveness of mass difference isotope separation techniques are described. Molecules in the flow containing atoms of the selected isotope type are selectively excited by infrared radiation in order to inhibit the formation of dimers and larger clusters of such molecules, while the molecules not containing atoms of the selected, excited type are encouraged to form dimers and higher order aggregates by the cooling of the gaseous flow. The molecules with the excited isotope will predominate in monomers and will constitute the enriched product stream, while the aggregated group comprising molecules having the unexcited isotope will predominate in dimers and larger clusters of molecules, forming the tails stream. The difference in diffusion coefficientts between particles of the excited and unexcited isotopes is enhanced by the greater mass differences resulting from aggregation of unexcited particles into dimers and larger clusters. Prior art separation techniques which exploit differences in isotopic diffusion rates will consequently exhibit enhanced enrichment per stage by the utilization of the present invention

  14. SAIL--stereo-array isotope labeling.

    Science.gov (United States)

    Kainosho, Masatsune; Güntert, Peter

    2009-11-01

    Optimal stereospecific and regiospecific labeling of proteins with stable isotopes enhances the nuclear magnetic resonance (NMR) method for the determination of the three-dimensional protein structures in solution. Stereo-array isotope labeling (SAIL) offers sharpened lines, spectral simplification without loss of information and the ability to rapidly collect and automatically evaluate the structural restraints required to solve a high-quality solution structure for proteins up to twice as large as before. This review gives an overview of stable isotope labeling methods for NMR spectroscopy with proteins and provides an in-depth treatment of the SAIL technology.

  15. High-order-harmonic generation from H2+ molecular ions near plasmon-enhanced laser fields

    Science.gov (United States)

    Yavuz, I.; Tikman, Y.; Altun, Z.

    2015-08-01

    Simulations of plasmon-enhanced high-order-harmonic generation are performed for a H2+ molecular cation near the metallic nanostructures. We employ the numerical solution of the time-dependent Schrödinger equation in reduced coordinates. We assume that the main axis of H2+ is aligned perfectly with the polarization direction of the plasmon-enhanced field. We perform systematic calculations on plasmon-enhanced harmonic generation based on an infinite-mass approximation, i.e., pausing nuclear vibrations. Our simulations show that molecular high-order-harmonic generation from plasmon-enhanced laser fields is possible. We observe the dispersion of a plateau of harmonics when the laser field is plasmon enhanced. We find that the maximum kinetic energy of the returning electron follows 4 Up . We also find that when nuclear vibrations are enabled, the efficiency of the harmonics is greatly enhanced relative to that of static nuclei. However, the maximum kinetic energy 4 Up is largely maintained.

  16. Morphology, molecular structure, and stable carbon isotopic composition of black carbon (BC) in urban topsoils.

    Science.gov (United States)

    Zong, Yutong; Xiao, Qing; Lu, Shenggao

    2018-02-01

    Urban soils contain significant amounts of black carbon (BC) from biomass and fossil fuel combustion and regard to be a pool of BC. BC in urban soils has multiple effects on environmental processes in urban system, such as global climate change, air quality, and public health. Urban topsoil samples (0-10 cm) were collected from Anshan, Liaoning Province, northeast China, which is one of the most important old steel industrial bases in China. The BC in urban topsoils was extracted using the density method. Their chemical composition, morphology, molecular structure, and stable carbon isotopic composition were examined using elemental analysis, scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and stable carbon isotope (δ 13 C). Elemental analysis shows that carbon content in the BC of studied soils ranged from 64.5 to 78.4%, with the average more than 70%. The O/C atomic ratio of BC is on average 0.18. The BC particle displays different morphology, including porous spherical, irregular porous fragmentary, and blocky shapes. The porous spherical BC particles has atomic molar O/C ratio determined by SEM-EDS ranging from 0.04 to 0.37. XRD indicates that BC exists in mainly combining with mineral phases hematite (Fe 2 O 3 ), kaolinite (Al 2 Si 2 O 5 (OH) 4 ), quartz (SiO 2 ), and calcite (CaCO 3 ). The FTIR spectra of BC particles show major bands at approximately 3400 cm -1 (O-H), 2920 cm -1 (C = H), 1600 cm -1 (C = C), 1230 cm -1 (C = O), and 1070 cm -1 (C = O). The stable carbon isotope (δ 13 C) of BC ranges from -24.48 to -23.18‰ with the average of -23.79 ± 0.39‰. The concentration of BC in the industrial area is significantly (p fuel combustion. Results indicated that a combination of atomic O/C ratio, porous structure, and stable carbon isotopic (δ 13 C) of BC could reflect effectively the origin of BC

  17. Exploring the isotopic niche: isotopic variance, physiological incorporation, and the temporal dynamics of foraging

    Directory of Open Access Journals (Sweden)

    Justin Douglas Yeakel

    2016-01-01

    Full Text Available Consumer foraging behaviors are dynamic, changing in response to prey availability, seasonality, competition, and even the consumer's physiological state. The isotopic composition of a consumer is a product of these factors as well as the isotopic `landscape' of its prey, i.e. the isotopic mixing space. Stable isotope mixing models are used to back-calculate the most likely proportional contribution of a set of prey to a consumer's diet based on their respective isotopic distributions, however they are disconnected from ecological process. Here we build a mechanistic framework that links the ecological and physiological processes of an individual consumer to the isotopic distribution that describes its diet, and ultimately to the isotopic composition of its own tissues, defined as its `isotopic niche’. By coupling these processes, we systematically investigate under what conditions the isotopic niche of a consumer changes as a function of both the geometric properties of its mixing space and foraging strategies that may be static or dynamic over time. Results of our derivations reveal general insight into the conditions impacting isotopic niche width as a function of consumer specialization on prey, as well as the consumer's ability to transition between diets over time. We show analytically that moderate specialization on isotopically unique prey can serve to maximize a consumer's isotopic niche width, while temporally dynamic diets will tend to result in peak isotopic variance during dietary transitions. We demonstrate the relevance of our theoretical findings by examining a marine system composed of nine invertebrate species commonly consumed by sea otters. In general, our analytical framework highlights the complex interplay of mixing space geometry and consumer dietary behavior in driving expansion and contraction of the isotopic niche. Because this approach is established on ecological mechanism, it is well-suited for enhancing the

  18. Chemical characterization and stable carbon isotopic composition of particulate Polycyclic Aromatic Hydrocarbons issued from combustion of 10 Mediterranean woods

    Directory of Open Access Journals (Sweden)

    A. Guillon

    2013-03-01

    Full Text Available The objectives of this study were to characterize polycyclic aromatic hydrocarbons from particulate matter emitted during wood combustion and to determine, for the first time, the isotopic signature of PAHs from nine wood species and Moroccan coal from the Mediterranean Basin. In order to differentiate sources of particulate-PAHs, molecular and isotopic measurements of PAHs were performed on the set of wood samples for a large panel of compounds. Molecular profiles and diagnostic ratios were measured by gas chromatography/mass spectrometry (GC/MS and molecular isotopic compositions (δ13C of particulate-PAHs were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS. Wood species present similar molecular profiles with benz(aanthracene and chrysene as dominant PAHs, whereas levels of concentrations range from 1.8 to 11.4 mg g−1 OC (sum of PAHs. Diagnostic ratios are consistent with reference ratios from literature but are not sufficient to differentiate the species of woods. Concerning isotopic methodology, PAH molecular isotopic compositions are specific for each species and contrary to molecular fingerprints, significant variations of δ13C are observed for the panel of PAHs. This work allows differentiating wood combustion (with δ13CPAH = −28.7 to −26.6‰ from others origins of particulate matter (like vehicular exhaust using isotopic measurements but also confirms the necessity to investigate source characterisation at the emission in order to help and complete source assessment models. These first results on woodburnings will be useful for the isotopic approach to source tracking.

  19. PALOMA : An instrument to measure the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform (MSL 09, EXOMARS)

    Science.gov (United States)

    Chassefière, E.; Paloma Team

    2003-04-01

    An instrument to analyze the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform is being developed under CNES funding. This instrument, called PALOMA (PAyload for Local Observation of Mars Atmosphere), will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. Noble gases (He, Ne, Ar, Xr, Xe) and stable isotopes (C, H, O, N) will be analyzed by using a system of gas purification and separation, coupled with a mass spectrometer. The heaviest, radioactive, noble gas (Rn) and its short-lived daughters will be measured using a small additional device (alpha particle detector). Detailed search for trace constituents of astrobiological interest, like CH_4, H_2CO, N_2O, H_2S (abundances, isotopic ratios, time variability) will be done on a regular temporal basis during one Martian year. Isotopic ratios will be measured with an accuracy of about 1 ppm, or better, in order to provide a clear diagnosis of possible life signatures, to allow a detailed comparison of Earth and Mars atmospheric fractionation patterns and, finally, to accurately disentangle escape, climatic, geochemical and hypothesized biological effects. High sensitivity is required for elemental and isotopic compositions of trace gases of interest (a small fraction of ppbv). Such an accurate monitoring of Mars atmosphere volatile composition is expected to provide the necessary reference for future composition studies of minerals, soils, bio-markers, polar cap material, either by in-situ measurement, or from laboratory analyses of returned samples. The PALOMA instrument consists of : a gas purification and separation line, using techniques of chemical and cryogenic trapping, and possibly membrane permeation, a mass spectrometer working in static mode, a turbo-molecular pump that provides the

  20. Fundamental studies in isotope chemistry. Progress report, 1 August 1981-1 August 1982

    International Nuclear Information System (INIS)

    Bigeleisen, J.

    1982-01-01

    This research program is concerned with isotope chemistry and its applications. A summary of isotope separation activities during the past 5 years is included. Isotope effects are used as probes for chemical reactions, geochemistry, meteorology, and molecular biology, and this report also summarizes progress made in this area

  1. 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.)

  2. The study of multicomponent separation of Xe isotope by centrifugal method

    International Nuclear Information System (INIS)

    Jinyan Wu; Fu Zhuge

    1996-01-01

    The element Xe has nine isotopes in nature, the separation performance of each component mutually affects the others, so the binary separation theory can't be employed to study the multicomponent separation. Especially, when the molecular wight of a certain component is in the middle of its isotope components, the effect of the others on this component must be considered. In this paper, first, the multicomponent separation of Xe isotopes in a gas centrifuge is studied, with the consideration of the effect of the concentration on the diffusion coefficient and average molecular weight. The multicomponent diffusion equations are solved by the finite difference method. Second, the enrichment of Xe isotopes in a cascade is studied. On the basis of the study of a gas centrifuge, the simplified separation equations of a gas centrifuge for cascade calculation are obtained. Furthermore, the complete equations of the cascade separation are established according to the conservation of mass of each component and solved by a numerical method. The study of this paper can be extended for other isotope separation calculations. (author)

  3. Testing the mutually enhanced magicity effect in nuclear incompressibility via the giant monopole resonance in the {sup 204,206,208}Pb isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Patel, D. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Garg, U., E-mail: garg@nd.edu [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Fujiwara, M. [Research Center for Nuclear Physics, Osaka University, Osaka 567-0047 (Japan); Adachi, T. [Kernfysisch Versneller Instituut, University of Groningen, 9747 AA Groningen (Netherlands); Akimune, H. [Department of Physics, Konan University, Kobe 568-8501 (Japan); Berg, G.P.A. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Harakeh, M.N. [Kernfysisch Versneller Instituut, University of Groningen, 9747 AA Groningen (Netherlands); GANIL, CEA/DSM-CNRS/IN2P3, 14076 Cean (France); Itoh, M. [Cyclotron and Radioisotope Center, Tohoku University, Sendai 980-8578 (Japan); Iwamoto, C. [Department of Physics, Konan University, Kobe 568-8501 (Japan); Long, A.; Matta, J.T. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Murakami, T. [Division of Physics and Astronomy, Kyoto University, Kyoto 606-8502 (Japan); Okamoto, A. [Department of Physics, Konan University, Kobe 568-8501 (Japan); Sault, K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Talwar, R. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame, IN 46556 (United States); Uchida, M. [Department of Physics, Tokyo Institute of Technology, Tokyo 152-8850 (Japan); and others

    2013-10-07

    Using inelastic α-scattering at extremely forward angles, including 0°, the strength distributions of the isoscalar giant monopole resonance (ISGMR) have been measured in the {sup 204,206,208}Pb isotopes in order to examine the proposed mutually enhanced magicity (MEM) effect on the nuclear incompressibility. The MEM effect had been suggested as a likely explanation of the “softness” of nuclear incompressibility observed in the ISGMR measurements in the Sn and Cd isotopes. Our experimental results rule out any manifestation of the MEM effect in nuclear incompressibility and leave the question of the softness of the open-shell nuclei unresolved still.

  4. High-precision gamma-ray spectroscopy for enhancing production and application of medical isotopes

    Science.gov (United States)

    McCutchan, E. A.; Sonzogni, A. A.; Smith, S. V.; Muench, L.; Nino, M.; Greene, J. P.; Carpenter, M. P.; Zhu, S.; Chillery, T.; Chowdhury, P.; Harding, R.; Lister, C. J.

    2015-10-01

    Nuclear medicine is a field which requires precise decay data for use in planning radionuclide production and in imaging and therapeutic applications. To address deficiencies in decay data, sources of medical isotopes were produced and purified at the Brookhaven Linear Isotope Producer (BLIP) then shipped to Argonne National Laboratory where high-precision, gamma-ray measurements were performed using Gammasphere. New decay schemes for a number of PET isotopes and the impact on dose calculations will be presented. To investigate the production of next-generation theranostic or radiotherapeutic isotopes, cross section measurements with high energy protons have also been explored at BLIP. The 100-200 MeV proton energy regime is relatively unexplored for isotope production, thus offering high discovery potential but at the same time a challenging analysis due to the large number of open channels at these energies. Results of cross sections deduced from Compton-suppressed, coincidence gamma-ray spectroscopy performed at Lowell will be presented, focusing on the production of platinum isotopes by irradiating natural platinum foils with 100 to 200 MeV protons. DOE Isotope Program is acknowledged for funding ST5001030. Work supported by the US DOE under Grant DE-FG02-94ER40848 and Contracts DE-AC02-98CH10946 and DE-AC02-06CH11357.

  5. Laser alteration of accommodation coefficient for isotope separation

    International Nuclear Information System (INIS)

    Keck, J.C.

    1976-01-01

    This patent describes a method and an apparatus for separating isotope types by inducing an isotopically selective vibrational excitation of molecules containing at least one atom of the element type whose isotopes are to be separated. Vibrational excitation is induced in the molecules by finely tuned, narrow bandwidth laser radiation applied to a gaseous flow of the molecules. Isotopic separation of the molecules is achieved from the enhanced difference in diffusion rates for the molecules due to an alteration of the accommodation coefficients in the excited molecules. 40 claims, 4 figures

  6. Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

    Science.gov (United States)

    Wirstrom, E. S.; Charnley, S. B.; Geppert, W. D.; Persson, C. M.

    2012-01-01

    Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes

  7. Process chemistry related to hydrogen isotopes

    International Nuclear Information System (INIS)

    Iwasaki, Matae; Ogata, Yukio

    1991-01-01

    Hydrogen isotopes, that is, protium, deuterium and tritium, are all related deeply to energy in engineering region. Deuterium and tritium exist usually as water in extremely thin state. Accordingly, the improvement of the technology for separating these isotopes is a large engineering subject. Further, tritium is radioactive and its half-life period is 12.26 years, therefore, it is desirable to fix it in more stable form besides its confinement in the handling system. As the chemical forms of hydrogen, the molecular hydrogen with highest reactivity, metal hydride, carbon-hydrogen-halogen system compounds, various inorganic hydrides, most stable water and hydroxides are enumerated. The grasping of the behavior from reaction to stable state of these hydrogen compounds and the related materials is the base of process chemistry. The reaction of exchanging isotopes between water and hydrogen on solid catalyzers, the decomposition of ethane halide containing hydrogen, the behavior of water and hydroxides in silicates are reported. The isotope exchange between water and hydrogen is expected to be developed as the process of separating and concentrating hydrogen isotopes. (K.I.) 103 refs

  8. Thermodynamics of calcium-isotope-exchange reactions. 1. Exchange between isotopic calcium carbonates and aqueous calcium ions

    International Nuclear Information System (INIS)

    Zhang, R.S.; Nash, C.P.; Rock, P.A.

    1988-01-01

    This paper reports the authors results for the direct experimental determination of the equilibrium constant for the calcium-isotope-exchange reaction 40 CaCO 3 (s) + 44 CaCl 2 (aq) reversible 44 CaCO 2 (s) + 40 CaCl 2 (aq). The reaction was studied in electrochemical double cells without liquid junction of the type shown in eq 2. The experimental value of the equilibrium constant at 295 +/- 2 K is K = 1.08 +/- 0.02. The experimental value for K is compared with the values of K calculated for various model reactions according to the statistical thermodynamic theory of isotope effects. The isotopic solid carbonates were modeled according to both the Debye and Kieffer theories. No structured models of solvated isotopic aqueous calcium ions yield calculated equilibrium constants in agreement with their experimental results. This conclusion is in agreement with published molecular dynamics calculations which show that the aqueous solvation of Ca 2 =(aq) is essentially unstructured

  9. Effects of molecular weight of natural organic matter on cadmium mobility in soil environments and its carbon isotope characteristics

    International Nuclear Information System (INIS)

    Mahara, Y.; Kubota, T.; Wakayama, R.; Nakano-Ohta, T.; Nakamura, T.

    2007-01-01

    We investigated the role of natural organic matter in cadmium mobility in soil environments. We collected the dissolved organic matter from two different types of natural waters: pond surface water, which is oxic, and deep anoxic groundwater. The collected organic matter was fractionated into four groups with molecular weights (unit: Da (Daltons)) of 3 , 1-10 x 10 3 , 10-100 x 10 3 , and > 100 x 10 3 . The organic matter source was land plants, based on the carbon isotope ratios (δ 13 C/ 12 C). The organic matter in surface water originated from presently growing land plants, based on 14 C dating, but the organic matter in deep groundwater originated from land plants that grew approximately 4000 years ago. However, some carbon was supplied by the high-molecular-weight fraction of humic substances in soil or sediments. Cadmium interacted in a system of siliceous sand, fractionated organic matter, and water. The lowest molecular weight fraction of organic matter ( 3 ) bound more cadmium than did the higher molecular weight fractions. Organic matter in deep groundwater was more strongly bound to cadmium than was organic matter in surface water. The binding behaviours of organic matter with cadmium depended on concentration, age, molecular weight, and degradation conditions of the organic matter in natural waters. Consequently, the dissolved, low-molecular-weight fraction in organic matter strongly influences cadmium migration and mobility in the environment

  10. Isotopically modified nanoparticles for enhanced detection in bioaccumulation studies

    Science.gov (United States)

    Misra, S.K.; Dybowska, A.; Berhanu, D.; Croteau, M.-N.; Luoma, S.N.; Boccaccini, A.R.; Valsami-Jones, E.

    2012-01-01

    This work presents results on synthesis of isotopically enriched (99% 65Cu) copper oxide nanoparticles and its application in ecotoxicological studies. 65CuO nanoparticles were synthesized as spheres (7 nm) and rods (7 ?? 40 nm). Significant differences were observed between the reactivity and dissolution of spherical and rod shaped nanoparticles. The extreme sensitivity of the stable isotope tracing technique developed in this study allowed determining Cu uptake at exposure concentrations equivalent to background Cu concentrations in freshwater systems (0.2-30 ??g/L). Without a tracer, detection of newly accumulated Cu was impossible, even at exposure concentrations surpassing some of the most contaminated water systems (>1 mg/L). ?? 2011 American Chemical Society.

  11. Interaction between shallow and deep aquifers in the Tivoli Plain (Central Italy) enhanced by groundwater extraction: A multi-isotope approach and geochemical modeling

    International Nuclear Information System (INIS)

    Carucci, Valentina; Petitta, Marco; Aravena, Ramon

    2012-01-01

    In the Tivoli Plain (Rome, Central Italy) the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using isotopic and chemical tracers. A conceptual model of the groundwater flowpaths has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as DIC/Cl − , Ca/(Ca + Mg)/SO 4 /(SO 4 + HCO 3 ), and environmental isotopes (δ 18 O, δ 2 H, 87 Sr/ 86 Sr, δ 34 S and δ 13 C) was carried out in order to determine the sources of recharge of the aquifer, the origin of solutes and the mixing processes in groundwater of Tivoli Plain. Multivariate statistical methods such as principal component analysis and Cluster analyses have confirmed the existence of different geochemical facies and the role of mixing in the chemical composition of the groundwater. Results indicate that the hydrochemistry of groundwater is characterized by mixing between end-members coming directly from carbonate recharge areas and to groundwater circulating in a deeply buried Meso-Cenozoic carbonate sequence. The travertine aquifer is fed by both flow systems, but a local contribution by direct input in the Plain has also been recognized. The stable isotope data ( 18 O, 2 H, 13 C and 34 S) supports the flow system conceptual model inferred from the geochemical data and represents key data to quantify the geochemical mixing in the different groundwaters of the Plain. The results of numerical modeling (PHREEQC) are consistent with the flowpaths derived from the hydrogeochemical conceptual model. The inverse models performed generated the main geochemical processes occurring in the groundwater flow system, which also included mixing. Geochemical and isotope modeling demonstrate an increasing influence of groundwater from the deeply buried aquifer in the travertine aquifer, enhanced by lowering of the travertine aquifer water table due to quarry pumping.

  12. Molecular dynamics based enhanced sampling of collective variables with very large time steps

    Science.gov (United States)

    Chen, Pei-Yang; Tuckerman, Mark E.

    2018-01-01

    Enhanced sampling techniques that target a set of collective variables and that use molecular dynamics as the driving engine have seen widespread application in the computational molecular sciences as a means to explore the free-energy landscapes of complex systems. The use of molecular dynamics as the fundamental driver of the sampling requires the introduction of a time step whose magnitude is limited by the fastest motions in a system. While standard multiple time-stepping methods allow larger time steps to be employed for the slower and computationally more expensive forces, the maximum achievable increase in time step is limited by resonance phenomena, which inextricably couple fast and slow motions. Recently, we introduced deterministic and stochastic resonance-free multiple time step algorithms for molecular dynamics that solve this resonance problem and allow ten- to twenty-fold gains in the large time step compared to standard multiple time step algorithms [P. Minary et al., Phys. Rev. Lett. 93, 150201 (2004); B. Leimkuhler et al., Mol. Phys. 111, 3579-3594 (2013)]. These methods are based on the imposition of isokinetic constraints that couple the physical system to Nosé-Hoover chains or Nosé-Hoover Langevin schemes. In this paper, we show how to adapt these methods for collective variable-based enhanced sampling techniques, specifically adiabatic free-energy dynamics/temperature-accelerated molecular dynamics, unified free-energy dynamics, and by extension, metadynamics, thus allowing simulations employing these methods to employ similarly very large time steps. The combination of resonance-free multiple time step integrators with free-energy-based enhanced sampling significantly improves the efficiency of conformational exploration.

  13. Molecularly imprinted solid phase extraction using stable isotope labeled compounds as template and liquid chromatography-mass spectrometry for trace analysis of bisphenol A in water sample

    International Nuclear Information System (INIS)

    Kawaguchi, Migaku; Hayatsu, Yoshio; Nakata, Hisao; Ishii, Yumiko; Ito, Rie; Saito, Koichi; Nakazawa, Hiroyuki

    2005-01-01

    We have developed a molecularly imprinted polymer (MIP) using a stable isotope labeled compound as the template molecule and called it the ''isotope molecularly imprinted polymer'' (IMIP). In this study, bisphenol A (BPA) was used as the model compound. None imprinted polymer (NIP), MIP, dummy molecularly imprinted polymer (DMIP) and IMIP were prepared by the suspension polymerization method using without template, BPA, 4-tert-butylphenol (BP) and bisphenol A-d 16 (BPA-d 16 ), respectively. The polymers were subjected to molecularly imprinted solid phase extraction (MI-SPE), and the extracted samples were subjected to liquid chromatography-mass spectrometry (LC-MS). Although the leakage of BPA-d 16 from the IMIP was observed and that of BPA was not observed. The selectivity factors of MIP and IMIP for BPA were 4.45 and 4.43, respectively. Therefore, IMIP had the same molecular recognition ability as MIP. When MI-SPE with IMIP was used and followed by LC-MS in the analysis of river water sample, the detection limit of BPA was 1 ppt with high sensitivity. Moreover, the average recovery was higher than 99.8% (R.S.D.: 3.7%) by using bisphenol A- 13 C 12 (BPA- 13 C 12 ) as the surrogate standard. In addition, the IMIP were employed in MI-SPE of BPA in river water sample by LC-MS. The concentration of BPA in the river water sample was determined to be 32 pg ml -1 . We confirmed that it was possible to measure trace amounts of a target analyte by MI-SPE using IMIP

  14. Studies of isotopic defined hydrogen beams scattering from Pd single-crystal surfaces

    International Nuclear Information System (INIS)

    Varlam, Mihai; Steflea, Dumitru

    2001-01-01

    An experimental investigation of hydrogen isotopes interaction with Pd single-crystal surface has been carried out using molecular beam technique. The energy dependence of the sticking probability and its relation with the trapping probability into the precursor state is studied by integrating the scattered angular distribution of hydrogen Isotopic defined beams from Pd (111) surface in the 40-400 K surface temperature range. The dependence has been evaluated by defining hydrogen molecular beams with different isotopic concentration - from the natural one to the 5% D/(D+H) ratio - and for different incident energies. The beam was directed onto a single-crystal Pd (111) surface. In the paper, we report the experimental results and some considerations related to it. (authors)

  15. Studies of isotopic defined hydrogen beams scattering from Pd single-crystal surfaces

    International Nuclear Information System (INIS)

    Varlam, Mihai; Steflea, Dumitru

    1999-01-01

    An experimental investigation of hydrogen isotopes interaction with Pd single-crystal surfaces has been carried out using molecular beam technique. The energy dependence of the sticking probability and its relation with the trapping probability into the precursor state is studied by integrating the scattered angular distribution of hydrogen isotopic defined beams from Pd (111) surfaces in the 40 - 400 K surface temperature range. The dependence has been evaluated by defining hydrogen molecular beams with different isotopic concentration - from the natural one until 5% D/(D + H) and different incident energies and directed onto a single - crystal Pd (111) surface. In the paper, we report the experimental results and some considerations related to them. (authors)

  16. Production of high-purity isotopes by electromagnetic separation; Production electromagnetique d'isotope tres purs

    Energy Technology Data Exchange (ETDEWEB)

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

    1958-07-01

    Improvement in isotopic purity of nuclides prepared by electromagnetic separation is searched into the principle of cascades of monochromators. The principal drawback of which is to allow the separation of only one isotope at a time. The electromagnetic separator of Saclay is equipped with an electrostatic post-analyzer, which is described. Significant results are obtained, concerning isotopic enhancements of uranium-235 and mercury-204. A schema of isotopic contagion is then proposed, the basis of it is the scattering of the primary ions in the residual atmosphere of the separator chamber. The most frequent type of collisions being accompanied by neutralisation of the ions, the schema explains the efficiency of the second stage. As a matter of conclusion, some particularities concerning the routine work at a high enhancement, small output machine, are given. (author) [French] L'accroissement de la purete isotopique des especes nucleaires preparees par separation electromagnetique est recherche dans l'emploi du principe des cascades de monochromateurs, moyennant la servitude de ne collecter qu'un isotope a la fois. Le separateur electromagnetique de Saclay est equipe dans ce but d'un post-analyseur electrostatique, qui est decrit. Des resultats significatifs sont donnes, portant sur les enrichissements obtenus dans les separations d'uranium-235 et de mercure-204. Un schema de contagion isotopique est propose. Il est fonde sur la diffusion a petit angle accompagnant la neutralisation des faisceaux primaires par collision avec le gaz residuel. Ce schema permet d'expliquer l'efficacite de l'etage electrostatique. En matiere de conclusion, la methode d'exploitation d'une machine a faible debit et a haut enrichissement est donnee. (auteur)

  17. Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

    Science.gov (United States)

    Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Retention of hydrogen isotopes and helium in nickel

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Mitsumasa; Sato, Rikiya; Yamaguchi, Kenji; Yamawaki, Michio [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab.

    1996-10-01

    In the present study, a thin foil of nickel was irradiated by H{sub 2}{sup +}, D{sub 2}{sup +} and He{sup +} to a fluence of 1.2-6.0x10{sup 20}/m{sup 2} using the TBTS (Tritium Beam Test System) apparatus. The thermal desorption spectroscopy (TDS) technique was employed to evaluate the total amount of retained hydrogen isotope and helium atoms in nickel. In the spectra, two peaks appeared at 440-585K and 720-735K for helium. Hydrogen isotopes irradiation after helium preirradiation were found to enhance the helium release and to decrease the peak temperatures. Helium irradiation after hydrogen isotopes preirradiation were found to enhance the helium release, but the peak temperature showed little difference from that without preirradiation. (author)

  19. Paloma: an instrument to measure the molecular, elemental and isotopic composition of the mars atmosphere from a landed platform (MSL 09, EXOMARS)

    Energy Technology Data Exchange (ETDEWEB)

    Sabroux, J.Ch

    2003-07-01

    An instrument to analyze the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform is being developed under CNES funding. This instrument, called PALOMA (Payload for Local Observation of Mars Atmosphere), will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. Noble gases (He, Ne, Ar, Xr, Xe) and stable isotopes (C, H, O, N) will be analyzed by using a system of gas purification and separation, coupled with a mass spectrometer. The heaviest, radioactive, noble gas (Rn) and its short-lived daughters will be measured using a small additional device (alpha particle detector). Detailed search for trace constituents of astro-biological interest, like CH{sub 4}, H{sub 2}CO, N{sub 2}O, H{sub 2}S (abundances, isotopic ratios, time variability) will be done on a regular temporal basis during one Martian year. Isotopic ratios will be measured with an accuracy of about 1 ppm, or better, in order to provide a clear diagnosis of possible life signatures, to allow a detailed comparison of Earth and Mars atmospheric fractionation patterns and, finally, to accurately disentangle escape, climatic, geochemical and hypothesized biological effects. High sensitivity is required for elemental and isotopic compositions of trace gases of interest. Such an accurate monitoring of Mars atmosphere volatile composition is expected to provide the necessary reference for future composition studies of minerals, soils, bio-markers, polar cap material, either by in-situ measurement, or from laboratory analyses of returned samples. (author)

  20. Paloma: an instrument to measure the molecular, elemental and isotopic composition of the mars atmosphere from a landed platform (MSL 09, EXOMARS)

    International Nuclear Information System (INIS)

    Sabroux, J.Ch.

    2003-01-01

    An instrument to analyze the molecular, elemental and isotopic composition of Mars atmosphere from a landed platform is being developed under CNES funding. This instrument, called PALOMA (Payload for Local Observation of Mars Atmosphere), will be proposed in response to the AO for the instrumentation of the NASA Mars Smart Lander mission, planned to be launched in 2009. It might be part as well of the EXOMARS mission presently studied at ESA in the frame of the Aurora program. Noble gases (He, Ne, Ar, Xr, Xe) and stable isotopes (C, H, O, N) will be analyzed by using a system of gas purification and separation, coupled with a mass spectrometer. The heaviest, radioactive, noble gas (Rn) and its short-lived daughters will be measured using a small additional device (alpha particle detector). Detailed search for trace constituents of astro-biological interest, like CH 4 , H 2 CO, N 2 O, H 2 S (abundances, isotopic ratios, time variability) will be done on a regular temporal basis during one Martian year. Isotopic ratios will be measured with an accuracy of about 1 ppm, or better, in order to provide a clear diagnosis of possible life signatures, to allow a detailed comparison of Earth and Mars atmospheric fractionation patterns and, finally, to accurately disentangle escape, climatic, geochemical and hypothesized biological effects. High sensitivity is required for elemental and isotopic compositions of trace gases of interest. Such an accurate monitoring of Mars atmosphere volatile composition is expected to provide the necessary reference for future composition studies of minerals, soils, bio-markers, polar cap material, either by in-situ measurement, or from laboratory analyses of returned samples. (author)

  1. Iron isotopic systematics of oceanic basalts

    Science.gov (United States)

    Teng, Fang-Zhen; Dauphas, Nicolas; Huang, Shichun; Marty, Bernard

    2013-04-01

    The iron isotopic compositions of 93 well-characterized basalts from geochemically and geologically diverse mid-ocean ridge segments, oceanic islands and back arc basins were measured. Forty-three MORBs have homogeneous Fe isotopic composition, with δ56Fe ranging from +0.07‰ to +0.14‰ and an average of +0.105 ± 0.006‰ (2SD/√n, n = 43, MSWD = 1.9). Three back arc basin basalts have similar δ56Fe to MORBs. By contrast, OIBs are slightly heterogeneous with δ56Fe ranging from +0.05‰ to +0.14‰ in samples from Koolau and Loihi, Hawaii, and from +0.09‰ to +0.18‰ in samples from the Society Islands and Cook-Austral chain, French Polynesia. Overall, oceanic basalts are isotopically heavier than mantle peridotite and pyroxenite xenoliths, reflecting Fe isotope fractionation during partial melting of the mantle. Iron isotopic variations in OIBs mainly reflect Fe isotope fractionation during fractional crystallization of olivine and pyroxene, enhanced by source heterogeneity in Koolau samples.

  2. Isotopic studies of trans- and cis-HOCO using rotational spectroscopy: Formation, chemical bonding, and molecular structures

    Energy Technology Data Exchange (ETDEWEB)

    McCarthy, Michael C., E-mail: mccarthy@cfa.harvard.edu; Martinez, Oscar; Crabtree, Kyle N.; Martin-Drumel, Marie-Aline [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, USA and School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138 (United States); McGuire, Brett A. [National Radio Astronomy Observatory, Charlottesville, Virginia 22901 (United States); Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, USA and School of Engineering and Applied Sciences, Harvard University, 29 Oxford Street, Cambridge, Massachusetts 02138 (United States); Stanton, John F. [Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165 (United States)

    2016-03-28

    HOCO is an important intermediate in combustion and atmospheric processes because the OH + CO → H + CO{sub 2} reaction represents the final step for the production of CO{sub 2} in hydrocarbon oxidation, and theoretical studies predict that this reaction proceeds via various intermediates, the most important being this radical. Isotopic investigations of trans- and cis-HOCO have been undertaken using Fourier transform microwave spectroscopy and millimeter-wave double resonance techniques in combination with a supersonic molecular beam discharge source to better understand the formation, chemical bonding, and molecular structures of this radical pair. We find that trans-HOCO can be produced almost equally well from either OH + CO or H + CO{sub 2} in our discharge source, but cis-HOCO appears to be roughly two times more abundant when starting from H + CO{sub 2}. Using isotopically labelled precursors, the OH + C{sup 18}O reaction predominately yields HOC{sup 18}O for both isomers, but H{sup 18}OCO is observed as well, typically at the level of 10%-20% that of HOC{sup 18}O; the opposite propensity is found for the {sup 18}OH + CO reaction. DO + C{sup 18}O yields similar ratios between DOC{sup 18}O and D{sup 18}OCO as those found for OH + C{sup 18}O, suggesting that some fraction of HOCO (or DOCO) may be formed from the back-reaction H + CO{sub 2}, which, at the high pressure of our gas expansion, can readily occur. The large {sup 13}C Fermi-contact term (a{sub F}) for trans- and cis-HO{sup 13}CO implicates significant unpaired electronic density in a σ-type orbital at the carbon atom, in good agreement with theoretical predictions. By correcting the experimental rotational constants for zero-point vibration motion calculated theoretically using second-order vibrational perturbation theory, precise geometrical structures have been derived for both isomers.

  3. Atomic and Molecular Data for State-Resolved Modelling of Hydrogen and Helium and Their Isotopes in Fusion Plasma. Summary Report of the First Research Coordination Meeting

    International Nuclear Information System (INIS)

    Braams, B. J.

    2013-12-01

    The First Research Coordination Meeting of the IAEA Coordinated Research Project (CRP) on 'Atomic and Molecular Data for State-Resolved Modelling of Hydrogen and Helium and Their Isotopes in Fusion Plasma' was held 10-12 August 2011 at IAEA Headquarters in Vienna. Participants reviewed the status of the database on molecular processes of H and He, identified data needs and made plans for development of new data in connection with the CRP. The proceedings of the meeting are summarized here. Participants' summaries and work plans are also provided. (author)

  4. Simplified simulation of multicomponent isotope separation by gas centrifuge

    International Nuclear Information System (INIS)

    Guo Zhixiong; Ying Chuntong

    1995-01-01

    The expressions of diffusion equation for multicomponent isotope separation by gas centrifuge are derived by utilizing the simplified diffusion transport vector. A method of radial averaging which was restricted to a binary mixture is extended to multicomponent isotope mixtures by using an iterative scheme. A numerical analysis of tetradic UF 6 or SF 6 gas isotope separation by centrifuge is discussed when a special model of velocity distribution is given. The dependence of mutual separation factor for the components on their molecular weights' difference is obtained. Some aspects of the given model of gas fluid are also discussed

  5. Method and apparatus for controlled condensation isotope separation

    International Nuclear Information System (INIS)

    Sullivan, J.A.; Lee, J.T. Jr.; Kim, K.C.

    1981-01-01

    The invention provides a method for producing controlled homogeneous condensation of a molecular feed gas containing several isotopes. The feed gas flows at supersonic rates through an expansion nozzle under conditions at which the gas would normally condense. The gas is irradiated with laser radiation of a wavelength that selectively excites those molecules in the feed gas that contain a particular isotope, thus preventing their condensation. Condensate particles may be aerodynamically separated from the flowing gas stream

  6. Calcium isotope fractionation in liquid chromatography with benzo-18-crown-6 resin in aqueous hydrobromic acid medium

    International Nuclear Information System (INIS)

    Sato, Takuya; Oi, Takao

    2015-01-01

    Liquid chromatography operated in a breakthrough mode was employed to study calcium isotope fractionation in the aqueous hydrobromic acid medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of calcium was observed in the frontal part of respective calcium chromatograms. The values of the isotope fractionation coefficient were on the order of 10 -3 . The observed isotope fractionation coefficient was dependent on the concentration of hydrobromic acid in the calcium feed solution; a higher HBr concentration resulted in a smaller fractionation coefficient value. The present calcium isotope effects were most probably mass-dependent, indicating that they mostly came from isotope effects based on molecular vibration. Molecular orbital calculations supported the present experimental results in a qualitative fashion. Chromatography operated in aqueous HBr media is a better system of Ca isotope separation than that operated in aqueous HCl media. (author)

  7. Stable isotope separation by thermal diffusion

    International Nuclear Information System (INIS)

    Vasaru, Gheorghe

    2001-01-01

    Thermal diffusion in both gaseous and liquid phase has been subject of extensive experimental and theoretical investigations, especially after the invention of K. Clusius and G. Dickel of the thermal diffusion column, sixty three years ago. This paper gives a brief overview of the most important research and developments performed during the time at the National Institute for Research and Development for Isotopic and Molecular Technology (ITIM) at Cluj - Napoca, Romania in the field of separation of stable isotopes by thermal diffusion. An retrospective analysis of the research and results concerning isotope separation by thermal diffusion entails the following conclusions: - thermal diffusion is an adequate method for hydrogen isotope separation (deuterium and tritium) and for noble gas isotope separation (He, Ne, Ar, Kr, Xe); - thermal diffusion is attractive also for 13 C enrichment using methane as raw material for separation, when annual yields of up to 100 g are envisaged; - lately, the thermal diffusion appears to be chosen as a final enrichment step for 17 O. An obvious advantage of this method is its non-specificity, i.e. the implied equipment can be utilized for isotope separation of other chemical elements too. Having in view the low investment costs for thermal diffusion cascades the method appears economically attractive for obtaining low-scale, laboratory isotope production. The paper has the following content: 1. The principle of method; 2. The method's application; 3. Research in the field of thermal diffusion at ITIM; 4. Thermal diffusion cascades for N, C, Ne, Ar and Kr isotope separation; 5. Conclusion

  8. Application of computational fluid dynamics for the simulation of cryogenic molecular sieve bed absorber of hydrogen isotopes recovery system for Indian LLCB-TBM

    Energy Technology Data Exchange (ETDEWEB)

    Gayathri Devi, V.; Sircar, A.; Sarkar, B. [Institute of Plasma Research, Bhat, Gandhinagar, Gujarar (India)

    2015-03-15

    One of the most challenging tasks in the design of the fuel cycle system lies in the effective design of Tritium Extraction System (TES) which involves proper extraction and purification of tritium in the fuel cycle of the fusion reactor. Indian Lead Lithium cooled Ceramic Breeder Test Blanket Module (LLCB-TBM) would extract hydrogen isotopes through Cryogenic Molecular Sieve Bed (CMSB) adsorber system. A prototype Hydrogen Isotopes Recovery System (HIRS) is being developed to validate the concepts for tritium extraction by adsorption mass transfer mechanism. In this study, a design model has been developed and analyzed to simulate the adsorption mass transfer kinetics in a fixed bed adsorption column. The simulation leads primarily to effective design of HIRS, which is a state-of-the-art technology. The paper describes the process simulation approach and the results of Computational Fluid Dynamics (CFD) analysis. The effects of different operating conditions are studied to investigate their influence on the hydrogen isotopes adsorption capacity. The results of the present simulation study would be used to understand the best optimized transport phenomenon before realizing the TES as a system for LLCB-TBM. (authors)

  9. Primordial Molecular Cloud Material in Metal-Rich Carbonaceous Chondrites

    Science.gov (United States)

    Taylor, G. J.

    2016-03-01

    The menagerie of objects that make up our Solar System reflects the composition of the huge molecular cloud in which the Sun formed, a late addition of short-lived isotopes from an exploding supernova or stellar winds from a neighboring massive star, heating and/or alteration by water in growing planetesimals that modified and segregated the primordial components, and mixing throughout the Solar System. Outer Solar System objects, such as comets, have always been cold, hence minimizing the changes experienced by more processed objects. They are thought to preserve information about the molecular cloud. Elishevah Van Kooten (Natural History Museum of Denmark and the University of Copenhagen) and co-authors in Denmark and at the University of Hawai'i, measured the isotopic compositions of magnesium and chromium in metal-rich carbonaceous chondrites. They found that the meteorites preserve an isotopic signature of primordial molecular cloud materials, providing a potentially detailed record of the molecular cloud's composition and of materials that formed in the outer Solar System.

  10. Raman spectroscopic studies of isotopic diatomic molecules and a technique for measuring stable isotope ratios using Raman scattering

    International Nuclear Information System (INIS)

    Harney, R.C.

    1976-01-01

    A method for measuring stable isotope ratios using Raman scattering has been developed. This method consists of simultaneously counting photons scattered out of a high-intensity laser beam by different isotopically-substituted molecules. A number of studies of isotopic diatomic molecules have been made. The Q-branches of the Raman spectra of the isotopic molecules 14 N 15 N and 16 O 18 O were observed at natural abundance in nitrogen and oxygen samples. Comparison of the ratios of the intensities of the Q-branches of the major nitrogen and oxygen isotopic molecules with mass spectrometric determinations of the isotopic compositions yielded scattering cross sections of 14 N 15 N relative to 14 N 14 N and 16 O 18 O relative to 16 O 16 O. These cross section ratios differ from unity, a difference which can be explained by considering nuclear mass effects on the Franck-Condon factors of the molecular transitions. The measured intensities of the 14 N 15 N and 16 O 18 O Q-branches provided the baseline data needed to make the previously-mentioned extrapolation. High-resolution (approximately 0.15 cm -1 ) spectra of the Q-branches of 14 N 14 N and 16 O 16 O yielded a direct determination of α/sub e/ (the difference between the rotational constant in the ground and first excited vibrational states) for these molecules. The measured values are in excellent agreement with those obtained by other means. Complete Raman spectra (pure rotation, rotation-vibration, and high-resolution Q-branch) were obtained on a sample of pure 18 O 18 O. Analysis of this data yielded the molecular parameters: the equilibrium internuclear separation r/sub e/, the moment of inertia I/sub e/, and the energy parameters α/sub e/, B/sub e/, and ΔG/sub 1 / 2 /. These are in good agreement with data obtained by microwave spectroscopy

  11. 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.

  12. Enhancing Irreversible Electroporation by Manipulating Cellular Biophysics with a Molecular Adjuvant.

    Science.gov (United States)

    Ivey, Jill W; Latouche, Eduardo L; Richards, Megan L; Lesser, Glenn J; Debinski, Waldemar; Davalos, Rafael V; Verbridge, Scott S

    2017-07-25

    Pulsed electric fields applied to cells have been used as an invaluable research tool to enhance delivery of genes or other intracellular cargo, as well as for tumor treatment via electrochemotherapy or tissue ablation. These processes involve the buildup of charge across the cell membrane, with subsequent alteration of transmembrane potential that is a function of cell biophysics and geometry. For traditional electroporation parameters, larger cells experience a greater degree of membrane potential alteration. However, we have recently demonstrated that the nuclear/cytoplasm ratio (NCR), rather than cell size, is a key predictor of response for cells treated with high-frequency irreversible electroporation (IRE). In this study, we leverage a targeted molecular therapy, ephrinA1, known to markedly collapse the cytoplasm of cells expressing the EphA2 receptor, to investigate how biophysical cellular changes resulting from NCR manipulation affect the response to IRE at varying frequencies. We present evidence that the increase in the NCR mitigates the cell death response to conventional electroporation pulsed-electric fields (∼100 μs), consistent with the previously noted size dependence. However, this same molecular treatment enhanced the cell death response to high-frequency electric fields (∼1 μs). This finding demonstrates the importance of considering cellular biophysics and frequency-dependent effects in developing electroporation protocols, and our approach provides, to our knowledge, a novel and direct experimental methodology to quantify the relationship between cell morphology, pulse frequency, and electroporation response. Finally, this novel, to our knowledge, combinatorial approach may provide a paradigm to enhance in vivo tumor ablation through a molecular manipulation of cellular morphology before IRE application. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  13. Theory of oxygen isotope exchange

    NARCIS (Netherlands)

    den Otter, M.W.; Boukamp, Bernard A.; Bouwmeester, Henricus J.M.

    2001-01-01

    Transients for oxygen molecular mass numbers 32, 34 and 36 are derived which can be used for the interpretation of oxygen isotope exchange data based on measurement of concentrations of 16O2, 16O18O and 18O2 in the gas phase. Key parameters in the theory are the rate at which oxygen molecules are

  14. Data mining for isotope discrimination in atom probe tomography

    Energy Technology Data Exchange (ETDEWEB)

    Broderick, Scott R. [Department of Materials Science and Engineering and Institute for Combinatorial Discovery, Iowa State University, Ames, IA 50011-2230 (United States); Bryden, Aaron [Ames National Laboratory, Ames, IA 50011-2230 (United States); Suram, Santosh K. [Department of Materials Science and Engineering and Institute for Combinatorial Discovery, Iowa State University, Ames, IA 50011-2230 (United States); Rajan, Krishna, E-mail: krajan@iastate.edu [Department of Materials Science and Engineering and Institute for Combinatorial Discovery, Iowa State University, Ames, IA 50011-2230 (United States)

    2013-09-15

    Ions with similar time-of-flights (TOF) can be discriminated by mapping their kinetic energy. While current generation position-sensitive detectors have been considered insufficient for capturing the isotope kinetic energy, we demonstrate in this paper that statistical learning methodologies can be used to capture the kinetic energy from all of the parameters currently measured by mathematically transforming the signal. This approach works because the kinetic energy is sufficiently described by the descriptors on the potential, the material, and the evaporation process within atom probe tomography (APT). We discriminate the isotopes for Mg and Al by capturing the kinetic energy, and then decompose the TOF spectrum into its isotope components and identify the isotope for each individual atom measured. This work demonstrates the value of advanced data mining methods to help enhance the information resolution of the atom probe. - Highlights: ► Atom probe tomography and statistical learning were combined for data enhancement. ► Multiple eigenvalue decompositions decomposed a spectrum with overlapping peaks. ► The isotope of each atom was determined by kinetic energy discrimination. ► Eigenspectra were identified and new chemical information was identified.

  15. Some connections between importance sampling and enhanced sampling methods in molecular dynamics.

    Science.gov (United States)

    Lie, H C; Quer, J

    2017-11-21

    In molecular dynamics, enhanced sampling methods enable the collection of better statistics of rare events from a reference or target distribution. We show that a large class of these methods is based on the idea of importance sampling from mathematical statistics. We illustrate this connection by comparing the Hartmann-Schütte method for rare event simulation (J. Stat. Mech. Theor. Exp. 2012, P11004) and the Valsson-Parrinello method of variationally enhanced sampling [Phys. Rev. Lett. 113, 090601 (2014)]. We use this connection in order to discuss how recent results from the Monte Carlo methods literature can guide the development of enhanced sampling methods.

  16. Availability of caesium isotopes in vegetation estimated from incubation and extraction experiments

    International Nuclear Information System (INIS)

    Salbu, B.; Oestby, G.; Garmo, T.H.; Hove, K.

    1992-01-01

    A rapid and inexpensive incubation and extraction technique for estimating the available low molecular weight and potentially bioavailable fraction of Cs isotopes in vegetation has been developed. Samples of contaminated vegetation (grass, herbage and fungi) and litter were exposed to rumen liquid from sheep, by in vitro incubation or by placing nylon bags in the rumen of sheep (in sacco). The results were compared with laboratory extractions using rumen buffer, NH 4 OAc, CsCl and de-ionized water. The release of low molecular weight 137 Cs species after in vitro incubation with rumen liquid for 4-8 h was 75-85% for grass, herbage and fungi, 30% for lichen and 10% for litter. The reproducibility of the method was 5% for digestible matrices and 10-20% for litter where the fraction of Cs isotopes released was small. Extractions with NH 4 OAc and CsCl released 75 and 80% of the Cs isotopes in grass, respectively. Significantly lower extraction yields were obtained with de-ionized water and buffer. During in sacco incubation, 90-100% of the Cs isotopes in vegetation was released within 1 h; however, potentially available low molecular weight forms and Cs-bearing colloidal material could not be differentiated. The results obtained by incubation with rumen liquid and by extraction with NH 4 OAc or CsCl were in good agreement with published data from a 3 week feeding trial. For practical reasons extraction with NH 4 OAc or CsCl rather than incubation with rumen liquid is recommended for estimating the fraction of available low molecular weight Cs species. Results from incubation with rumen liquid showed that the availability of Cs isotopes in grass collected in 1986 was low (15%), but increased with time up to 1989 (75-80%). It is probable that the high fraction of inert 137 Cs species reflects surface contamination in 1986. (author)

  17. Gas-chromatographic separation of hydrogen isotopic mixtures

    International Nuclear Information System (INIS)

    Preda, Anisoara; Bidica, Nicolae

    2005-01-01

    Full text: Gas chromatographic separation of hydrogen isotopes have been reported in the literature since late of 1950's. Gas chromatography is primarily an analytical method, but because of its properties it may be used in many other fields with excellent results. A simple method is proposed for the gas-chromatographic analysis of complex gas mixtures containing hydrogen isotopes; the method is based on the substantial difference in the thermal conductivity of these isotopes. One of the main disadvantages of the conventional gas chromatography is the long retention times required for the analysis of hydrogen gas mixtures while the column is operated at very low temperature. The method described in this paper was based on using a capillary molecular sieve 5A column operated for this kind of separation at 173 K. The carrier gas was Ne and the detector was TCD. In the paper chromatograms for various carrier flow rates and various hydrogen isotope mixtures are presented. (authors)

  18. Selective laser ionization for mass-spectral isotopic analysis

    International Nuclear Information System (INIS)

    Miller, C.M.; Nogar, N.S.; Downey, S.W.

    1983-01-01

    Resonant enhancement of the ionization process can provide a high degree of elemental selectivity, thus eliminating or drastically reducing the interference problem. In addition, extension of this method to isotopically selective ionization has the potential for greatly increasing the range of isotope ratios that can be determined experimentally. This gain can be realized by reducing or eliminating the tailing of the signal from the high-abundance isotope into that of the low-abundance isotope, augmenting the dispersion of the mass spectrometer. We briefly discuss the hardware and techniques used in both our pulsed and cw RIMS experiments. Results are presented for both cw ionization experiments on Lu/Yb mixtures, and spectroscopic studies of multicolor RIMS of Tc. Lastly, we discuss practical limits of cw RIMS analysis in terms of detection limits and measurable isotope ratios

  19. Isotopic and geochemical tools to assess the feasibility of methanogenesis as a way to enhance hydrocarbon recovery in oil reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, N.; Morris, B.E.L.; Richnow, H.H. [Helmholtz-Zentrum fuer Umweltforschung (UFZ), Leipzig (Germany). Abt. Isotopenbiogeochemie; Cai, M.; Yao, Jun [Helmholtz-Zentrum fuer Umweltforschung (UFZ), Leipzig (Germany). Abt. Isotopenbiogeochemie; University of Sicence and Technology, Beijing (China). School of Civil and Environment Engineering; Straaten, N.; Krueger, M. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany). Fachbereich Geochemie

    2013-08-01

    In situ biotransformation of oil to methane was investigated in a thermophilic reservoir in Dagang, China using isotopic analyzes, chemical fingerprinting and molecular and biological methods. Our first results, which were already published, demonstrated that anaerobic oil degradation concomitant with methane production was occurring. The reservoir was highly methanogenic and the oil exhibited varying degrees of degradation between different parts of the reservoir, although it was mainly highly weathered, and nearly devoid of nalkanes, alkylbenzenes, alkyltoluenes, and light PAHs. In addition, the isotopic data from reservoir oil, water and gas was used to elucidate the origin of the methane. The average {delta}{sup 13}C for methane was around -47 permille and CO{sub 2} was highly enriched in {sup 13}C. The bulk isotopic discrimination ({Delta}{delta}{sup 13}C) between methane and CO{sub 2} was between 32 and 65 permille, in accordance with previously reported results for methane formation during hydrocarbon degradation. Subsequent microcosm experiments revealed that autochthonous microbiota are capable of degrading oil under methanogenic conditions and of producing methane and/or CO{sub 2} from {sup 13}C-labelled n-hexadecane, 2-methylnaphthalene or toluene ({delta}{sup 13}C values up to 550 permille). These results demonstrate that methanogenesis is linked to aliphatic and aromatic hydrocarbon degradation. Further experiments will elucidate the activation mechanisms for the different compounds. (orig.)

  20. Basic separative power of multi-component isotopes separation in a gas centrifuge

    International Nuclear Information System (INIS)

    Jiang, Hongmin; Lei, Zengguang; Zhuge, Fu

    2008-01-01

    On condition that the overall separation factor per unit exists in centrifuge for multi-component isotopes separation, the relations between separative power of each component and molecular weight have been investigated in the paper while the value function and the separative power of binary-component separation are adopted. The separative power of each component is proportional to the square of the molecular weight difference between its molecular weight and the average molecular weight of other remnant components. In addition, these relations are independent on the number of the components and feed concentrations. The basic separative power and related expressions, suggested in the paper, can be used for estimating the separative power of each component and analyzing the separation characteristics. The most valuable application of the basic separative power is to evaluate the separative capacity of centrifuge for multi-component isotopes. (author)

  1. Colon-targeted delivery of piceatannol enhances anti-colitic effects of the natural product: potential molecular mechanisms for therapeutic enhancement

    Directory of Open Access Journals (Sweden)

    Yum S

    2015-08-01

    Full Text Available Soohwan Yum, Seongkeun Jeong, Sunyoung Lee, Joon Nam, Wooseong Kim, Jin-Wook Yoo, Min-Soo Kim, Bok Luel Lee, Yunjin Jung College of Pharmacy, Pusan National University, Busan, Republic of Korea Abstract: Piceatannol (PCT, an anti-colitic natural product, undergoes extensive Phase II hepatic metabolism, resulting in very low bioavailability. We investigated whether colon-targeted delivery of PCT could enhance anti-colitic effects and how therapeutic enhancement occurred at the molecular level. Molecular effects of PCT were examined in human colon carcinoma cells and inflamed colons. The anti-colitic effects of PCT in a colon-targeted capsule (colon-targeted PCT were compared with PCT in a gelatin capsule (conventional PCT in a trinitrobenzene sulfonic acid-induced rat colitis model. Colon-targeted PCT elicited greatly enhanced recovery of the colonic inflammation. In HCT116 cells, PCT inhibited nuclear factor kappaB while activating anti-colitic transcription factors, nuclear factor-erythroid 2 (NF-E2 p45-related factor 2, and hypoxia-inducible factor-1. Colon-targeted PCT, but not conventional PCT, modulated production of the target gene products of the transcription factors in the inflamed colonic tissues. Rectal administration of PCT, which simulates the therapeutic action of colon-targeted PCT, also ameliorated rat colitis and reproduced the molecular effects in the inflamed colonic tissues. Colon-targeted delivery increased therapeutic efficacy of PCT against colitis, likely resulting from multitargeted effects exerted by colon-targeted PCT. The drug delivery technique may be useful for therapeutic optimization of anti-colitic lead compounds including natural products. Keywords: piceatannol, colitis, colon-targeted delivery, multitarget, polypharmacology

  2. Adsorption methods for hydrogen isotope storage on zeolite sieves

    International Nuclear Information System (INIS)

    Cristescu, Ioana; Cristescu, Ion; Vasut, Felicia; Brad, Sebastian; Lazar, Alin

    2001-01-01

    Adsorption molecular sieves and activated carbon were used for hydrogen isotopes. The adsorption process proceeds at liquid nitrogen and liquid hydrogen temperatures. The synthetic zeolites have similar properties as natural zeolites, but they have a regular pore structure and affinity for molecules of different size with defined shapes. Experimental results obtained at liquid nitrogen and liquid hydrogen temperatures evidenced the efficient behavior of the activated carbon and zeolite sieves for hydrogen isotope temporary storage. (authors)

  3. 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.

  4. Extended phase-space methods for enhanced sampling in molecular simulations: a review

    Directory of Open Access Journals (Sweden)

    Hiroshi eFujisaki

    2015-09-01

    Full Text Available Molecular Dynamics simulations are a powerful approach to study biomolecular conformational changes or protein-ligand, protein-protein and protein-DNA/RNA interactions. Straightforward applications however are often hampered by incomplete sampling, since in a typical simulated trajectory the system will spend most of its time trapped by high energy barriers in restricted regions of the configuration space. Over the years, several techniques have been designed to overcome this problem and enhance space sampling. Here, we review a class of methods that rely on the idea of extending the set of dynamical variables of the system by adding extra ones associated to functions describing the process under study. In particular, we illustrate the Temperature Accelerated Molecular Dynamics (TAMD, Logarithmic Mean Force Dynamics (LogMFD, andMultiscale Enhanced Sampling (MSES algorithms. We also discuss combinations with techniques for searching reaction paths. We show the advantages presented by this approach and how it allows to quickly sample important regions of the free energy landscape via automatic exploration.

  5. Measurement system analysis (MSA) of the isotopic ratio for uranium isotope enrichment process control

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Josue C. de; Barbosa, Rodrigo A.; Carnaval, Joao Paulo R., E-mail: josue@inb.gov.br, E-mail: rodrigobarbosa@inb.gov.br, E-mail: joaocarnaval@inb.gov.br [Industrias Nucleares do Brasil (INB), Rezende, RJ (Brazil)

    2013-07-01

    Currently, one of the stages in nuclear fuel cycle development is the process of uranium isotope enrichment, which will provide the amount of low enriched uranium for the nuclear fuel production to supply 100% Angra 1 and 20% Angra 2 demands. Determination of isotopic ration n({sup 235}U)/n({sup 238}U) in uranium hexafluoride (UF{sub 6} - used as process gas) is essential in order to control of enrichment process of isotopic separation by gaseous centrifugation cascades. The uranium hexafluoride process is performed by gas continuous feeding in separation unit which uses the centrifuge force principle, establishing a density gradient in a gas containing components of different molecular weights. The elemental separation effect occurs in a single ultracentrifuge that results in a partial separation of the feed in two fractions: an enriched on (product) and another depleted (waste) in the desired isotope ({sup 235}UF{sub 6}). Industrias Nucleares do Brasil (INB) has used quadrupole mass spectrometry (QMS) by electron impact (EI) to perform isotopic ratio n({sup 235}U)/n({sup 238}U) analysis in the process. The decision of adjustments and change te input variables are based on the results presented in these analysis. A study of stability, bias and linearity determination has been performed in order to evaluate the applied method, variations and systematic errors in the measurement system. The software used to analyze the techniques above was the Minitab 15. (author)

  6. 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)

  7. Isotopic quantum correction to liquid methanol at -30 C

    CERN Document Server

    Benmore, C J; Egelstaff, P A; Neuefeind, J

    2002-01-01

    Hydrogen/deuterium (H/D) substitution of molecular liquids in neutron diffraction is a powerful tool for structure determination. However, recent high-energy X-ray studies have found observable differences in the structures of many H and D liquids at the same temperature. In some cases this isotopic quantum effect can be corrected for by measuring the D sample at a slightly different temperature to the H sample. The example of hydroxyl isotopic substitution in liquid methanol at -30 C is presented. The magnitude of the quantum effect is shown to be significant when compared to the size of the first-order isotopic neutron-difference function. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

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

  9. The calculation of isotopic partition function ratios by a perturbation theory technique

    International Nuclear Information System (INIS)

    Singh, G.; Wolfsberg, M.

    1975-01-01

    The vibrational Hamiltonian of a molecule in the harmonic approximation, H = (1/2) Σ (g/subi/jp/subi/p/subj/ + f/subi/jq/subi/q/subj/), has been divided into a diagonal part (terms with i=j) and an off-diagonal part (inot-equalj), which is regarded as the perturbation. The vibrational partition function of the molecule is then calculated by Schwinger perturbation theory as the partition function of the unperturbed problem, corresponding to a collection of oscillators with frequencies 2πν/subi/' = (f/subi/ig/subi/i)/sup 1 / 2 /, plus perturbation correction terms which are calculated to second order. With the usual assumptions of isotope effect calculations that the molecular translations and rotations are classical and separable from the vibrations, the perturbation formulation of the vibrational partition function is easily transformed into a perturbation theory formulation of (reduced) isotopic partition function ratios. If, for example, the molecular potential function is expressed in terms of the displacements of bond stretches and bond angle bends from their respective equilibrium values, the unperturbed partition function ratio corresponds to the isotope effect expected for noninteracting bond-stretch and bond-angle-bend oscillators. Detailed comparison is made for a number of molecular systems of perturbation theory calculations of partition functions and isotopic partition function ratios with exact calculations carried out by actually obtaining the normal mode vibrational frequencies of the vibrational Hamiltonian. Good agreement is found. The utility of the perturbation theory formulation resides in the fact that it permits one to look at isotope effects in a very simple manner; some demonstrations are given

  10. Fundamental studies in isotope chemistry. Progress report, 1 July 1976--30 Jun 1977

    International Nuclear Information System (INIS)

    Bigeleisen, J.; Harris, T.H.

    1977-01-01

    The current thrust of the program is the use of isotope effects to study the fundamental properties of matter, measurement and calculation of isotope fractionation factors of systems of potential technological importance and the correlation of isotope effects with molecular structure. The first measurements of the isotopic fractionation factors for two components in a solution were completed by the study of argon-krypton mixtures. The measurements cover the range from pure argon to pure krypton and extrapolate very well to previous measurements on the pure components. The vapor pressure isotope effects between solid-vapor and liquid-vapor for the rare gases neon, argon, and krypton is given

  11. Enhancing genetic gain in the era of molecular breeding.

    Science.gov (United States)

    Xu, Yunbi; Li, Ping; Zou, Cheng; Lu, Yanli; Xie, Chuanxiao; Zhang, Xuecai; Prasanna, Boddupalli M; Olsen, Michael S

    2017-05-17

    As one of the important concepts in conventional quantitative genetics and breeding, genetic gain can be defined as the amount of increase in performance that is achieved annually through artificial selection. To develop pro ducts that meet the increasing demand of mankind, especially for food and feed, in addition to various industrial uses, breeders are challenged to enhance the potential of genetic gain continuously, at ever higher rates, while they close the gaps that remain between the yield potential in breeders' demonstration trials and the actual yield in farmers' fields. Factors affecting genetic gain include genetic variation available in breeding materials, heritability for traits of interest, selection intensity, and the time required to complete a breeding cycle. Genetic gain can be improved through enhancing the potential and closing the gaps, which has been evolving and complemented with modern breeding techniques and platforms, mainly driven by molecular and genomic tools, combined with improved agronomic practice. Several key strategies are reviewed in this article. Favorable genetic variation can be unlocked and created through molecular and genomic approaches including mutation, gene mapping and discovery, and transgene and genome editing. Estimation of heritability can be improved by refining field experiments through well-controlled and precisely assayed environmental factors or envirotyping, particularly for understanding and controlling spatial heterogeneity at the field level. Selection intensity can be significantly heightened through improvements in the scale and precision of genotyping and phenotyping. The breeding cycle time can be shortened by accelerating breeding procedures through integrated breeding approaches such as marker-assisted selection and doubled haploid development. All the strategies can be integrated with other widely used conventional approaches in breeding programs to enhance genetic gain. More transdisciplinary

  12. System and method for high precision isotope ratio destructive analysis

    Science.gov (United States)

    Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

    2013-07-02

    A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

  13. Gas chromatography-mass spectrometry with supersonic molecular beams.

    Science.gov (United States)

    Amirav, Aviv; Gordin, Alexander; Poliak, Marina; Fialkov, Alexander B

    2008-02-01

    Gas chromatography-mass spectrometry (GC-MS) with supersonic molecular beams (SMBs) (also named Supersonic GC-MS) is based on GC and MS interface with SMBs and on the electron ionization (EI) of vibrationally cold analytes in the SMBs (cold EI) in a fly-through ion source. This ion source is inherently inert and further characterized by fast response and vacuum background filtration capability. The same ion source offers three modes of ionization including cold EI, classical EI and cluster chemical ionization (CI). Cold EI, as a main mode, provides enhanced molecular ions combined with an effective library sample identification, which is supplemented and complemented by a powerful isotope abundance analysis method and software. The range of low-volatility and thermally labile compounds amenable for analysis is significantly increased owing to the use of the contact-free, fly-through ion source and the ability to lower sample elution temperatures through the use of high column carrier gas flow rates. Effective, fast GC-MS is enabled particularly owing to the possible use of high column flow rates and improved system selectivity in view of the enhancement of the molecular ion. This fast GC-MS with SMB can be further improved via the added selectivity of MS-MS, which by itself benefits from the enhancement of the molecular ion, the most suitable parent ion for MS-MS. Supersonic GC-MS is characterized by low limits of detection (LOD), and its sensitivity is superior to that of standard GC-MS, particularly for samples that are hard for analysis. The GC separation of the Supersonic GC-MS can be improved with pulsed flow modulation (PFM) GC x GC-MS. Electron ionization LC-MS with SMB can also be combined with the Supersonic GC-MS, with fast and easy switching between these two modes of operation. (c) 2008 John Wiley & Sons, Ltd.

  14. Isotope separation process

    International Nuclear Information System (INIS)

    Kaldor, A.; Rabinowitz, P.

    1979-01-01

    A method of separating the isotopes of an element is described, which comprises the steps of (i) subjecting molecules of a gaseous compound of the element simultaneously to two infrared radiations of different wavelengths, the first radiation having a wavelength which corresponds to an absorption band of the compound, which in turn corresponds to a mode of molecular motion in which there is participation by atoms of the element, and the second radiation having a power density greater than 10 6 watts per cm 2 , thereby exciting molecules of the compound in an isotopically selective manner, this step being conducted in such manner that the excited molecules either receive a level of energy sufficient to cause them to undergo conversion by unimolecular decomposition or receive a level of energy sufficient to cause them to undergo conversion by reaction with molecules of another gas present for that purpose; and (ii) separating and recovering converted molecules from unconverted molecules. (author)

  15. Amino acid stable isotope applications to deep-sea corals: A molecular geochemistry approach to reconstructing past ocean conditions

    Science.gov (United States)

    McMahon, K.; McCarthy, M. D.; Guilderson, T. P.; Sherwood, O.; Williams, B.; Larsen, T.; Glynn, D. S.

    2017-12-01

    Future climate change is predicted to alter ocean productivity, food web dynamics, biogeochemical cycling, and the efficacy of the biological pump. Proteinaceous deep-sea corals act as "living sediment traps," providing long-term, high-resolution records of exported surface ocean production and a window into past changes in ocean condition as a historical context for potential future changes. Here, we present recent work developing the application of compound-specific stable isotope analysis of individual amino acids to proteinaceous deep-sea corals to reconstruct past changes in phytoplankton community composition and biogeochemical cycling. We present new calibrations for molecular isotope comparisons between metabolically active coral polyp tissue and bioarchival proteinaceous skeleton. We then applied these techniques to deep-sea corals from the North Pacific Subtropical Gyre (NPSG) to reconstruct centennial to millennial time scale changes in phytoplankton community composition and biogeochemical cycling as a function of regional climate change. This work suggests that the NPSG has undergone multiple major phytoplankton regime shifts over the last millennium between prokaryotic and eukaryotic phytoplankton communities and associated sources of nitrogen fueling production. The most recent regime, which started around the end of the Little Ice Age and the onset of the Industrial era, is unprecedented in the last 1000 years and resulted in a 30-50% increase in diazotrophic cyanobacteria contribution to export production and an associated 17-27% increase in N2-fixation in the NPSG over last century. By offering the first direct phylogenetic context for long-term shifts in isotopic records of exported particulate organic matter, our data represent a major step forward in understanding the evolution of marine plankton community dynamics, food web architecture, biogeochemical cycling, and the climate feedback loops through the biological pump.

  16. Confinement of Aggregation-Induced Emission Molecular Rotors in Ultrathin Two-Dimensional Porous Organic Nanosheets for Enhanced Molecular Recognition.

    Science.gov (United States)

    Dong, Jinqiao; Li, Xu; Zhang, Kang; Di Yuan, Yi; Wang, Yuxiang; Zhai, Linzhi; Liu, Guoliang; Yuan, Daqiang; Jiang, Jianwen; Zhao, Dan

    2018-03-21

    Despite the rapid development of molecular rotors over the past decade, it still remains a huge challenge to understand their confined behavior in ultrathin two-dimensional (2D) nanomaterials for molecular recognition. Here, we report an all-carbon, 2D π-conjugated aromatic polymer, named NUS-25, containing flexible tetraphenylethylene (TPE) units as aggregation-induced emission (AIE) molecular rotors. NUS-25 bulk powder can be easily exfoliated into micrometer-sized lamellar freestanding nanosheets with a thickness of 2-5 nm. The dynamic behavior of the TPE rotors is partially restricted through noncovalent interactions in the ultrathin 2D nanosheets, which is proved by comparative experimental studies including AIE characteristics, size-selective molecular recognition, and theoretical calculations of rotary energy barrier. Because of the partially restricted TPE rotors, NUS-25 nanosheets are highly fluorescent. This property allows NUS-25 nanosheets to be used as a chemical sensor for the specific detection of acenaphthylene among a series of polycyclic aromatic hydrocarbons (PAHs) via fluorescent quenching mechanism. Further investigations show that NUS-25 nanosheets have much higher sensitivity and selectivity than their stacked bulk powder and other similar polymers containing dynamic TPE rotors. The highly efficient molecular recognition can be attributed to the photoinduced electron transfer (PET) from NUS-25 nanosheets to acenaphthylene, which is investigated by time-resolved photoluminescence measurements (TRPL), excitation and emission spectra, and density functional theory (DFT) calculations. Our findings demonstrate that confinement of AIE molecular rotors in 2D nanomaterials can enhance the molecular recognition. We anticipate that the material design strategy demonstrated in this study will inspire the development of other ultrathin 2D nanomaterials equipped with smart molecular machines for various applications.

  17. Separation and enrichment of isotopes using laser photochemistry - fundamentals and prospectives

    International Nuclear Information System (INIS)

    Guesten, H.

    1978-01-01

    Basic knowledge is summed up on isotope separation by laser photochemistry. The principal prerequisites are explained of the application of atomic and molecular spectroscopy for this purpose. Practical examples are given of isotope separation of uranium, nitrogen, chlorine, carbon, sulfur, and molybdenum showing the application of two basic techniques, i.e., of gradual atom photoionization or gradual molecule photodissociation and of selective photochemical reactions. (L.K.)

  18. 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)

  19. Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

    Science.gov (United States)

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

    2011-01-01

    One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

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

    OpenAIRE

    Gang, Zhang; Li, Baowen

    2005-01-01

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

  1. Organization of a radioisotope based molecular biology laboratory

    International Nuclear Information System (INIS)

    2006-12-01

    Polymerase chain reaction (PCR) has revolutionized the application of molecular techniques to medicine. Together with other molecular biology techniques it is being increasingly applied to human health for identifying prognostic markers and drug resistant profiles, developing diagnostic tests and genotyping systems and for treatment follow-up of certain diseases in developed countries. Developing Member States have expressed their need to also benefit from the dissemination of molecular advances. The use of radioisotopes, as a step in the detection process or for increased sensitivity and specificity is well established, making it ideally suitable for technology transfer. Many molecular based projects using isotopes for detecting and studying micro organisms, hereditary and neoplastic diseases are received for approval every year. In keeping with the IAEA's programme, several training activities and seminars have been organized to enhance the capabilities of developing Member States to employ in vitro nuclear medicine technologies for managing their important health problems and for undertaking related basic and clinical research. The background material for this publication was collected at training activities and from feedback received from participants at research and coordination meetings. In addition, a consultants' meeting was held in June 2004 to compile the first draft of this report. Previous IAEA TECDOCS, namely IAEA-TECDOC-748 and IAEA-TECDOC-1001, focused on molecular techniques and their application to medicine while the present publication provides information on organization of the laboratory, quality assurance and radio-safety. The technology has specific requirements of the way the laboratory is organized (e.g. for avoiding contamination and false positives in PCR) and of quality assurance in order to provide accurate information to decision makers. In addition while users of the technology accept the scientific rationale of using radio-isotopes

  2. 77 FR 40072 - Assessment of the Program for Enhanced Review Transparency and Communication for New Molecular...

    Science.gov (United States)

    2012-07-06

    ... DEPARTMENT OF HEALTH AND HUMAN SERVICES Food and Drug Administration [Docket No. FDA-2012-N-0603] Assessment of the Program for Enhanced Review Transparency and Communication for New Molecular Entity New... statement of work for an assessment of the Program for Enhanced Review Transparency and Communication for...

  3. Molecular Fin Effect from Heterogeneous Self-Assembled Monolayer Enhances Thermal Conductance across Hard-Soft Interfaces.

    Science.gov (United States)

    Wei, Xingfei; Zhang, Teng; Luo, Tengfei

    2017-10-04

    Thermal transport across hard-soft interfaces is critical to many modern applications, such as composite materials, thermal management in microelectronics, solar-thermal phase transition, and nanoparticle-assisted hyperthermia therapeutics. In this study, we use equilibrium molecular dynamics (EMD) simulations combined with the Green-Kubo method to study how molecularly heterogeneous structures of the self-assembled monolayer (SAM) affect the thermal transport across the interfaces between the SAM-functionalized gold and organic liquids (hexylamine, propylamine and hexane). We focus on a practically synthesizable heterogeneous SAM featuring alternating short and long molecular chains. Such a structure is found to improve the thermal conductance across the hard-soft interface by 46-68% compared to a homogeneous nonpolar SAM. Through a series of further simulations and analyses, it is found that the root reason for this enhancement is the penetration of the liquid molecules into the spaces between the long SAM molecule chains, which increase the effective contact area. Such an effect is similar to the fins used in macroscopic heat exchanger. This "molecular fin" structure from the heterogeneous SAM studied in this work provides a new general route for enhancing thermal transport across hard-soft material interfaces.

  4. Fine- and hyperfine-structure effects in molecular photoionization. II. Resonance-enhanced multiphoton ionization and hyperfine-selective generation of molecular cations

    Energy Technology Data Exchange (ETDEWEB)

    Germann, Matthias; Willitsch, Stefan, E-mail: stefan.willitsch@unibas.ch [Department of Chemistry, University of Basel, Klingelbergstrasse 80, 4056 Basel (Switzerland)

    2016-07-28

    Resonance-enhanced multiphoton ionization (REMPI) is a widely used technique for studying molecular photoionization and producing molecular cations for spectroscopy and dynamics studies. Here, we present a model for describing hyperfine-structure effects in the REMPI process and for predicting hyperfine populations in molecular ions produced by this method. This model is a generalization of our model for fine- and hyperfine-structure effects in one-photon ionization of molecules presented in Paper I [M. Germann and S. Willitsch, J. Chem. Phys. 145, 044314 (2016)]. This generalization is achieved by covering two main aspects: (1) treatment of the neutral bound-bound transition including the hyperfine structure that makes up the first step of the REMPI process and (2) modification of our ionization model to account for anisotropic populations resulting from this first excitation step. Our findings may be used for analyzing results from experiments with molecular ions produced by REMPI and may serve as a theoretical background for hyperfine-selective ionization experiments.

  5. Research on aerodynamic means of isotope enrichment

    International Nuclear Information System (INIS)

    Cattolica, R.J.; Gallagher, R.J.; Talbot, L.; Willis, D.R.; Hurlbut, F.C.; Fiszdon, W.; Anderson, J.B.

    1978-03-01

    The results of a research program directed toward the understanding of the fundamental gas dynamics involved in aerodynamic isotope enrichment are summarized. The specific aerodynamic isotope enrichment method which was examined in this research is based on a velocity slip phenomenon which occurs in the rarefied hypersonic expansion of a heavy molecular weight gas and a light carrier gas in a nozzle or free jet. This particular aerodynamic method was chosen for study because it contains the fundamental molecular physics of other more complex techniques within the context of a one-dimensional flow without boundary effects. From both an experimental and theoretical modeling perspective this provides an excellent basis for testing the experimental and numerical tools with which to investigate more complex aerodynamic isotope enrichment processes. This report consists of three separate parts. Part I contains a theoretical analysis of the velocity slip effect in free jet expansions of binary and ternary gas mixtures. The analysis, based on a source flow model and using moment equations is derived from the Boltzmann equation using the hypersonic approximation. Part II contains the experimental measurements of velocity slip. The numerical simulation of the slip process was carried out by using a Monte-Carlo numerical technique. In addition, comparisons between the theoretical analysis of Part I and the experiments are presented. Part III describes impact pressure measurements of free jet expansions from slot shaped two dimensional nozzles. At least two methods of aerodynamic isotope enrichment (opposed jet and velocity slip) would depend on the use of this type of two dimensional expansion. Flow surveys of single free jet and the interferene of crossed free jets are presented

  6. Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

    Science.gov (United States)

    Xie, Xueshu; Zubarev, Roman A.

    2015-03-01

    Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p biotechnology, medicine, chemistry and other areas.

  7. Dissipation enhanced vibrational sensing in an olfactory molecular switch

    International Nuclear Information System (INIS)

    Chęcińska, Agata; Heaney, Libby; Pollock, Felix A.; Nazir, Ahsan

    2015-01-01

    Motivated by a proposed olfactory mechanism based on a vibrationally activated molecular switch, we study electron transport within a donor-acceptor pair that is coupled to a vibrational mode and embedded in a surrounding environment. We derive a polaron master equation with which we study the dynamics of both the electronic and vibrational degrees of freedom beyond previously employed semiclassical (Marcus-Jortner) rate analyses. We show (i) that in the absence of explicit dissipation of the vibrational mode, the semiclassical approach is generally unable to capture the dynamics predicted by our master equation due to both its assumption of one-way (exponential) electron transfer from donor to acceptor and its neglect of the spectral details of the environment; (ii) that by additionally allowing strong dissipation to act on the odorant vibrational mode, we can recover exponential electron transfer, though typically at a rate that differs from that given by the Marcus-Jortner expression; (iii) that the ability of the molecular switch to discriminate between the presence and absence of the odorant, and its sensitivity to the odorant vibrational frequency, is enhanced significantly in this strong dissipation regime, when compared to the case without mode dissipation; and (iv) that details of the environment absent from previous Marcus-Jortner analyses can also dramatically alter the sensitivity of the molecular switch, in particular, allowing its frequency resolution to be improved. Our results thus demonstrate the constructive role dissipation can play in facilitating sensitive and selective operation in molecular switch devices, as well as the inadequacy of semiclassical rate equations in analysing such behaviour over a wide range of parameters

  8. Lithium-isotope evidence for enhanced silicate weathering during OAE 1a (Early Aptian Selli event)

    Science.gov (United States)

    Lechler, Maria; Pogge von Strandmann, Philip A. E.; Jenkyns, Hugh C.; Prosser, Giacomo; Parente, Mariano

    2015-12-01

    An abrupt rise in temperature, forced by a massive input of CO2 into the atmosphere, is commonly invoked as the main trigger for Oceanic Anoxic Events (OAEs). Global warming initiated a cascade of palaeoenvironmental perturbations starting with increased continental weathering and an accelerated hydrological cycle that delivered higher loads of nutrients to coastal areas, stimulating biological productivity. The end-result was widespread anoxia and deposition of black shales: the hallmarks of OAEs. In order to assess the role of weathering as both an OAE initiator and terminator (via CO2 sequestration) during the Early Aptian OAE 1a (Selli Event, ∼120 Ma) the isotopic ratio of lithium isotopes was analysed in three sections of shallow-marine carbonates from the Pacific and Tethyan realms and one basinal pelagic section from the Tethyan domain. Because the isotopic composition of lithium in seawater is largely controlled by continental silicate weathering and high- and low-temperature alteration of basaltic material, a shift to lighter δ7Li values is expected to characterize OAEs. The studied sections illustrate this phenomenon: δ7Li values decrease to a minimum coincident with the negative carbon-isotope excursion that effectively records the onset of OAE 1a. A second negative δ7Li excursion occurs coeval with the minimum in strontium isotopes after the event. The striking similarity to the strontium-isotope record argues for a common driver. The formation and destruction (weathering) of an oceanic LIP could account for the parallel trend in both isotope systems. The double-spike in lithium isotopes is probably related to a change in weathering congruencies. Such a chemostratigraphy is consistent with the hypothesis that an increase in silicate weathering, in conjunction with organic-carbon burial, led to drawdown of atmospheric CO2 during the early Aptian OAE 1a.

  9. 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

  10. Stable isotope deltas: Tiny, yet robust signatures in nature

    Science.gov (United States)

    Brand, Willi A.; Coplen, Tyler B.

    2012-01-01

    Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg

  11. Molecular biological enhancement of coal biodesulfurization. [Rhodococcus rhodochrous

    Energy Technology Data Exchange (ETDEWEB)

    Kilbane, J.J.; Bielaga, B.A.

    1990-07-01

    The overall objective of this project is to sue molecular genetics to develop strains of bacteria with enhanced ability to remove sulfur from coal and to obtain data that will allow the performance and economics of a coal biodesulfurization process to be predicted. The work planned for the current quarter (May 1990 to July 1990) includes the following activities: (1) Construct a cloning vector that can be used in Rhodococcus rhodochrous IGTS8 from the small cryptic plasmid found in Rhodococcus rhodochrous ATCC 190607; (2) Develop techniques for the genetic analysis of IGTS8; (3) Continue biochemical experiments, particularly those that may allow the identification of desulfurization-related enzymes; (4) Continue experiments with coal to determine the kinetics of organic sulfur removal.

  12. Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

    Science.gov (United States)

    Demopoulos, Amanda W. J.; Sikkel, Paul C.

    2015-01-01

    Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

  13. Enhanced understanding of ectoparasite–host trophic linkages on coral reefs through stable isotope analysis

    Directory of Open Access Journals (Sweden)

    Amanda W.J. Demopoulos

    2015-04-01

    Full Text Available Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi and permanently parasitic cymothoids (Anilocra. To further track the transfer of fish-derived carbon (energy from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in 13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

  14. Preservation of terrestrial plant biomarkers from Nachukui Formation sediments and their viability for stable isotope analysis

    Science.gov (United States)

    Kahle, E.; Uno, K. T.; Polissar, P. J.; Lepre, C. J.; deMenocal, P. B.

    2013-12-01

    Plio-Pleistocene sedimentary records from the Turkana Basin in eastern Africa provide a unique opportunity to compare a high-resolution record of climate and terrestrial vegetation with important changes in the record of human evolution. Molecular biomarkers from terrestrial vegetation can yield stable isotope ratios of hydrogen and carbon that reflect ancient climate and vegetation. However, the preservation of long-chain plant wax biomarkers in these paleosol, fluvial, and lacustrine sediments is not known, and this preservation must be studied to establish their utility for molecular stable isotope studies. We investigated leaf wax biomarkers in Nachukui Formation sediments deposited between 2.3 and 1.7 Ma to assess biomarker preservation. We analyzed n alkane and n alkanoic acid concentrations and, where suitable, molecular carbon and hydrogen isotope ratios. Molecular abundance distributions show a great deal of variance in biomarker preservation and plant-type source as indicated by the carbon preference index and average chain length. This variation suggests that some samples are suitable for isotopic analysis, while other samples lack primary terrestrial plant biomarker signatures. The biomarker signal in many samples contains significant additional material from unidentified sources. For example, the n-alkane distributions contain an unresolved complex mixture underlying the short and mid-chain n-alkanes. Samples from lacustrine intervals include long-chain diacids, hydroxy acids and (ω-1) ketoacids that suggest degradation of the original acids. Degradation of poorly preserved samples and the addition of non-terrestrial plant biomarkers may originate from a number of processes including forest fire or microbial alteration. Isotopic analysis of well-preserved terrestrial plant biomarkers will be presented along with examples where the original biomarker distribution has been altered.

  15. Prediction, Detection, and Validation of Isotope Clusters in Mass Spectrometry Data

    Directory of Open Access Journals (Sweden)

    Hendrik Treutler

    2016-10-01

    Full Text Available Mass spectrometry is a key analytical platform for metabolomics. The precise quantification and identification of small molecules is a prerequisite for elucidating the metabolism and the detection, validation, and evaluation of isotope clusters in LC-MS data is important for this task. Here, we present an approach for the improved detection of isotope clusters using chemical prior knowledge and the validation of detected isotope clusters depending on the substance mass using database statistics. We find remarkable improvements regarding the number of detected isotope clusters and are able to predict the correct molecular formula in the top three ranks in 92 % of the cases. We make our methodology freely available as part of the Bioconductor packages xcms version 1.50.0 and CAMERA version 1.30.0.

  16. Real-time molecular imaging throughout the entire cell cycle by targeted plasmonic-enhanced Rayleigh/Raman spectroscopy.

    Science.gov (United States)

    Kang, Bin; Austin, Lauren A; El-Sayed, Mostafa A

    2012-10-10

    Due to their strong enhancement of scattered light, plasmonic nanoparticles have been utilized for various biological and medical applications. Here, we describe a new technique, Targeted Plasmonic-Enhanced Single-Cell Rayleigh/Raman Spectroscopy, to monitor the molecular changes of any cell-component, such as the nucleus, during the different phases of its full cell cycle by simultaneously recording its Rayleigh images and Raman vibration spectra in real-time. The analysis of the observed Raman DNA and protein peaks allowed the different phases of the cell cycle to be identified. This technique could be used for disease diagnostics and potentially improve our understanding of the molecular mechanisms of cellular functions such as division, death, signaling, and drug action.

  17. Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

    Science.gov (United States)

    Smallwood, Barbara J; Wooller, Matthew J; Jacobson, Myrna E; Fogel, Marilyn L

    2003-01-01

    Rhizophora mangle L. (red mangrove) is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ) red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m). These height differences are coupled with very different stable carbon and nitrogen isotopic values[1] (mean tall δ13C = -28.3‰, δ15N = 0‰; mean tall δ13C = -25.3‰, δ15N = -10‰). To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ13C and δ15N) composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds) in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ13C and δ15N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ13C and δ15N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ15N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in mangrove

  18. Isotopic and molecular distributions of biochemicals from fresh and buried Rhizophora mangle leaves†

    Directory of Open Access Journals (Sweden)

    Jacobson Myrna E

    2003-12-01

    Full Text Available Rhizophora mangle L. (red mangrove is the dominant species of mangrove in the Americas. At Twin Cays, Belize (BZ red mangroves are present in a variety of stand structures (tall >5 m in height, transition ~2–4 m and dwarf ~1–1.5 m. These height differences are coupled with very different stable carbon and nitrogen isotopic values1 (mean tall δ13C = -28.3‰, δ15N = 0‰; mean tall δ13C = -25.3‰, δ15N = -10‰. To determine the utility of using these distinct isotopic compositions as 'biomarkers' for paleoenvironmental reconstruction of mangrove ecosystems and nutrient availability, we investigated the distribution and isotopic (δ13C and δ15N composition of different biochemical fractions (water soluble compounds, free lipids, acid hydrolysable compounds, individual amino acids, and the residual un-extractable compounds in fresh and preserved red mangrove leaves from dwarf and tall trees. The distribution of biochemicals are similar in dwarf and tall red mangrove leaves, suggesting that, regardless of stand structure, red mangroves use nutrients for biosynthesis and metabolism in a similar manner. However, the δ13C and δ15N of the bulk leaf, the biochemical fractions, and seven amino acids can be used to distinguish dwarf and tall trees at Twin Cays, BZ. The data support the theory that the fractionation of carbon and nitrogen occurs prior to or during uptake in dwarf and tall red mangrove trees. Stable carbon and nitrogen isotopes could, therefore, be powerful tools for predicting levels of nutrient limitation at Twin Cays. The δ13C and δ15N of biochemical fractions within preserved leaves, reflect sedimentary cycling and nitrogen immobilization. The δ15N of the immobilized fraction reveals the overlying stand structure at the time of leaf deposition. The isotopic composition of preserved mangrove leaves could yield significant information about changes in ecosystem dynamics, nutrient limitation and past stand structure in

  19. Peculiarities of spectroscopic determination of the isotopic hydrogen composition in a mixture with neon and argon

    International Nuclear Information System (INIS)

    Nemets, V.M.; Petrov, A.A.; Solov'ev, A.A.

    1987-01-01

    The dependence of the relative intensity of atomic lines of hydrogen isotopes in the mixture with neon and argon during excitation in a high-frequency discharge under medium and high pressures is investigated. A physical model is suggested for processes determining the isotopic effects in the atomic hydrogen spectrum due to isotopic differences in velocity constants of dissociation-association, transfer and ionic-molecular reactions in a gas discharge plasma

  20. Environmental Development Plan for advanced isotope separation

    International Nuclear Information System (INIS)

    1979-05-01

    This EDP identifies the planning and management requirements and schedules needed to evaluate and assess the environmental, health, and safety aspects of the Advanced Isotope Separation (AIS) program. Current AIS processes include the molecular and atomic vapor laser processes and the plasma process. This document covers the technology program, environmental concerns and requirements, and environmental strategy

  1. How does the plasmonic enhancement of molecular absorption depend on the energy gap between molecular excitation and plasmon modes: a mixed TDDFT/FDTD investigation.

    Science.gov (United States)

    Sun, Jin; Li, Guang; Liang, WanZhen

    2015-07-14

    A real-time time-dependent density functional theory coupled with the classical electrodynamics finite difference time domain technique is employed to systematically investigate the optical properties of hybrid systems composed of silver nanoparticles (NPs) and organic adsorbates. The results demonstrate that the molecular absorption spectra throughout the whole energy range can be enhanced by the surface plasmon resonance of Ag NPs; however, the absorption enhancement ratio (AER) for each absorption band differs significantly from the others, leading to the quite different spectral profiles of the hybrid complexes in contrast to those of isolated molecules or sole NPs. Detailed investigations reveal that the AER is sensitive to the energy gap between the molecular excitation and plasmon modes. As anticipated, two separate absorption bands, corresponding to the isolated molecules and sole NPs, have been observed at a large energy gap. When the energy gap approaches zero, the molecular excitation strongly couples with the plasmon mode to form the hybrid exciton band, which possesses the significantly enhanced absorption intensity, a red-shifted peak position, a surprising strongly asymmetric shape of the absorption band, and the nonlinear Fano effect. Furthermore, the dependence of surface localized fields and the scattering response functions (SRFs) on the geometrical parameters of NPs, the NP-molecule separation distance, and the external-field polarizations has also been depicted.

  2. Aerodynamic isotope separation processes for uranium enrichment: process requirements

    International Nuclear Information System (INIS)

    Malling, G.F.; Von Halle, E.

    1976-01-01

    The pressing need for enriched uranium to fuel nuclear power reactors, requiring that as many as ten large uranium isotope separation plants be built during the next twenty years, has inspired an increase of interest in isotope separation processes for uranium enrichment. Aerodynamic isotope separation processes have been prominently mentioned along with the gas centrifuge process and the laser isotope separation methods as alternatives to the gaseous diffusion process, currently in use, for these future plants. Commonly included in the category of aerodynamic isotope separation processes are: (a) the separation nozzle process; (b) opposed gas jets; (c) the gas vortex; (d) the separation probes; (e) interacting molecular beams; (f) jet penetration processes; and (g) time of flight separation processes. A number of these aerodynamic isotope separation processes depend, as does the gas centrifuge process, on pressure diffusion associated with curved streamlines for the basic separation effect. Much can be deduced about the process characteristics and the economic potential of such processes from a simple and elementary process model. In particular, the benefit to be gained from a light carrier gas added to the uranium feed is clearly demonstrated. The model also illustrates the importance of transient effects in this class of processes

  3. Search for unknown isotopes using the TIARA-ISOL and the JAERI-ISOL

    Energy Technology Data Exchange (ETDEWEB)

    Asai, Masato [Nagoya Univ. (Japan). School of Engineering

    1997-07-01

    The new neutron-deficient isotopes {sup 127}Pr and {sup 125}Pr, and the new neutron-rich isotopes {sup 166}Tb, {sup 165}Gd and {sup 161}Sm were identified using the TIARA-ISOL with {sup 36}Ar + {sup 92,94}Mo reactions, and the gas-jet coupled JAERI-ISOL with a proton-induced fission of {sup 238}U, respectively. The element-selective oxidation technique was used to reduce large contamination from isobars and molecular ions with production cross sections about one or two orders of magnitude as large as those of the new isotopes. The good signal-to-noise ratios achieved in the present measurements were essential to observe and identify weak X/{gamma} rays from the new isotopes. (author)

  4. Precise and accurate isotope ratio measurements by ICP-MS.

    Science.gov (United States)

    Becker, J S; Dietze, H J

    2000-09-01

    The precise and accurate determination of isotope ratios by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) is important for quite different application fields (e.g. for isotope ratio measurements of stable isotopes in nature, especially for the investigation of isotope variation in nature or age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, quality assurance of fuel material, for reprocessing plants, nuclear material accounting and radioactive waste control, for tracer experiments using stable isotopes or long-lived radionuclides in biological or medical studies). Thermal ionization mass spectrometry (TIMS), which used to be the dominant analytical technique for precise isotope ratio measurements, is being increasingly replaced for isotope ratio measurements by ICP-MS due to its excellent sensitivity, precision and good accuracy. Instrumental progress in ICP-MS was achieved by the introduction of the collision cell interface in order to dissociate many disturbing argon-based molecular ions, thermalize the ions and neutralize the disturbing argon ions of plasma gas (Ar+). The application of the collision cell in ICP-QMS results in a higher ion transmission, improved sensitivity and better precision of isotope ratio measurements compared to quadrupole ICP-MS without the collision cell [e.g., for 235U/238U approximately 1 (10 microg x L(-1) uranium) 0.07% relative standard deviation (RSD) vs. 0.2% RSD in short-term measurements (n = 5)]. A significant instrumental improvement for ICP-MS is the multicollector device (MC-ICP-MS) in order to obtain a better precision of isotope ratio measurements (with a precision of up to 0.002%, RSD). CE- and HPLC-ICP-MS are used for the separation of isobaric interferences of long-lived radionuclides and stable isotopes by determination of spallation nuclide abundances in an irradiated tantalum target.

  5. Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

    Science.gov (United States)

    Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

    2015-03-01

    Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

  6. Calcium Isotope Analysis with "Peak Cut" Method on Column Chemistry

    Science.gov (United States)

    Zhu, H.; Zhang, Z.; Liu, F.; Li, X.

    2017-12-01

    To eliminate isobaric interferences from elemental and molecular isobars (e.g., 40K+, 48Ti+, 88Sr2+, 24Mg16O+, 27Al16O+) on Ca isotopes during mass determination, samples should be purified through ion-exchange column chemistry before analysis. However, large Ca isotopic fractionation has been observed during column chemistry (Russell and Papanastassiou, 1978; Zhu et al., 2016). Therefore, full recovery during column chemistry is greatly needed, otherwise uncertainties would be caused by poor recovery (Zhu et al., 2016). Generally, matrix effects could be enhanced by full recovery, as other elements might overlap with Ca cut during column chemistry. Matrix effects and full recovery are difficult to balance and both need to be considered for high-precision analysis of stable Ca isotopes. Here, we investigate the influence of poor recovery on δ44/40Ca using TIMS with the double spike technique. The δ44/40Ca values of IAPSO seawater, ML3B-G and BHVO-2 in different Ca subcats (e.g., 0-20, 20-40, 40-60, 60-80, 80-100%) with 20% Ca recovery on column chemistry display limited variation after correction by the 42Ca-43Ca double spike technique with the exponential law. Notably, δ44/40Ca of each Ca subcut is quite consistent with δ44/40Ca of Ca cut with full recovery within error. Our results indicate that the 42Ca-43Ca double spike technique can simultaneously correct both of the Ca isotopic fractionation that occurred during column chemistry and thermal ionization mass spectrometry (TIMS) determination properly, because both of the isotopic fractionation occurred during analysis follow the exponential law well. Therefore, we propose the "peak cut" method on Ca column chemistry for samples with complex matrix effects. Briefly, for samples with low Ca contents, we can add the double spike before column chemistry, and only collect the middle of the Ca eluate and abandon the both sides of Ca eluate that might overlap with other elements (e.g., K, Sr). This method would

  7. Implementation of molecularly imprinted polymer beads for surface enhanced Raman detection.

    Science.gov (United States)

    Kamra, Tripta; Zhou, Tongchang; Montelius, Lars; Schnadt, Joachim; Ye, Lei

    2015-01-01

    Molecularly imprinted polymers (MIPs) have a predesigned molecular recognition capability that can be used to build robust chemical sensors. MIP-based chemical sensors allow label-free detection and are particularly interesting due to their simple operation. In this work we report the use of thiol-terminated MIP microspheres to construct surfaces for detection of a model organic analyte, nicotine, by surface enhanced Raman scattering (SERS). The nicotine-imprinted microspheres are synthesized by RAFT precipitation polymerization and converted into thiol-terminated microspheres through aminolysis. The thiol groups on the MIP surface allow the microspheres to be immobilized on a gold-coated substrate. Three different strategies are investigated to achieve surface enhanced Raman scattering in the vicinity of the imprinted sites: (1) direct sputtering of gold nanoparticles, (2) immobilization of gold colloids through the MIP's thiol groups, and (3) trapping of the MIP microspheres in a patterned SERS substrate. For the first time we show that large MIP microspheres can be turned into selective SERS surfaces through the three different approaches of assembly. The MIP-based sensing surfaces are used to detect nicotine to demonstrate the proof of concept. As synthesis and surface functionalization of MIP microspheres and nanoparticles are well established, the methods reported in this work are handy and efficient for constructing label-free chemical sensors, in particular for those based on SERS detection.

  8. Molecular modification of highly degenerate semiconductor as an active electrode to enhance the performance of supercapacitors

    Science.gov (United States)

    Mundinamani, S. P.; Rabinal, M. K.

    2014-12-01

    Highly conducting antimony doped tin oxide (SnO2:Sb) films are electrografted with suitable organic molecules to study their electrolytic behavior. A series of organic molecules, such as heptanethiol, dodecanethiol and octadecanethiol are bonded to electrode surfaces. Electrolytic capacitors were formed on both unmodified and chemically modified electrodes using KCl and H2SO4 as electrolytes. This molecular modification significantly enhances the current levels in cyclic voltammograms, and there is a clear shift in oxidation/reduction peaks of these capacitors with scan rate. The results obey Randles-Sevcik relation, which indicates that there is enhancement of ionic diffusion at the electrode-electrolyte interface. There is a large enhancement in the values of specific capacitance (almost by 104 times) after the chemical modification. These measurements show that Faradaic reactions are responsible for charge storage/discharge process in these capacitors. Hence, the molecularly modified electrodes can be a good choice to increase the specific capacitance.

  9. Isotopic Discrimination During Leaf Litter Decomposition

    Science.gov (United States)

    Ngao, J.; Rubino, M.

    2006-12-01

    Methods involving stable isotopes have been successfully applied since decades in various research fields. Tracing 13C natural abundance in ecosystem compartments greatly enhanced the understanding of the C fluxes in the plant-soil-atmosphere C exchanges when compartments present different C isotopic signatures (i.e. atmospheric CO2 vs photosynthetic leaves, C3 vs C4; etc.). However, the assumption that no isotopic discrimination occurs during respiration is commonly made in numbers of C isotope-based ecological studies. Furthermore, verifications of such assumption are sparse and not enough reliable. The aim of our study is to assess the potential isotopic discrimination that may occur during litter decomposition. Leaf litter from an Arbutus unedo (L.) stand (Tolfa, Italy) was incubated in 1L jars, under constant laboratory conditions (i.e. 25 ° C and 135% WC). During the entire incubation period, gravimetric mass loss, litter respiration rates and the isotopic composition of respired CO2 are monitored at regular intervals. Data from 7 months of incubation will be presented and discussed. After two months, the litter mass loss averaged 16% of initial dry mass. During the same time-period, the respiration rate decreased significantly by 58% of the initial respiration rate. Isotopic compositions of respired CO2 ranged between -27.95‰ and - 25.69‰. Mean values did not differ significantly among the sampling days, in spite of an apparent enrichment in 13C of respired CO2 with time. The significance of these isotopic enrichment will be determined at a longer time scale. They may reveal both/either a direct microbial discrimination during respiration processes and/or a use of different litter compounds as C source along time. Further chemical and compound-specific isotopic analysis of dry matter will be performed in order to clarify these hypotheses. This work is part of the "ALICE" project, funded by the European Union's Marie Curie Fellowship Actions that aims to

  10. Isotope Fractionation of Water During Evaporation Without Condensation

    International Nuclear Information System (INIS)

    Cappa, Christopher D.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.; Cohen, Ronald C.

    2005-01-01

    The microscopic events engendering liquid water evaporation have received much attention over the last century, but remain incompletely understood. We present measurements of isotope fractionation occurring during free molecular evaporation from liquid microjets and show that the isotope ratios of evaporating molecules exhibit dramatic differences from equilibrium vapor values, strong variations with the solution deuterium mole fraction, and a clear temperature dependence. These results indicate the existence of an energetic barrier to evaporation and that the evaporation coefficient of water is less than unity. These new insights into water evaporation promise to advance our understanding of the processes that control the formation and lifetime of clouds in the atmosphere.

  11. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    Science.gov (United States)

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  12. Radioactive isotopes in clinical medicine and research. Abstracts

    International Nuclear Information System (INIS)

    2007-01-01

    The review on the International Symposium on radioactive isotopes in clinical medicine and research in Bad Hofgastein, Austria, 9-12 January 2008, contains 42 papers and 29 poster contributions on the following topics: radiopharmaceutical sciences; radiopharmaceutical sciences in oncology and cardiology; therapy; endocrinology; molecular imaging; clinical PET; physics: image processing; instrumentation, neurology, psychiatry

  13. Radioactive isotopes in clinical medicine and research. Abstracts

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-07-01

    The review on the International Symposium on radioactive isotopes in clinical medicine and research in Bad Hofgastein, Austria, 9-12 January 2008, contains 42 papers and 29 poster contributions on the following topics: radiopharmaceutical sciences; radiopharmaceutical sciences in oncology and cardiology; therapy; endocrinology; molecular imaging; clinical PET; physics: image processing; instrumentation, neurology, psychiatry.

  14. Origin of Organic Matter in Sediments of the Campos Basin (SE Brazilian Continental Margin) by Means of Stable Isotopes and Molecular Markers

    Energy Technology Data Exchange (ETDEWEB)

    Wagener, A. L.R.; Carreira, R. S.; Baeta, A.; Scofield, A. L. [Departamento de Quimica, Pontificia Universidade Catolica, Rio de Janeiro, RJ (Brazil); Farias, C. O.; Cordeiro, L. G.M.S.; Oliveira, D. R. [Faculdade de Oceanografia, Universidade do Estado do Rio de Janeiro, Rio de Janeiro, RJ (Brazil); Rezende, C. E.; Almeida, M. [Centro de Biociencias e Biotecnologia, Universidade Estadual do Norte Fluminense, Campos dos Goytacazes, RJ (Brazil)

    2013-07-15

    Sediment samples were taken from a total of 133 stations in two sampling campaigns (winter 2008/2009 and summer 2009) distributed on the shelf and in transects which extended from 25 m to 3000 m water depth. The region under study is influenced by upwelling, river discharge and beyond the platform by five different water masses. The goal of the work was to examine by means of carbon isotopic composition and lipid biomarkers the provenance of the organic matter pool in the sediments so as to evaluate source strength, degradation and relevance to sustain a benthic community. Isotopic and molecular indicators show the influence of the outflow of the Paraiba do Sul river on the quality and quantity of organic matter (OM) that accumulates on the shelf; however, this influence is dependent on the hydrological regime on the river's basin. In the upwelling region of Cabo Frio, the OM is mainly of autochthonous sources, and evidence of export of labile OM produced on the shelf to the slope was found, which can potentially influence the benthic process at depths between 700 and 1000 m. (author)

  15. Isotopic exchange of nitrogen and ammonia synthesis on uranium nitride

    International Nuclear Information System (INIS)

    Panov, G.I.; Boreskov, G.K.; Kharitonov, A.S.; Moroz, Eh.M.; Sobolev, V.I.

    1984-01-01

    The catalytic properties of uranium nitride samples of different chemical composition: α - U 2 N 3 and UNsub(1, 70) are compared. The isotopic exchange at 553-623 K in both cases is realized by reversible dissociative nitrogen adsorption. Despite the proximity of structural and thermodynamic phase characteristics, the nitrogen adsorption heat differs by 120 kJ/mol which leads to strong differences in catalytic sample properties. It is shown that the isotopic exchange serves a reliable characteristic of activation of molecular nitrogen and its ability to react with the ammonia synthesis

  16. Isotopic evidence for climatic conditions in Southeast Asia at the last glacial maximum

    International Nuclear Information System (INIS)

    Aggarwal, P.K.; Gibson, J.J.; Kulkarni, K.M.; Froehlich, K.

    2002-01-01

    Stable isotope composition of dated groundwater archives from the Philippines, Vietnam, Thailand and Bangladesh trace changes in monsoon conditions, primarily rainout processes between the Last Glacial Maximum (LGM) and present day in southeast Asia. Today, isotope-climate relations are well established by the IAEA/WMO Global Network of Isotopes in Precipitation survey which reveals more depleted δ 18 O and δ 2 H for the Pacific Ocean monsoon regime than for the Indian Ocean monsoon regime, primarily due to proximal ocean sources and subdued continental moisture recycling for the latter region. Groundwater archives, reflecting past isotopic composition of precipitation, strongly suggest that this distinction was preserved or slightly enhanced at the time of the LGM, despite an apparent weakening of the summer monsoon and associated rainout processes. Overall, precipitation and moisture recycling, and enhanced continental effects are inferred to be the primary controls on δ 18 O signals in groundwater in southeast Asia. Comparison of groundwater isotope signatures and an ECHAM4 model simulation of the isotopic distribution in precipitation at 21ka reveal similar patterns, but the impacts of increased air mass contributions from high latitudes and reduced Eurasian moisture recycling at the LGM are shown to be potentially greater for the Pacific region than predicted by the model. (author)

  17. In vivo EPR oximetry using an isotopically-substituted nitroxide: Potential for quantitative measurement of tissue oxygen

    Science.gov (United States)

    Weaver, John; Burks, Scott R.; Liu, Ke Jian; Kao, Joseph P.Y.; Rosen, Gerald M.

    2017-01-01

    Variations in brain oxygen (O2) concentration can have profound effects on brain physiology. Thus, the ability to quantitate local O2 concentrations noninvasively in vivo could significantly enhance understanding of several brain pathologies. However, quantitative O2 mapping in the brain has proven difficult. The electron paramagnetic resonance (EPR) spectra of nitroxides are sensitive to molecular O2 and can be used to estimate O2 concentrations in aqueous media. We recently synthesized labile-ester-containing nitroxides, such as 3-acetoxymethoxycarbonyl-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl (nitroxide 4), which accumulate in cerebral tissue after in situ hydrolysis, and thus enable spatial mapping of O2 concentrations in the mouse brain by EPR imaging. In an effort to improve O2 quantitation, we prepared 3-acetoxymethox ycarbonyl-2,2,5,5-tetra(2H3)methyl-1-(3,4,4-2H3,1-15N)pyrrolidinyloxyl (nitroxide 2), which proved to be a more sensitive probe than its normo-isotopic version for quantifying O2 in aqueous solutions of various O2 concentrations. We now demonstrate that this isotopically substituted nitroxide is ~2-fold more sensitive in vivo than the normo-isotopic nitroxide 4. Moreover, in vitro and in vivo EPR spectral-spatial imaging results with nitroxide 2 demonstrate significant improvement in resolution, reconstruction and spectral response to local O2 concentrations in cerebral tissue. Thus, isotopic-substituted nitroxides, such as 2, are excellent sensors for in vivo O2 quantitation in tissues, such as the brain. PMID:27567323

  18. Tip-Enhanced Raman Scattering Microscopy: A Step toward Nanoscale Control of Intrinsic Molecular Properties

    Science.gov (United States)

    Yano, Taka-aki; Hara, Masahiko

    2018-06-01

    Tip-enhanced Raman scattering microscopy, a family of scanning probe microscopy techniques, has been recognized as a powerful surface analytical technique with both single-molecule sensitivity and angstrom-scale spatial resolution. This review covers the current status of tip-enhanced Raman scattering microscopy in surface and material nanosciences, including a brief history, the basic principles, and applications for the nanoscale characterization of a variety of nanomaterials. The focus is on the recent trend of combining tip-enhanced Raman scattering microscopy with various external stimuli such as pressure, voltage, light, and temperature, which enables the local control of the molecular properties and functions and also enables chemical reactions to be induced on a nanometer scale.

  19. Isotopic diagnosis and molecular identification of cucumber mosaic virus and satellite RNA infecting tomato in Shanghai

    International Nuclear Information System (INIS)

    Zhang Huarong; Du Zhiyou; Liao Qiansheng; Zhang Hen

    2006-01-01

    In summer of 2004 and 2005, typical viral disease symptoms were found on field tomato from Shanghai, which remarkably reduced the yield of tomato. Total RNA of tomato leaves and purified virions were detected by hybridization with 32 P probes conducted with partial sequence of CMV RNA3 and full cDNA of CMV satRNA. Viruses were also confirmed by analyzing dsRNA extracted from tomato leaves. Full sequence of CMV RNA3 was gained by RT-PCR and the result of sequencing indicated that genomic RNA3 belongs to subgroup II. Two 15nt complementary ssDNA as amplification primers. Phylogenetic analysis showed that the identity of this 383nt satellite and some documented satRNAs was 72.6 to 99.5% at the nucleotide level. Several mutation sites were found at the 3' terminus of the newly discovered satRNA. By Isotopic diagnosis and molecular Identification, variation of CMV and its satRNA were found in Tomato from Shanghai, Which may influence the viral disease prevalence and the emergence of new symptom. (authors)

  20. Improved molecular fingerprint analysis employing multi-branched gold nanoparticles in conjunction with surface-enhanced Raman scattering

    Directory of Open Access Journals (Sweden)

    Johnston J

    2015-12-01

    Full Text Available Jencilin Johnston,1 Erik N Taylor,1,2 Richard J Gilbert,2 Thomas J Webster1,3 1Department of Chemical Engineering, 2Department of Chemistry and Chemical Biology, Northeastern University, Boston, MA, USA; 3Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia Abstract: Vibrational spectroscopy is a powerful analytical tool that assesses molecular properties based on spectroscopic signatures. In this study, the effect of gold nanoparticle morphology (spherical vs multi-branched was assessed for the characterization of a Raman signal (ie, molecular fingerprint that may be helpful for numerous medical applications. Multi-branched gold nanoparticles (MBAuNPs were fabricated using a green chemistry method which employed the reduction of gold ion solute by 2-[4-(2-hydroxyethyl-1-piperazyl] ethane sulfonic acid. Two types of reporter dyes, indocyanine (IR820 and IR792 and carbocyanine (DTTC [3,3'-diethylthiatricarbocyanine iodide] and DTDC [3,3'-diethylthiadicarbocyanine iodide], were functionalized to the surface of the MBAuNPs and stabilized with denatured bovine serum albumin, thus forming the surface-enhanced Raman spectroscopy tag. Fluorescein isothiocyanate-conjugated anti-epidermal growth factor receptor to the surface-enhanced Raman spectroscopy tags and the properties of the resulting conjugates were assessed through determination of the Raman signal. Using the MBAuNP Raman probes synthesized in this manner, we demonstrated that MBAuNP provided significantly more surface-enhanced Raman scattering signal when compared with the associated spherical gold nanoparticle of similar size and concentration. MBAuNP enhancements were retained in the surface-enhanced Raman spectroscopy tags complexed to anti-epidermal growth factor receptor, providing evidence that this could be a useful biological probe for enhanced Raman molecular fingerprinting. Furthermore, while utilizing IR820 as a novel reporter dye

  1. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

  2. Characterization of natural anaerobic dechlorination of TCE and 1,1,1-TCA in clay till including isotope fractionation and molecular biological tools

    DEFF Research Database (Denmark)

    Damgaard, Ida; Bælum, J.; Hunkeler, D.

    2010-01-01

    One of the major challenges when using enhanced reductive dechlorination (ERD) as a remediation technology at clay till sites is to obtain good contact between added agents such as donor, bacteria and the contamination. It is unclear whether degradation only takes place in fractures and/or sand l...... including the location of degradation in the fracture matrix geology. An extensive field collection of cores and discrete soil sampling has been conducted and samples have been analysed using state of the art microbial and chemical tools including isotope fractionation....

  3. Monitoring in situ biodegradation of hydrocarbons by using stable carbon isotopes

    International Nuclear Information System (INIS)

    Aggarwal, P.K.; Hinchee, R.E.

    1991-01-01

    Spilled or leaked nonhalogenated petroleum hydrocarbons in the soil can generally be metabolized by indigenous, aerobic bacteria. In situ biological degradation of hydrocarbons may be accelerated by supplying inorganic nutrients and/or oxygen. Approaches to monitoring and verifying enhanced in situ biodegradation have included measurements of changes over time in the (a) concentration of hydrocarbons, (b) temperature, (c) number of hydrocarbon-degrading microorganisms, (d) ratio of fast-degrading hydrocarbons (e.g., pristanes or phytanes), and (e) metabolic intermediates. Measurements of oxygen consumption over time and elevated carbon dioxide concentrations in soil gas also have been used as indicators of hydrocarbon degradation. An alternative approach that may help substantiate biodegradation is to measure stable carbon isotope ratios in soil gas CO 2 . Stable carbon isotope ratio analysis is inexpensive and commercially available at many laboratories. Carbon dioxide produced by hydrocarbon degradation may be distinguished from that produced by other processes based on the carbon isotopic compositions characteristic of the source material and/or fractionation accompanying microbial metabolism. Here the authors demonstrate the applicability of the stable isotope technique for monitoring enhanced. aerobic biodegradation of hydrocarbons using data from three locations in the United States

  4. 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.

  5. Gas-chromatographic separation of hydrogen isotopes mixtures on capillary molecular sieve 5 A column at 173 K

    International Nuclear Information System (INIS)

    Bidica, N.; Preda, A.; Stanciu, V.

    2002-01-01

    Analysis of a gas mixture of hydrogen species, is not too easy because the differences in their physical-chemical properties are very small; the most different are their masses, and consequently most common analytical method appear to be the mass-spectrometry. However, the impossibility to distinguish between two ions (atomic or molecular) with the same mass renders this method as unapplicable. Another problem is the decay of tritium with production of 3 He. These disadvantages of mass-spectrometry have made that other analytical methods, like gas chromatography, to be considered and developed. Thus, there are many papers about various chromatographic columns especially prepared for hydrogen species separation but the preparation and treatment of these columns are very difficult to reproduce. Besides these, there are two other main disadvantages: column operating temperature is very low and long retention times for hydrogen species (more than half an hour) are required. However, the gas-chromatography method still remains an appropriate one. The method described in this paper was based on using a capillary molecular sieve 5A column which has been operated for this kind of separation. The retention times were relatively short, about 8-9 minutes. The carrier gas was Ne and the detector - TCD. In the paper chromatograms for various carrier flow rates and various hydrogen isotope mixtures are presented. The results demonstrated a quite good efficiency for H 2 , HD, D 2 and a not very good one for orthoH 2 -paraH 2 . (authors)

  6. Conformational Smear Characterization and Binning of Single-Molecule Conductance Measurements for Enhanced Molecular Recognition.

    Science.gov (United States)

    Korshoj, Lee E; Afsari, Sepideh; Chatterjee, Anushree; Nagpal, Prashant

    2017-11-01

    Electronic conduction or charge transport through single molecules depends primarily on molecular structure and anchoring groups and forms the basis for a wide range of studies from molecular electronics to DNA sequencing. Several high-throughput nanoelectronic methods such as mechanical break junctions, nanopores, conductive atomic force microscopy, scanning tunneling break junctions, and static nanoscale electrodes are often used for measuring single-molecule conductance. In these measurements, "smearing" due to conformational changes and other entropic factors leads to large variances in the observed molecular conductance, especially in individual measurements. Here, we show a method for characterizing smear in single-molecule conductance measurements and demonstrate how binning measurements according to smear can significantly enhance the use of individual conductance measurements for molecular recognition. Using quantum point contact measurements on single nucleotides within DNA macromolecules, we demonstrate that the distance over which molecular junctions are maintained is a measure of smear, and the resulting variance in unbiased single measurements depends on this smear parameter. Our ability to identify individual DNA nucleotides at 20× coverage increases from 81.3% accuracy without smear analysis to 93.9% with smear characterization and binning (SCRIB). Furthermore, merely 7 conductance measurements (7× coverage) are needed to achieve 97.8% accuracy for DNA nucleotide recognition when only low molecular smear measurements are used, which represents a significant improvement over contemporary sequencing methods. These results have important implications in a broad range of molecular electronics applications from designing robust molecular switches to nanoelectronic DNA sequencing.

  7. Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

    Science.gov (United States)

    Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk

    2017-10-11

    We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO 2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO 2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; V OC = 0.73 V, J SC = 15.4 mA·cm -2 , and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m -2 ), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO 2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only J SC through improved ICT but also V OC through the evenly distributed sensitizer surface coverage.

  8. Isotope dilution mass spectrometry: some present limitations and possibilities to overcome these

    International Nuclear Information System (INIS)

    De Bievre, P.

    1981-01-01

    Thermionic mass spectrometry still has great potential for more precise and accurate measurements but it is going to place tremendous requirements on (1) the chemical purity of the samples we measure, (2) the temperature of both ionization and the filaments and (3) the number of molecular species being handled in ion sources which could increase to several dozen for one type of isotopic analysis. The lack of control by mass spectrometrists over the chemical preparation of the samples for isotopic analysis is an inherent limitation to further improvement of isotope dilution mass spectrometry. A limiting factor in isotope dilution is the ability to measure the ratio. At present, uranium isotopic reference materials are 0.1% and recently one was prepared at 0.05%. As these serve to calibrate isotope ratio measurements one cannot do better than these valves. There is no way in which isotope dilution can be improved until these reference values improve. For plutonium there are not even absolute isotope ratio standards. An agreement has been established between CBNM, Geel and the National Bureau of Standards, Washington, to prepare isotope ratio reference materials jointly so that they will be common to both communities. It is recommended that common batches of reference be established and stored at several places to guarantee accessibility at all times

  9. Kinetics of isotopic exchanges by using radioactive indicators

    International Nuclear Information System (INIS)

    May, S.

    1958-12-01

    After having noticed that iodine 131 under the form of sodium iodide has always been used as radioactive indicator in the CEA atomic pile located in Chatillon, this research report recalls the counting technique and some historical aspects of the notion of isotopic exchange and qualitative works, and presents some generalities on isotopic exchanges (reactions and calculation of rate constants of order 1 and 2, calculation of activation energy, spectro-photometric studies, Walden inversion, alkaline hydrolysis, influence of solvent on exchange kinetics, influence of the nature of the mineral halide). The author then addresses exchanges in aliphatic series (exchange with sodium iodide and with molecular iodine), exchanges in olefin series, exchanges in alicyclic series, and exchanges in aromatic series

  10. THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

    Energy Technology Data Exchange (ETDEWEB)

    Pizzarello, Sandra, E-mail: pizzar@asu.edu [Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85018-1604 (United States)

    2014-12-01

    HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organic compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.

  11. A revision in hydrogen isotopic composition of USGS42 and USGS43 human-hair stable isotopic reference materials for forensic science

    Science.gov (United States)

    Coplen, Tyler B.; Qi, Haiping

    2016-01-01

    The hydrogen isotopic composition (δ2HVSMOW-SLAP) of USGS42 and USGS43 human hair stable isotopic reference materials, normalized to the VSMOW (Vienna-Standard Mean Ocean Water)–SLAP (Standard Light Antarctic Precipitation) scale, was originally determined with a high temperature conversion technique using an elemental analyzer (TC/EA) with a glassy carbon tube and glassy carbon filling and analysis by isotope-ratio mass spectrometer (IRMS). However, the TC/EA IRMS method can produce inaccurate δ2HVSMOW-SLAPresults when analyzing nitrogen-bearing organic substances owing to the formation of hydrogen cyanide (HCN), leading to non-quantitative conversion of a sample into molecular hydrogen (H2) for IRMS analysis. A single-oven, chromium-filled, elemental analyzer (Cr-EA) coupled to an IRMS substantially improves the measurement quality and reliability of hydrogen isotopic analysis of hydrogen- and nitrogen-bearing organic material because hot chromium scavenges all reactive elements except hydrogen. USGS42 and USGS43 human hair isotopic reference materials have been analyzed with the Cr-EA IRMS method, and the δ2HVSMOW-SLAP values of their non-exchangeable hydrogen fractions have been revised:where mUr = 0.001 = ‰. On average, these revised δ2HVSMOW-SLAP values are 5.7 mUr more positive than those previously measured. It is critical that readers pay attention to the δ2HVSMOW-SLAP of isotopic reference materials in publications as they may need to adjust the δ2HVSMOW–SLAP measurement results of human hair in previous publications to ensure all results are on the same isotope-delta scale.

  12. The H+3 + H2 isotopic system. Origin of deuterium astrochemistry

    International Nuclear Information System (INIS)

    Hugo, Edouard Jean-Marie

    2008-01-01

    Dense cold molecular clouds reckoned to be stellar nurseries are the scene of an extreme molecular deuteration. Despite the cosmic D/H ratio of ∝10 -5 , molecular species in prestellar cores are observed to contain nearly as much deuterium as hydrogen. This astonishing deuterium enrichment promoted by low temperatures is the work of H + 3 . It is the key species which unlocks the deuterium from its HD reservoir via reactions like H + 3 +HD ↔ H 2 D + +H 2 and drags it further to other species in successive reactions. For this reason, the H + 3 +H 2 isotopic system is outstandingly critical for the astrochemistry of cold environments. However, its understanding is yet incomplete and insufficient. This thesis thus focuses on the H + 3 +H 2 isotopic system from a theoretical, experimental and astronomical point of view giving a particular look into the role of nuclear spins. As a first step, the stringent nuclear spin selection rules in associative, dissociative and reactive collisions are investigated. This purely theoretical study zooms into the details of the nuclear spin wavefunctions and shows that their permutation symmetry representation is necessary and sufficient, contrary to their angular momentum representation. Additionally, a new deterministic interpretation of nuclear spins in chemical reactions is proposed. Based on these considerations, a complete set of state-to-state rate coefficients for all H + 3 + H 2 isotopic variants is calculated using a microcanonical model leaned on phase space theory. An experimental study is conducted in parallel with a 22-pole ion trap apparatus in order to inspect the influences of temperature and H 2 ortho-to-para ratio. The good overall agreement between experimental and theoretical results supports the validity and utility of the calculated set of rate coefficients. Furthermore, the potentiality of the 22-pole ion trap apparatus is explored via the Laser Induced Reaction (LIR) technique applied to our system of

  13. Structure and isotopic ratios of aliphatic side chains in the insoluble organic matter of the Murchison carbonaceous chondrite

    Science.gov (United States)

    Huang, Yongsong; Alexandre, Marcelo R.; Wang, Yi

    2007-07-01

    We report in this paper the first molecular and isotopic characterization of individual aliphatic side chains from the insoluble organic matter (IOM) in the Murchison carbonaceous chondrite using a novel combined approach of RuO 4 oxidation and solid phase microextraction (SPME). The aliphatic side chains in the IOM of Murchison were first released by oxidizing aromatic structures using RuO 4. Because the IOM of carbonaceous chondrites contains predominantly short (C 1 to C 9) aliphatic substitutions, the resulting low molecular weight monocarboxylic acids (MCAs) are highly volatile and water-soluble. The conventional aqueous extraction and derivatization procedures following RuO 4 oxidation are unable to recover MCAs for subsequent analyses. We overcame this problem by employing SPME to directly capture the MCAs from the aqueous solution. We selected a SPME fiber with greater affinity for longer chain monoacids to compensate for the exponential decline of monoacid concentrations with increasing carbon numbers in meteorite IOM, allowing more accurate identification and quantification for the less abundant monoacids. We also determined the carbon and hydrogen isotopic ratios of individual MCAs derived from Murchinson IOM. Our results reveal significant similarity in both molecular structures and hydrogen isotopic ratios between the IOM aliphatic side chains and water-soluble MCAs in Murchison, suggesting that these compounds had common precursors. Our combined new approach of RuO 4 oxidation-SPME provides a new way to probe the molecular and isotopic characteristics of aliphatic side chains in carbonaceous chondrites.

  14. Molecular and isotope constraints on the formation of the insoluble organic matter of carbonaceous meteorites

    Science.gov (United States)

    Derenne, Sylvie; Robert, François

    2017-04-01

    The origin of the insoluble organic matter (IOM) of the carbonaceous meteorites remains an unsolved issue despite major achievements in the knowledge of its chemical structure. The latter led us to propose a model for its molecular structure. Based on the relationship between the aromatic moieties of the macromolecular structure and their aliphatic linkages, it was recently suggested that, its synthesis has taken place in the gas phase of the disk surrounding the Sun in its early T-Tauri phase and that organic radicals have played a central role in this organo-synthesis. To test experimentally this pathway, we submitted short hydrocarbons (methane, pentane, octane) to a microwave plasma discharge so as to produce in situ CHx radicals. The black organic residue deposited contained both soluble and insoluble OM. The comparison at the molecular level between the thus synthesized IOM and that of meteorite led to strong similarities thus supporting the proposed pathway for its organo-synthesis. Moreover, in the meteorite IOM, systematic deuterium enrichment relative to the protosolar value is observed at the bulk sample scale and micrometer-sized grains exhibit dramatic enrichments in deuterium interpreted as a heritage of the interstellar medium or resulting from ion-molecule reactions taking place in the diffuse part of the solar disk. In the aforementioned synthesized IOM, NanoSIMS analyses revealed large variations at a sub-micrometric spatial resolution. They likely reflect the differences in the D/H ratios of the CHx radicals whose polymerization is at the origin of the IOM. These isotopic heterogeneities are commensurable with those observed in meteorite IOM. As a consequence, the appearance of organic radicals in the ionized regions of the T-Tauri solar disk may have triggered the formation of organic compounds. This laboratory synthesis thus shed a new light on the formation conditions and pathways of the IOM of carbonaceous chondrites.

  15. Use of compound-specific stable carbon isotope ratio measurements of asphaltene-bound polycyclic aromatic hydrocarbons (PAHs) as a novel aid to source apportionment of environmental PAHs

    Energy Technology Data Exchange (ETDEWEB)

    C. Sun; C. Snape; M. Cooper; W. Ivwurie [University of Nottingham, Nottingham (United Kingdom). Nottingham Energy & Fuel Centre

    2005-07-01

    In this study, the PAHs from hydropyrolysis of asphaltenes from different primary sources (e.g. crude oil, low and high temperature coal tars) were characterized by their molecular distributions and {sup 13}C/{sup 12}C isotope ratios. It was found that for all oil samples, the molecular and isotopic profiles for their asphaltene-derived PAHs are both similar to those observed for their contained free aromatics, with {sup 13}C-isotopic values varying from -25 to -27{per_thousand} for the Nigerian and -27 to -30{per_thousand} for North Sea oil samples. For low and high temperature coal tar samples, however, similar molecular but different isotopic profiles were observed for their asphaltene-bound PAHs. The free aromatics are significantly isotopically lighter (by nearly -3{per_thousand}) than their asphaltene-derived counterparts having isotopic values typically between -22 and -23{per_thousand} for all coal tar samples examined, and this leads to a larger isotopic difference of up to 7{per_thousand} between the two sources of PAHs than that already observed between their free aromatics (3{per_thousand}). Applying these results to samples previously examined in an area where unambiguous source apportionment could not be conducted for the PAHs due to likely biodegradation, it was found that the bound PAHs released from the asphaltenes recovered from the soil samples in this area are extremely similar to low temperature tar as the source, in terms of their both molecular (highly alkylated) and isotopic profiles. The free PAHs are much less alkyl substituted confirming that the aromatics detected in this area have been subjected to intensiveenvironmental degradation with alkylated aromatic constituents being preferentially removed from their initial matrix.

  16. Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

    Science.gov (United States)

    Lasher, G. E.; Axford, Y.; Blair, N. E.

    2017-12-01

    Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

  17. Thermal Conductivity of Nanotubes Revisited: Effects of Chirality, Isotope Impurity, Tube Length, and Temperature

    OpenAIRE

    Zhang, Gang; Li, Baowen

    2004-01-01

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

  18. Radioactive isotopes are use wide in medicine

    International Nuclear Information System (INIS)

    Vargas, Celso

    2011-01-01

    The radioactive isotopes are used in medicine to view the status of an organ under different conditions; especially in the evolution of an organism after treatment of a cancer. In this process, three key areas have combined; first, the production of isotopes by developing of accelerators or reactors both linear accelerator and cyclotrons. Second, the use of suitable equipment such as PET (Positron emission tomography) for accurate scan of internal organs at physiological and biochemical level or molecular for diagnosis and effective treatment of diseases such as cancer. Currently, the trend has been to combine PET with other technologies such as CAT (computed axial tomographic) or SPECT (Single photon emission computer tomography). Third and finally, the development of molecules increasingly specific that have allowed to obtain several chemical compounds for different uses [es

  19. Three-dimensional hybrid silicon nanostructures for surface enhanced Raman spectroscopy based molecular detection

    Science.gov (United States)

    Vendamani, V. S.; Nageswara Rao, S. V. S.; Venugopal Rao, S.; Kanjilal, D.; Pathak, A. P.

    2018-01-01

    Three-dimensional silver nanoparticles decorated vertically aligned Si nanowires (Si NWs) are effective surface-enhanced Raman spectroscopy (SERS) substrates for molecular detection at low concentration levels. The length of Si NWs prepared by silver assisted electroless etching is increased with an increase in etching time, which resulted in the reduced optical reflection in the visible region. These substrates were tested and optimized by measuring the Raman spectrum of standard dye Rhodamine 6G (R6G) of 10 nM concentration. Further, effective SERS enhancements of ˜105 and ˜104 were observed for the cytosine protein (concentration of 50 μM) and ammonium perchlorate (oxidizer used in explosives composition with a concentration of 10 μM), respectively. It is established that these three-dimensional SERS substrates yielded considerably higher enhancement factors for the detection of R6G when compared to previous reports. The sensitivity can further be increased and optimized since the Raman enhancement was found to increase with an increase in the density of silver nanoparticles decorated on the walls of Si NWs.

  20. Diet-consumer nitrogen isotope fractionation for prolonged fasting arthropods.

    Science.gov (United States)

    Mizota, Chitoshi; Yamanaka, Toshiro

    2011-12-01

    Nitrogen acquisition for cellular metabolism during diapause is a primary concern for herbivorous arthropods. Analyses of naturally occurring stable isotopes of nitrogen help elucidate the mechanism. Relevant articles have cited (58 times up to mid-June 2011) anomalously elevated δ(15)N (per mil deviation of (15)N/(14)N, relative to atmospheric nitrogen=0 ‰) values (diet-consumer nitrogen isotope fractionation; up to 12 ‰) for a prolonged fasting raspberry beetle (Byturus tomentosus Degeer (Coleoptera: Byturidae)), which feeds on red raspberries (Rubus idaeus: δ(15)N= ~ +2 ‰). Biologists have hypothesised that extensive recycling of amino acid nitrogen is responsible for the prolonged fasting. Since this hypothesis was proposed in 1995, scientists have integrated biochemical and molecular knowledge to support the mechanism of prolonged diapausing of animals. To test the validity of the recycling hypothesis, we analysed tissue nitrogen isotope ratios for four Japanese arthropods: the shield bug Parastrachia japonensis Scott (Hemiptera: Cydnidae), the burrower bug Canthophorus niveimarginatus Scott (Hemiptera: Cydnidae), leaf beetle Gastrophysa atrocyanea Motschulsky (Coleoptera: Chrysomelidae) and the Japanese oak silkworm Antheraea yamamai (Lepidoptera: Saturniidae), all of which fast for more than 6 months as part of their life-history strategy. Resulting diet-consumer nitrogen isotope discrimination during fasting ranged from 0 to 7‰, as in many commonly known terrestrial arthropods. We conclude that prolonged fasting of arthropods does not always result in anomalous diet-consumer nitrogen isotope fractionation, since the recycling process is closed or nearly closed with respect to nitrogen isotopes.

  1. 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)

  2. Molecular imaging and the unification of multilevel mechanisms and data in medical physics

    International Nuclear Information System (INIS)

    Nikiforidis, George C.; Sakellaropoulos, George C.; Kagadis, George C.

    2008-01-01

    Molecular imaging (MI) constitutes a recently developed approach of imaging, where modalities and agents have been reinvented and used in novel combinations in order to expose and measure biologic processes occurring at molecular and cellular levels. It is an approach that bridges the gap between modalities acquiring data from high (e.g., computed tomography, magnetic resonance imaging, and positron-emitting isotopes) and low (e.g., PCR, microarrays) levels of a biological organization. While data integration methodologies will lead to improved diagnostic and prognostic performance, interdisciplinary collaboration, triggered by MI, will result in a better perception of the underlying biological mechanisms. Toward the development of a unifying theory describing these mechanisms, medical physicists can formulate new hypotheses, provide the physical constraints bounding them, and consequently design appropriate experiments. Their new scientific and working environment calls for interventions in their syllabi to educate scientists with enhanced capabilities for holistic views and synthesis.

  3. 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

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

    International Nuclear Information System (INIS)

    Jin, Biao; Rolle, Massimo

    2016-01-01

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

  5. 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.

  6. Surface enhanced raman scattering on tardigrada - Towards monitoring and imaging molecular structures in live cryptobiotic organisms

    DEFF Research Database (Denmark)

    Kneipp, Harald; Møbjerg, Nadja; Jørgensen, Aslak

    2013-01-01

    Tardigrades are microscopic metazoans which are able to survive extreme physical and chemical conditions by entering a stress tolerant state called cryptobiosis. At present, the molecular mechanisms behind cryptobiosis are still poorly understood. We show that surface enhanced Raman scattering su...

  7. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS

    International Nuclear Information System (INIS)

    Wallner, A.; Melber, K.; Merchel, S.; Ott, U.; Forstner, O.; Golser, R.; Kutschera, W.; Priller, A.; Steier, P.

    2013-01-01

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of 198 Pt/ 195 Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction.

  8. Stable platinum isotope measurements in presolar nanodiamonds by TEAMS

    Energy Technology Data Exchange (ETDEWEB)

    Wallner, A., E-mail: anton.wallner@univie.ac.at [University of Vienna, Faculty of Physics, VERA Laboratory, Waehringer Strasse 17, A-1090 Vienna (Austria); Department of Nuclear Physics, Research School of Physics and Engineering, Australian National University, Canberra (Australia); Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights (Australia); Melber, K. [University of Vienna, Faculty of Physics, VERA Laboratory, Waehringer Strasse 17, A-1090 Vienna (Austria); Merchel, S. [Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01314 Dresden (Germany); Ott, U. [Max-Planck-Institut fuer Chemie, Joh.-J.-Becherweg 27, D-55128 Mainz (Germany); Forstner, O.; Golser, R.; Kutschera, W.; Priller, A.; Steier, P. [University of Vienna, Faculty of Physics, VERA Laboratory, Waehringer Strasse 17, A-1090 Vienna (Austria)

    2013-01-15

    Nanodiamonds are stardust grains commonly found in primitive meteorites. They survived the formation of the solar system and kept their own individuality. Measurements of trace-element isotopic signatures in these grains will help understanding heavy element nucleosynthesis in massive stars and dust formation from their ejecta. We have continued previous attempts to search for stable Pt isotope anomalies in nanodiamonds via trace element accelerator mass spectrometry (TEAMS). The installation of a new injector beam line at the VERA facility allowed studying low traces of stable elements in different materials. Moreover, recent experiments showed that VERA provides the required measurement precision together with a low Pt machine background. Here, we observed for the first time an indication for enhancements of {sup 198}Pt/{sup 195}Pt isotope ratios in two diamond residues prepared by different chemical separation techniques from the Allende meteorite. Variations in other isotopic ratios were within analytical uncertainty, and no anomaly was identified in a third diamond fraction.

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

    International Nuclear Information System (INIS)

    Ishida, Takanobu

    2002-01-01

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

  10. Free Energy Calculations using a Swarm-Enhanced Sampling Molecular Dynamics Approach.

    Science.gov (United States)

    Burusco, Kepa K; Bruce, Neil J; Alibay, Irfan; Bryce, Richard A

    2015-10-26

    Free energy simulations are an established computational tool in modelling chemical change in the condensed phase. However, sampling of kinetically distinct substates remains a challenge to these approaches. As a route to addressing this, we link the methods of thermodynamic integration (TI) and swarm-enhanced sampling molecular dynamics (sesMD), where simulation replicas interact cooperatively to aid transitions over energy barriers. We illustrate the approach by using alchemical alkane transformations in solution, comparing them with the multiple independent trajectory TI (IT-TI) method. Free energy changes for transitions computed by using IT-TI grew increasingly inaccurate as the intramolecular barrier was heightened. By contrast, swarm-enhanced sampling TI (sesTI) calculations showed clear improvements in sampling efficiency, leading to more accurate computed free energy differences, even in the case of the highest barrier height. The sesTI approach, therefore, has potential in addressing chemical change in systems where conformations exist in slow exchange. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Control of electron localization to isolate and enhance molecular harmonic plateau in asymmetric HeH2+ system

    International Nuclear Information System (INIS)

    Lu, Ruifeng; Yu, Chao; Wang, Yunhui; Shi, Qi; Zhang, Yadong

    2014-01-01

    High-order harmonic generation from the asymmetric molecular ion HeH 2+ exposed to intense laser fields was investigated by quantum wave packet calculations in which the initial wave packet of HeH 2+ was prepared in the first excited 2pσ state. The calculated molecular harmonic plateau at low frequencies was effectively isolated and enhanced by adjusting the carrier-envelope phase (CEP) of the laser field. Furthermore, double-well model, time-dependent electronic density, electronic state population, and time-frequency analyses were presented to explain the underlying mechanism of the efficient isolated molecular plateau. By taking advantage of the CEP effect to control the electronic dynamics, this isolated molecular plateau can be used to generate high-intensity single attosecond pulses.

  12. Automatic isotope gas analysis of tritium labelled organic materials Pt. 1

    International Nuclear Information System (INIS)

    Gacs, I.; Mlinko, S.

    1978-01-01

    A new automatic procedure developed to convert tritium in HTO hydrogen for subsequent on-line gas counting is described. The water containing tritium is introduced into a column prepared from molecular sieve-5A and heated to 550 deg C. The tritium is transferred by isotopic exchange into hydrogen flowing through the column. The radioactive gas is led into an internal detector for radioactivity measurement. The procedure is free of memory effects, provides quantitative recovery with analytical reproducibility better than 0.5% rel. at a preset number of counts. The experimental and analytical results indicate that isotopic exchange between HTO and hydrogen over a column prepared from alumina or molecular sieve-5A can be successfully applied for the quantitative transfer of tritium from HTO into hydrogen for on-line gas countinq. This provides an analytical procedure for the automatic determination of tritium in water with an analytical reproducibility better than 0.5% rel. The exchange process will also be suitable for rapid tritium transfer from water formed during the decomposition of tritium-labelled organic compounds or biological materials. The application of the procedure in automatic isotope gas analysis of organic materials labelled with tritium will be described in subsequent papers (Parts II and III). (T.G.)

  13. Isotopic studies in soil and plant nutrition

    International Nuclear Information System (INIS)

    Pasricha, N.S.

    2001-01-01

    One of the most important peaceful applications of isotopes is in research for the enhancement of our understanding for increased crop production and better management of resources with higher economic efficiency and environmental safety. Nuclear techniques helped in generating useful information on such aspects as use-efficiency of fertilizer nutrients, quantifying their losses from soil and their biological transformations. Such information was, hitherto, obtained indirectly by conventional methods. Radio and stable isotopes have also been successfully employed for getting information in such diverse fields as soil erosion, turnover of soil organic matter, pesticide retention in soil ground water recharge etc. The property of 137 Cs adhering tightly to certain exchange surface in soil and its chemically inert nature has made it a useful tool for soil erosion studies. In this paper, applications of isotopes in the research and other such studies as degradation, movement and retention of pesticides, movement of nitrate in soil, biological and ammoniacal nitrogen fixation in soil is discussed

  14. Adsorption methods for hydrogen isotope storage on zeolitic sieves

    International Nuclear Information System (INIS)

    Cristescu, Ioana; Cristescu, Ion; Vasut, F.; Brad, S.; Lazar, A.

    2001-01-01

    For hydrogen isotope separation, adsorption molecular sieves and active carbon were used. Adsorption process proceeds at liquid nitrogen and liquid hydrogen temperatures. Commercial zeolites have the same proprieties with natural zeolites, but they have a regular pore structure. They also have affinity for molecules of different size with defined shapes. Experimental results obtained at liquid nitrogen temperature (77.4 K) and liquid hydrogen revealed the efficient behaviour of the active carbon and zeolitic sieves for hydrogen isotopes temporary storage. We study adsorption of the synthetic zeolites in a wide range of temperatures and pressures and we used the molecular sieves 4A, 5A and active carbon. The 4A and 5A zeolites have a tridimensional structure with 11.4 A diameter. When the hydration water is eliminated, the material keeps a porous structure. The porous volume represents 45% from the zeolite mass for 4A and 5A sieves. The activation temperature of the zeolite and the carbon is very important for obtaining a high adsorption capacity. If the temperature used for activation is low, the structural water will be not eliminated and the adsorption capacity will be low. The excessive temperature will destroy the porous structure. The adsorption capacity for the hydrogen isotopes was calculated with the relation: A = V ads /m (cm 3 /g). The adsorption capacity and efficiency for the adsorbent materials, are given. Physical adsorption process of the hydrogen isotopes was carried out at liquid nitrogen temperature. The flux gas used in the adsorption system is composed of dry deuterium and protium. This mixture is cooled in liquid nitrogen and then is passed to the adsorbent getter at the same temperature (77.4 K). The gas flux in the adsorbent getter is 5 and 72 l/h (which correspond to 0.008 and 0.134 discharge velocity, respectively). (authors)

  15. High precision analysis of trace lithium isotope by thermal ionization mass spectrometry

    International Nuclear Information System (INIS)

    Tang Lei; Liu Xuemei; Long Kaiming; Liu Zhao; Yang Tianli

    2010-01-01

    High precision analysis method of ng lithium by thermal ionization mass spectrometry is developed. By double-filament measurement,phosphine acid ion enhancer and sample pre-baking technique,the precision of trace lithium analysis is improved. For 100 ng lithium isotope standard sample, relative standard deviation is better than 0.086%; for 10 ng lithium isotope standard sample, relative standard deviation is better than 0.90%. (authors)

  16. [Research progress on food sources and food web structure of wetlands based on stable isotopes].

    Science.gov (United States)

    Chen, Zhan Yan; Wu, Hai Tao; Wang, Yun Biao; Lyu, Xian Guo

    2017-07-18

    The trophic dynamics of wetland organisms is the basis of assessing wetland structure and function. Stable isotopes of carbon and nitrogen have been widely applied to identify trophic relationships in food source, food composition and food web transport in wetland ecosystem studies. This paper provided an overall review about the current methodology of isotope mixing model and trophic level in wetland ecosystems, and discussed the standards of trophic fractionation and baseline. Moreover, we characterized the typical food sources and isotopic compositions of wetland ecosystems, summarized the food sources in different trophic levels of herbivores, omnivores and carnivores based on stable isotopic analyses. We also discussed the limitations of stable isotopes in tra-cing food sources and in constructing food webs. Based on the current results, development trends and upcoming requirements, future studies should focus on sample treatment, conservation and trophic enrichment measurement in the wetland food web, as well as on combing a variety of methodologies including traditional stomach stuffing, molecular markers, and multiple isotopes.

  17. Ion Mobility Mass Spectrometry Direct Isotope Abundance Analysis

    International Nuclear Information System (INIS)

    Manard, Manuel J.; Weeks, Stephan; Kyle, Kevin

    2010-01-01

    The nuclear forensics community is currently engaged in the analysis of illicit nuclear or radioactive material for the purposes of non-proliferations and attribution. One technique commonly employed for gathering nuclear forensics information is isotope analysis. At present, the state-of-the-art methodology for obtaining isotopic distributions is thermal ionization mass spectrometry (TIMS). Although TIMS is highly accurate at determining isotope distributions, the technique requires an elementally pure sample to perform the measurement. The required radiochemical separations give rise to sample preparation times that can be in excess of one to two weeks. Clearly, the nuclear forensics community is in need of instrumentation and methods that can expedite their decision making process in the event of a radiological release or nuclear detonation. Accordingly, we are developing instrumentation that couples a high resolution IM drift cell to the front end of a MS. The IM cell provides a means of separating ions based upon their collision cross-section and mass-to-charge ratio (m/z). Two analytes with the same m/z, but with different collision cross-sections (shapes) would exit the cell at different times, essentially enabling the cell to function in a similar manner to a gas chromatography (GC) column. Thus, molecular and atomic isobaric interferences can be effectively removed from the ion beam. The mobility selected chemical species could then be introduced to a MS for high-resolution mass analysis to generate isotopic distributions of the target analytes. The outcome would be an IM/MS system capable of accurately measuring isotopic distributions while concurrently eliminating isobaric interferences and laboratory radiochemical sample preparation. The overall objective of this project is developing instrumentation and methods to produce near real-time isotope distributions with a modular mass spectrometric system that performs the required gas-phase chemistry and

  18. Stable isotope studies: Progress report, March 1985--August 1987

    International Nuclear Information System (INIS)

    Ishida, Takanobu.

    1987-01-01

    Studies have been carried out in the following areas: Stable Isotope Fractionation (1) Effects of chemical poisons and surface modifiers on polycrystalline platinum electrode surfaces have been investigated with a goal to develop a new form of heterogeneous catalyst for the hydrogen isotope exchange between dihydrogen and water. (2) A new nitrogen-15 fractionation process has been developed, based on the isotope exchange between liquid N 2 O 3 -N 2 O 4 mixture and their vapor phase at a subambient temperature and a raised pressure. (3) A closed chemical recycle process has been developed for use in connection with the refluxer in the Nitrox-type nitrogen-15 plant. Isotope Effects (1) The vapor pressure isotope effect (VPIE) study of liquid fluoromethanes have been completed. (2) The VPIE study of solid and liquid ammonia has been completed. (3) A theoretical foundation of the additivity for the vibrational zero-point energy (ZPE) has been developed. Studies of Liquid Ammonia. With an aim to study intermolecular interaction (and the inversion phenomenon, in particular) in liquid ammonia, and to further investigate various ammonia solutions, a molecular dynamics (MD) study has been initiated. An MD program has been completed, and force field functions have been developed for an ensemble of non-rigid ammonia molecules. 107 refs., 41 figs., 10 tabs

  19. Isotope tracers in global water and climate studies of the past and present

    International Nuclear Information System (INIS)

    Edwards, T.W.D.; Birks, S.J.; Gibson, J.J.

    2002-01-01

    To date the global distribution of isotopes in modern precipitation has been characterized almost exclusively from the IAEA/WMO GNIP database, although patchiness of GNIP station records in both time and space has limited the potential of isotope hydrology and climate applications in some areas. Herein, we discuss the prospect of utilizing GCMs for simulating global isotope distributions as a supplementary tool for modern and paleoclimate isotope studies to bridge this gap. Such models currently generate reliable zonal isotope fields, and it is anticipated that future enhancements in finescale resolution of GCMs, and incorporation of land-surface feedbacks and topography will allow for future development of a global reanalysis data set ground-truthed by GNIP. Compilation of time-slice maps of past isotope distribution in precipitation from archival records of meteoric waters also offers significant potential to ground-truth paleoclimate simulations extending back tens to hundreds of thousands of years. (author)

  20. Stable Isotope Systematics of Coalbed Gas during Desorption and Production

    Directory of Open Access Journals (Sweden)

    Martin Niemann

    2017-06-01

    Full Text Available The stable carbon isotope ratios of coalbed methane (CBM demonstrate diagnostic changes that systematically vary with production and desorption times. These shifts can provide decisive, predictive information on the behaviour and potential performance of CBM operations. Samples from producing CBM wells show a general depletion in 13C-methane with increasing production times and corresponding shifts in δ13C-CH4 up to 35.8‰. Samples from canister desorption experiments show mostly enrichment in 13C for methane with increasing desorption time and isotope shifts of up to 43.4‰. Also, 13C-depletion was observed in some samples with isotope shifts of up to 32.1‰. Overall, the magnitudes of the observed isotope shifts vary considerably between different sample sets, but also within samples from the same source. The δ13C-CH4 values do not have the anticipated signature of methane generated from coal. This indicates that secondary processes, including desorption and diffusion, can influence the values. It is also challenging to deconvolute these various secondary processes because their molecular and isotope effects can have similar directions and/or magnitudes. In some instances, significant alteration of CBM gases has to be considered as a combination of secondary alteration effects.

  1. Hydrogen isotope fractionation in methane plasma

    Science.gov (United States)

    Robert, François; Derenne, Sylvie; Lombardi, Guillaume; Hassouni, Khaled; Michau, Armelle; Reinhardt, Peter; Duhamel, Rémi; Gonzalez, Adriana; Biron, Kasia

    2017-01-01

    The hydrogen isotope ratio (D/H) is commonly used to reconstruct the chemical processes at the origin of water and organic compounds in the early solar system. On the one hand, the large enrichments in deuterium of the insoluble organic matter (IOM) isolated from the carbonaceous meteorites are interpreted as a heritage of the interstellar medium or resulting from ion-molecule reactions taking place in the diffuse part of the protosolar nebula. On the other hand, the molecular structure of this IOM suggests that organic radicals have played a central role in a gas-phase organosynthesis. So as to reproduce this type of chemistry between organic radicals, experiments based on a microwave plasma of CH4 have been performed. They yielded a black organic residue in which ion microprobe analyses revealed hydrogen isotopic anomalies at a submicrometric spatial resolution. They likely reflect differences in the D/H ratios between the various CHx radicals whose polymerization is at the origin of the IOM. These isotopic heterogeneities, usually referred to as hot and cold spots, are commensurable with those observed in meteorite IOM. As a consequence, the appearance of organic radicals in the ionized regions of the disk surrounding the Sun during its formation may have triggered the formation of organic compounds.

  2. 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

  3. Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites

    Science.gov (United States)

    Jones, R. H.; Leshin, L. A.; Guan, Y.

    2004-01-01

    Some of the biggest challenges to understanding the early history of the solar system include determining the distribution of oxygen isotopes amongst materials that existed in the solar nebula, and interpreting the processes that might have resulted in the observed isotopic distributions. Oxygen isotope ratios in any individual mineral grain from a chondritic meteorite may be the cumulative product of a variety of processes, including stellar nucleosynthetic events, gas/solid interactions in the molecular cloud, mixing of independent isotopic reservoirs in the nebula, mass-independent processing in the nebula, and mass-dependent fractionation effects in various environments. It is not possible to unravel this complex isotopic record unless the distribution of oxygen isotope ratios in chondritic materials is fully understood.

  4. Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

    Science.gov (United States)

    Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

    2013-12-01

    Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other

  5. Galaxy pairs in the SDSS - XIII. The connection between enhanced star formation and molecular gas properties in galaxy mergers

    Science.gov (United States)

    Violino, Giulio; Ellison, Sara L.; Sargent, Mark; Coppin, Kristen E. K.; Scudder, Jillian M.; Mendel, Trevor J.; Saintonge, Amelie

    2018-05-01

    We investigate the connection between star formation and molecular gas properties in galaxy mergers at low redshift (z ≤ 0.06). The study we present is based on IRAM 30-m CO(1-0) observations of 11 galaxies with a close companion selected from the Sloan Digital Sky Survey (SDSS). The pairs have mass ratios ≤4, projected separations rp ≤ 30 kpc and velocity separations ΔV ≤ 300 km s-1, and have been selected to exhibit enhanced specific star formation rates (sSFRs). We calculate molecular gas (H2) masses, assigning to each galaxy a physically motivated conversion factor αCO, and we derive molecular gas fractions and depletion times. We compare these quantities with those of isolated galaxies from the extended CO Legacy Data base for the GALEX Arecibo SDSS Survey sample (xCOLDGASS; Saintonge et al.) with gas quantities computed in an identical way. Ours is the first study which directly compares the gas properties of galaxy pairs and those of a control sample of normal galaxies with rigorous control procedures and for which SFR and H2 masses have been estimated using the same method. We find that the galaxy pairs have shorter depletion times and an average molecular gas fraction enhancement of 0.4 dex compared to the mass matched control sample drawn from xCOLDGASS. However, the gas masses (and fractions) in galaxy pairs and their depletion times are consistent with those of non-mergers whose SFRs are similarly elevated. We conclude that both external interactions and internal processes may lead to molecular gas enhancement and decreased depletion times.

  6. Wetting phenomena in films of molecular hydrogen isotopes

    International Nuclear Information System (INIS)

    Albrecht, U.; Conradt, R.; Herminghaus, S.; Leiderer, P.

    1996-01-01

    We have investigated various aspects of the wetting behavior of hydrogen films (including the heavier isotopes) using surface plasmon resonance, light scattering, and photoelectron emission. Studies in the vicinity of the triple point (T 3 (H 2 )=13,96 K) confirmed the known >, and gave no indications for a prewetting transition in this range. At low temperatures (T 3 /3) the equilibrium film thickness reaches only a few monolayers. Thicker films, prepared by quench-condensation of H 2 gas at 1.5 K, undergo a dewetting process during annealing: most of the film material contracts to clusters, and in between the films thins down to its equilibrium thickness. This surface diffusion process is thermally activated, with an activation energy of 23 K (in the case of H 2 ). The dewetting kinetics has not revealed any indication for a surface-molten layer on the solid films at low temperatures, or for a superfluid component

  7. Laser enhanced microwave plasma isotope separation. Final report, September 30, 1992--September 29, 1995

    International Nuclear Information System (INIS)

    Brake, M.L.; Gilgenbach, R.M.

    1996-06-01

    The experimental research was to focus on laser excitation of a low abundance isotope and then ionize and separate the isotope of low abundance using a microwave/ECR discharge at 2.45 GHz. A small compact electron cyclotron resonance ion source, which uses permanent magnets, was constructed during this project. The dye laser was purchased and later an excimer laser had to also be purchased because it turned out that the dye laser could not be pumped by our copper laser. It was intended that the dye laser be tuned to a wavelength of 670.8 nm, which would excite 6 Li which would then be preferentially ionized by the ECR source and collected with a charged grid. The degree of enrichment was to be determined using thermal ionization mass spectrometry. The final objective of this project was to assess the feasibility of this system to large-scale production of stable isotopes. However the funding of this project was interrupted and we were not able to achieve all of our goals

  8. Determination of the hydrogen isotopic compositions of organic materials and hydrous minerals using thermal combustion laser spectroscopy.

    Science.gov (United States)

    Koehler, Geoff; Wassenaar, Leonard I

    2012-04-17

    Hydrogen isotopic compositions of hydrous minerals and organic materials were measured by combustion to water, followed by optical isotopic analysis of the water vapor by off-axis integrated cavity output spectroscopy. Hydrogen and oxygen isotopic compositions were calculated by numerical integration of the individual isotopologue concentrations measured by the optical spectrometer. Rapid oxygen isotope exchange occurs within the combustion reactor between water vapor and molecular oxygen so that only hydrogen isotope compositions may be determined. Over a wide range in sample sizes, precisions were ±3-4 per mil. This is comparable but worse than continuous flow-isotope ratio mass spectroscopy (CF-IRMS) methods owing to memory effects inherent in water vapor transfer. Nevertheless, the simplicity and reduced cost of this analysis compared to classical IRMS or CF-IRMS methods make this an attractive option to determine the hydrogen isotopic composition of organic materials where the utmost precision or small sample sizes are not needed.

  9. Detection of Molecular Oxygen at Low Concentrations Using Quartz Enhanced Photoacoustic Spectroscopy

    Directory of Open Access Journals (Sweden)

    Andreas Pohlkötter

    2010-09-01

    Full Text Available Molecular oxygen is detected at low concentrations using photoacoustic spectroscopy despite its unfavorable photoacoustic properties. The system consists of a seed laser diode, a tapered amplifier and a quartz tuning fork based spectrophone, thus employing quartz enhanced photoacoustic spectroscopy (QEPAS. With this system a detection limit of 13 ppm is reached with a compact and long term stable setup. Further improvement of the detection limit is possible by adding suitable gases to the sample gas that promote the radiationless de-excitation of the oxygen molecules.

  10. Enhanced Sampling in Molecular Dynamics Using Metadynamics, Replica-Exchange, and Temperature-Acceleration

    Directory of Open Access Journals (Sweden)

    Cameron Abrams

    2013-12-01

    Full Text Available We review a selection of methods for performing enhanced sampling in molecular dynamics simulations. We consider methods based on collective variable biasing and on tempering, and offer both historical and contemporary perspectives. In collective-variable biasing, we first discuss methods stemming from thermodynamic integration that use mean force biasing, including the adaptive biasing force algorithm and temperature acceleration. We then turn to methods that use bias potentials, including umbrella sampling and metadynamics. We next consider parallel tempering and replica-exchange methods. We conclude with a brief presentation of some combination methods.

  11. Pressure measurements of TO-phonon anharmonicity in isotopic ZnS

    Energy Technology Data Exchange (ETDEWEB)

    Tallman, R.E.; Weinstein, B.A. [SUNY at Buffalo, Department of Physics, Buffalo, NY 14260 (United States); Ritter, T.M. [Dept. of Chemistry and Physics, UNC Pembroke, NC 28372 (United States); Cantarero, A. [Dept. of Physics and Institute of Materials Science, University of Valencia (Spain); Serrano, J.; Lauck, R.; Cardona, M. [Max-Planck-Institut fuer Festkoerperforschung, 70569 Stuttgart (Germany)

    2004-03-01

    We have measured the dependence on pressure of the line-widths of the TO and LO Raman phonons of {beta}-ZnS. In order to enhance the phenomena observed, and to eliminate possible effects of isotopic disorder, we have measured a nearly isotopically pure crystal, {sup 68}Zn{sup 32}S. The strongly structured pressure effects observed are interpreted on the basis of anharmonic decay and the corresponding two-phonon density of states. (copyright 2004 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. DNA stable-isotope probing (DNA-SIP).

    Science.gov (United States)

    Dunford, Eric A; Neufeld, Josh D

    2010-08-02

    DNA stable-isotope probing (DNA-SIP) is a powerful technique for identifying active microorganisms that assimilate particular carbon substrates and nutrients into cellular biomass. As such, this cultivation-independent technique has been an important methodology for assigning metabolic function to the diverse communities inhabiting a wide range of terrestrial and aquatic environments. Following the incubation of an environmental sample with stable-isotope labelled compounds, extracted nucleic acid is subjected to density gradient ultracentrifugation and subsequent gradient fractionation to separate nucleic acids of differing densities. Purification of DNA from cesium chloride retrieves labelled and unlabelled DNA for subsequent molecular characterization (e.g. fingerprinting, microarrays, clone libraries, metagenomics). This JoVE video protocol provides visual step-by-step explanations of the protocol for density gradient ultracentrifugation, gradient fractionation and recovery of labelled DNA. The protocol also includes sample SIP data and highlights important tips and cautions that must be considered to ensure a successful DNA-SIP analysis.

  13. Static, Mixed-Array Total Evaporation for Improved Quantitation of Plutonium Minor Isotopes in Small Samples

    Science.gov (United States)

    Stanley, F. E.; Byerly, Benjamin L.; Thomas, Mariam R.; Spencer, Khalil J.

    2016-06-01

    Actinide isotope measurements are a critical signature capability in the modern nuclear forensics "toolbox", especially when interrogating anthropogenic constituents in real-world scenarios. Unfortunately, established methodologies, such as traditional total evaporation via thermal ionization mass spectrometry, struggle to confidently measure low abundance isotope ratios (evaporation techniques as a straightforward means of improving plutonium minor isotope measurements, which have been resistant to enhancement in recent years because of elevated radiologic concerns. Results are presented for small sample (~20 ng) applications involving a well-known plutonium isotope reference material, CRM-126a, and compared with traditional total evaporation methods.

  14. Anomalous isotopic composition of cosmic rays

    International Nuclear Information System (INIS)

    Woosley, S.E.; Weaver, T.A.

    1980-01-01

    Recent measurements of nonsolar isotopic patterns for the elements neon and (perhaps) magnesium in cosmic rays are interpreted within current models of stellar nucleosynthesis. One possible explanation is that the stars currently responsible for cosmic-ray synthesis in the Galaxy are typically super-metal-rich by a factor of two to three. Other possibilities include the selective acceleration of certain zones or masses of supernovas or the enhancement of 22 Ne in the interstellar medium by mass loss from red giant stars and planetary nebulas. Measurements of critical isotopic ratios are suggested to aid in distinguishing among the various possibilities. Some of these explanations place significant constraints on the fraction of cosmic ray nuclei that must be fresh supernova debris and the masses of the supernovas involved. 1 figure, 3 tables

  15. To problem of experimental determination of parameters of μ-atom charge-exchange process of hydrogen isotopes on He nuclei

    International Nuclear Information System (INIS)

    Bystritskij, V.M.; Stolupin, V.A.

    1990-01-01

    The kinetics of μ-atomic and μ-molecular processes occuring in hydrogen isotopes-helium mixture is observed. The expressions are obtained to determine the parameters of a process of the muon transition from hydrogen isotope μ atoms to helium nuclei with the use of different experimental methods. 18 refs.; 3 figs.; 1 tab

  16. Isotopic shift in even-even barium isotopes

    International Nuclear Information System (INIS)

    Karim, Afaque; Naz, Tabassum; Ahmad, Shakeb

    2017-01-01

    We have discussed the correlation between a nuclear shape and its matter distribution. Here, we present the root-mean-square radii (r rms ) and rms charge radius (r ch ). We have also discussed the isotopic shift in terms of the observable ‹Δr 2 c › N,82 and its differential ‹Δr 2 c › N-2,N . We present nuclear radii evaluated using different interactions. Neutron radii and charge radii for all the isotopic chains are shown. Neutron radii for Ba isotopes show an increasing trend with the neutron number for all isotopic chains. One can observe a clear kink about magic number N=82

  17. Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

    Science.gov (United States)

    Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

    2015-03-01

    We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

  18. Elucidation of C{sub 2} and CN formation mechanisms in laser-induced plasmas through correlation analysis of carbon isotopic ratio

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Meirong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Chan, George C.-Y.; Mao, Xianglei; Gonzalez, Jhanis J. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lu, Jidong [School of Electric Power, South China University of Technology, Guangzhou, Guangdong 510640 (China); Russo, Richard E., E-mail: RERusso@lbl.gov [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2014-10-01

    Laser ablation molecular isotopic spectrometry (LAMIS) was recently reported for rapid isotopic analysis by measuring molecular emission from laser-induced plasmas at atmospheric pressure. With {sup 13}C-labeled benzoic acid as a model sample, this research utilized the LAMIS approach to clarify the formation mechanisms of C{sub 2} and CN molecules during laser ablation of organic materials. Because the isotopic ratios in the molecular bands could deviate from statistical distribution depending on their formation pathways, the dominant mechanism can be identified through a comparison of the experimental observed isotopic patterns in the molecular emission with the theoretical statistical pattern. For C{sub 2} formation, the experimental {sup 12}C{sup 12}C/{sup 13}C{sup 12}C ratios not only support a recombination mechanism through atomic carbon at early delay time but also indicate the presence of other operating mechanisms as the plasma evolves; it is proposed that some of the C{sub 2} molecules are released directly from the aromatic ring of the sample as molecular fragments. In contrast, the temporal profiles in the {sup 12}C/{sup 13}C ratios derived from CN emission exhibited opposite behavior with those derived from C{sub 2} emission, which unambiguously refutes mechanisms that require C{sub 2} as a precursor for CN formation; CN formation likely involves atomic carbon or species with a single carbon atom. - Highlights: • C{sub 2} and CN formation mechanisms during laser ablation of organic material studied • Some C{sub 2} molecules are directly desorbed from the organic compound. • C{sub 2} molecules are not important precursor for CN-radical formation.

  19. Carbon Monoxide Stable Isotopes: Extraction Technique Development and Urban Atmospheric Analysis

    Science.gov (United States)

    Vimont, Isaac Josef

    We have developed an extraction system to analyze isotopes of carbon monoxide (CO). We then analyzed CO isotopes for two years at Indianapolis, IN, USA. These measurements were done at three towers, one of which measured incoming, background air into the city. We quantitatively removed the background signal and determined the urban CO mole fraction and isotopic enhancements. During the winter months, we constrained the isotopic signature and concluded that the majority of CO produced during the winter was produced by fossil fuel combustion. We found that the Indianapolis fossil fuel signature differed from that of studies done in Europe. Further, we performed a limited traffic study to look at CO isotopes from traffic. While this was not conclusive, it did support our hypothesis that a larger fraction of the Indianapolis vehicle fleet may have malfunctioning catalytic systems, which biases the isotopic results, particularly for delta18O. We used the wintertime fossil fuel isotopic signature to help constrain the summertime budget. It was hypothesized that a second source of CO was significant during the summer months. Oxidation of biogenically produced volatile organic compounds (BVOC's) was one possible source. Oxidized BVOC's were consistent with the changes between our winter and summer isotopic source signatures. We then used the isotopic signatures to determine that between zero and sixty percent of the summertime CO budget was produced from oxidized VOC's. This provided the first direct evidence of a larger percentage of urban CO being produced by oxidized VOC's.

  20. Lasers in atomic, molecular and nuclear physics

    International Nuclear Information System (INIS)

    Letokhov, V.S.

    1986-01-01

    This book presents papers on laser applications in atomic, molecular and nuclear physics. Specifically discussed are: laser isotope separation; laser spectroscopy of chlorophyll; laser spectroscopy of molecules and cell membranes; laser detection of atom-molecule collisions and lasers in astrophysics

  1. Stable isotopes

    International Nuclear Information System (INIS)

    Evans, D.K.

    1986-01-01

    Seventy-five percent of the world's stable isotope supply comes from one producer, Oak Ridge Nuclear Laboratory (ORNL) in the US. Canadian concern is that foreign needs will be met only after domestic needs, thus creating a shortage of stable isotopes in Canada. This article describes the present situation in Canada (availability and cost) of stable isotopes, the isotope enrichment techniques, and related research programs at Chalk River Nuclear Laboratories (CRNL)

  2. Selective isotope determination of lanthanum by diode-laser-initiated resonance-ionization mass spectrometry

    International Nuclear Information System (INIS)

    Young, J.P.; Shaw, R.W.

    1995-01-01

    A diode-laser step has been incorporated into a resonance-ionization mass spectrometry optical excitation process to enhance the isotopic selectivity of the technique. Lanthanum isotope ratio enhancements as high as 10 3 were achieved by use of a single-frequency cw diode laser tuned to excite the first step of a three-step excitation--ionization optical process; the subsequent steps were excited by use of a pulsed dye laser. Applying the same optical technique, we measured atomic hyperfine constants for the high-lying even-parity 4 D 5/2 state of lanthanum at 30 354 cm --1 . The general utility of this spectral approach is discussed

  3. Properties of Fe, Ni and Zn isotopes near the drip-lines

    International Nuclear Information System (INIS)

    Tarasov, V.N.; Tarasaov, D.V.; Gridnev, K.A.; Gridnev, D.K.; Kartavenko, V.G.; Greiner, W.

    2008-01-01

    The position of the neutron and proton drip-lines as well as properties of the isotopes Fe, Ni and Zn with neutron excess and neutron deficit are studied within the Hartree–Fock approach with the Skyrme interaction (Ska, SkM*, Sly4). The pairing is taken into account on the basis of the BCS approach with the pairing constant G = (19.5/A)[1 ± 0.51(N-Z)/A]. Our calculations predict that for Ni isotopes around N = 62 there appears a sudden increase of the deformation parameter up to β = 0.4. The zone with such big deformation, where Ni isotopes are stable against one neutron emission stretches up to N = 78. The magic numbers effects for the isotopes 48 Ni, 56 Ni, 78 Ni, 110 Ni are discussed. The universality of the reasons standing behind the enhancement of stability of the isotopes 40 O and 110 Ni which are beyond the drip-line is demonstrated. Calculated values of the two-neutron separation energy, and proton and neutron root mean square radii for the chain of Ni isotopes show a good agreement with existing Hartree–Fock–Bogoliubov calculations of these values. (author)

  4. Separation of hydrogen isotopes for tritium waste removal

    International Nuclear Information System (INIS)

    Wilkes, W.R.

    1975-01-01

    A distillation cascade for separating hydrogen isotopes was simulated by means of a multicomponent, multistage computer code. A hypothetical test mixture containing equal atomic fractions of protium, deuterium and tritium, equilibrated to high temperature molecular concentrations was used as feed. The results show that a two-column cascade can be used to separate the protium from the tritium. Deuterium appears both in the protium and the tritium product streams. (auth)

  5. Uranium Isotopic Analysis with the FRAM Isotopic Analysis Code

    International Nuclear Information System (INIS)

    Vo, D.T.; Sampson, T.E.

    1999-01-01

    FRAM is the acronym for Fixed-Energy Response-Function Analysis with Multiple efficiency. This software was developed at Los Alamos National Laboratory originally for plutonium isotopic analysis. Later, it was adapted for uranium isotopic analysis in addition to plutonium. It is a code based on a self-calibration using several gamma-ray peaks for determining the isotopic ratios. The versatile-parameter database structure governs all facets of the data analysis. User editing of the parameter sets allows great flexibility in handling data with different isotopic distributions, interfering isotopes, and different acquisition parameters such as energy calibration and detector type

  6. Isotope enrichment

    International Nuclear Information System (INIS)

    Garbuny, M.

    1979-01-01

    The invention discloses a method for deriving, from a starting material including an element having a plurality of isotopes, derived material enriched in one isotope of the element. The starting material is deposited on a substrate at less than a critical submonatomic surface density, typically less than 10 16 atoms per square centimeter. The deposit is then selectively irradiated by a laser (maser or electronic oscillator) beam with monochromatic coherent radiation resonant with the one isotope causing the material including the one istope to escape from the substrate. The escaping enriched material is then collected. Where the element has two isotopes, one of which is to be collected, the deposit may be irradiated with radiation resonant with the other isotope and the residual material enriched in the one isotope may be evaporated from the substrate and collected

  7. The Permeability Enhancing Mechanism of DMSO in Ceramide Bilayers Simulated by Molecular Dynamics

    Science.gov (United States)

    Notman, Rebecca; den Otter, Wouter K.; Noro, Massimo G.; Briels, W. J.; Anwar, Jamshed

    2007-01-01

    The lipids of the topmost layer of the skin, the stratum corneum, represent the primary barrier to molecules penetrating the skin. One approach to overcoming this barrier for the purpose of delivery of active molecules into or via the skin is to employ chemical permeability enhancers, such as dimethylsulfoxide (DMSO). How these molecules exert their effect at the molecular level is not understood. We have investigated the interaction of DMSO with gel-phase bilayers of ceramide 2, the predominant lipid in the stratum corneum, by means of molecular dynamics simulations. The simulations satisfactorily reproduce the phase behavior and the known structural parameters of ceramide 2 bilayers in water. The effect of DMSO on the gel-phase bilayers was investigated at various concentrations over the range 0.0−0.6 mol fraction DMSO. The DMSO molecules accumulate in the headgroup region and weaken the lateral forces between the ceramides. At high concentrations of DMSO (≥0.4 mol fraction), the ceramide bilayers undergo a phase transition from the gel phase to the liquid crystalline phase. The liquid-crystalline phase of ceramides is expected to be markedly more permeable to solutes than the gel phase. The results are consistent with the experimental evidence that high concentrations of DMSO fluidize the stratum corneum lipids and enhance permeability. PMID:17513383

  8. Derivation of basic equations for rigorous dynamic simulation of cryogenic distillation column for hydrogen isotope separation

    International Nuclear Information System (INIS)

    Kinoshita, Masahiro; Naruse, Yuji

    1981-08-01

    The basic equations are derived for rigorous dynamic simulation of cryogenic distillation columns for hydrogen isotope separation. The model accounts for such factors as differences in latent heat of vaporization among the six isotopic species of molecular hydrogen, decay heat of tritium, heat transfer through the column wall and nonideality of the solutions. Provision is also made for simulation of columns with multiple feeds and multiple sidestreams. (author)

  9. TU-H-CAMPUS-TeP3-05: Evaluation of the Microscopic Dose Enhancement in the Nanoparticle-Enhanced Auger Therapy

    International Nuclear Information System (INIS)

    Sung, W; Jung, S; Ye, S

    2016-01-01

    Purpose: The aim of this study is to apply Monte Carlo simulations to investigate the nanoparticle dose enhancement for Auger therapy. Methods: Two nanoparticle fabrications were considered: nanoshell and nanosphere. In the first step, a single nanoparticle was irradiated with Auger emitters. The electrons were scored in a phase space at the outer surface of the nanoparticle with Geant4-Penelope. In the second step, the previously recorded phase space was used as a source and placed at the center of a cell-size water phantom. The nanoscale dose was evaluated in water around the nanoparticle with Geant4-DNA. The dose enhancement factor (DEF) is defined as the ratio of doses with and without nanoparticles. The nanoparticles were replaced by corresponding water nanoparticle with the same size and volume source which represents typical situation of Auger emitters without nanoparticle. Various sizes/materials of nanoparticles and isotopes were considered. Results: Nanoshell - Microscopic dose was increased up to 130% at 20 – 100 nm distances from the surface of Au- 125 I nanoshell. However, dose at less than 20 nm distance was reduced due to absorbed low energy electrons in gold nanoshell. The amounts and regions of the dose enhancement were dependent on nanoshell size, materials, and isotopes. Nanosphere - The increased amounts of electrons up to 300% and reduced average energy with nanosphere were observed compared with water nanoparticle. We observed localized dose enhancement (up to a factor 3.6) in the immediate vicinity (< 50 nm) of Au- 125 I nanosphere. The dose enhancement patterns vary according to nanosphere sizes and isotopes. Conclusion: We conclude that Auger therapy with nanoparticles can lead to change of electron energy spectrum and dose enhancements at certain range. The dose enhancement patterns vary according to nanoparticle sizes, materials, and isotopes. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the

  10. 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

  11. The stable isotopic composition of molecular hydrogen in the tropopause region probed by the CARIBIC aircraft

    Directory of Open Access Journals (Sweden)

    A. M. Batenburg

    2012-05-01

    Full Text Available More than 450 air samples that were collected in the upper troposphere – lower stratosphere (UTLS region by the CARIBIC aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container have been analyzed for molecular hydrogen (H2 mixing ratios (χ(H2 and H2 isotopic composition (deuterium content, δD.

    More than 120 of the analyzed samples contained air from the lowermost stratosphere (LMS. These show that χ(H2 does not vary appreciably with O3-derived height above the thermal tropopause (TP, whereas δD does increase with height. The isotope enrichment is caused by H2 production and destruction processes that enrich the stratospheric H2 reservoir in deuterium (D; the exact shapes of the profiles are mainly determined by mixing of stratospheric with tropospheric air. Tight negative correlations are found between δD and the mixing ratios of methane (χ(CH4 and nitrous oxide (χ(N2O, as a result of the relatively long lifetimes of these three species. The correlations are described by δD[‰]=−0.35 · χ(CH4[ppb]+768 and δD[‰]=−1.90· χ(N2O[ppb]+745. These correlations are similar to previously published results and likely hold globally for the LMS.

    Samples that were collected from the Indian subcontinent up to 40° N before, during and after the summer monsoon season show no significant seasonal change in χ(H2, but δD is up to 12.3‰ lower in the July, August and September monsoon samples. This δD decrease is correlated with the χ(CH4 increase in these samples. The significant correlation with χ(CH4 and the absence of a perceptible χ(H2 increase that accompanies the δD decrease indicates that microbial production of

  12. Feeding strategies for groundwater enhanced biodenitrification in an alluvial aquifer: Chemical, microbial and isotope assessment of a 1D flow-through experiment

    Energy Technology Data Exchange (ETDEWEB)

    Vidal-Gavilan, G., E-mail: georginavidal@biorem.cat [D D' ENGINY BIOREM S.L., Madrazo 68, bxs., 08006 Barcelona (Spain); Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits MInerals, Universitat de Barcelona, Martí i Franquès s/n, 08028 Barcelona (Spain); Carrey, R., E-mail: rcarrey@ub.edu [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits MInerals, Universitat de Barcelona, Martí i Franquès s/n, 08028 Barcelona (Spain); Solanas, A., E-mail: asolanas@ub.edu [Departament de Microbiologia, Facultat de Biologia, Universitat de Barcelona, Avgda. Diagonal 645, 08028 Barcelona (Spain); Soler, A., E-mail: albertsolergil@ub.edu [Grup de Mineralogia Aplicada i Medi Ambient, Departament de Cristallografia, Mineralogia i Dipòsits MInerals, Universitat de Barcelona, Martí i Franquès s/n, 08028 Barcelona (Spain)

    2014-10-01

    Nitrate-removal through enhanced in situ biodenitrification (EISB) is an existing alternative for the recovery of groundwater quality, and is often suggested for use in exploitation wells pumping at small flow-rates. Innovative approaches focus on wider-scale applications, coupling EISB with water-management practices and new monitoring tools. However, before this approach can be used, some water-quality issues such as the accumulation of denitrification intermediates and/or of reduced compounds from other anaerobic processes must be addressed. With such a goal, a flow-through experiment using 100 mg-nitrate/L groundwater was built to simulate an EISB for an alluvial aquifer. Heterotrophic denitrification was induced through the periodic addition of a C source (ethanol), with four different C addition strategies being evaluated to improve the quality of the denitrified water. Chemical, microbial and isotope analyses of the water were performed. Biodenitrification was successfully stimulated by the daily addition of ethanol, easily achieving drinking water standards for both nitrate and nitrite, and showing an expected linear trend for nitrogen and oxygen isotope fractionation, with a εN/εO value of 1.1. Nitrate reduction to ammonium was never detected. Water quality in terms of remaining C, microbial counts, and denitrification intermediates was found to vary with the experimental time, and some secondary microbial respiration processes, mainly manganese reduction, were suspected to occur. Carbon isotope composition from the remaining ethanol also changed, from an initial enrichment in {sup 13}C-ethanol compared to the value of the injected ethanol (− 30.6‰), to a later depletion, achieving δ{sup 13}C values well below the initial isotope composition (to a minimum of − 46.7‰). This depletion in the heavy C isotope follows the trend of an inverse fractionation. Overall, our results indicated that most undesired effects on water quality may be controlled

  13. Calculation of Site-specific Carbon-isotope Fractionation in Pedogenic Oxide Minerals

    Energy Technology Data Exchange (ETDEWEB)

    Rustad, James R.; Zarzycki, Piotr

    2008-07-29

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

  14. 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.

  15. Co-deposition of palladium with hydrogen isotopes

    International Nuclear Information System (INIS)

    Dash, J.; Ambadkar, A.

    2006-01-01

    Palladium was co-deposited with hydrogen isotopes on a Pd cathode. This resulted in enhanced production of excess thermal power. After electrolysis the Pd Lβ/ Lα ratio was found to be increased in characteristic X-ray spectra from localized, microscopic areas on the surface of the Pd cathode. This suggests the possibility that appreciable amounts of silver are present in these areas. (authors)

  16. Paleogene Seawater Osmium Isotope Records

    Science.gov (United States)

    Rolewicz, Z.; Thomas, D. J.; Marcantonio, F.

    2012-12-01

    Paleoceanographic reconstructions of the Late Cretaceous and early Cenozoic require enhanced geographic coverage, particularly in the Pacific, in order to better constrain meridional variations in environmental conditions. The challenge with the existing inventory of Pacific deep-sea cores is that they consist almost exclusively of pelagic clay with little existing age control. Pelagic clay sequences are useful for reconstructions of dust accumulation and water mass composition, but accurate correlation of these records to other sites requires improved age control. Recent work indicates that seawater Os isotope analyses provide useful age control for red clay sequences. The residence time of Os in seawater is relatively long compared to oceanic mixing, therefore the global seawater 187Os/188Os composition is practically homogeneous. A growing body of Late Cretaceous and Cenozoic data has constrained the evolution of the seawater Os isotopic composition and this curve is now a viable stratigraphic tool, employed in dating layers of Fe-Mn crusts (e.g., Klemm et al., 2005). Ravizza (2007) also demonstrated that the seawater Os isotopic composition can be extracted reliably from pelagic red clay sediments by analyzing the leached oxide minerals. The drawback to using seawater Os isotope stratigraphy to date Paleogene age sediments is that the compilation of existing data has some significant temporal gaps, notably between ~38 and 55 Ma. To improve the temporal resolution of the seawater Os isotope curve, we present new data from Ocean Drilling Program (ODP) Site 865 in the equatorial Pacific. Site 865 has excellent biostratigraphic age control over the interval ~38-55Ma. Preliminary data indicate an increase in the seawater composition from 0.427 at 53.4 Ma to 0.499 by 43 Ma, consistent with the apparent trend in the few existing data points. We also analyzed the Os isotopic composition recorded by oxide minerals at Integrated Ocean Drilling Program (IODP) Site U1370

  17. Isotope separation

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1979-01-01

    A method of isotope separation is described which involves the use of a laser photon beam to selectively induce energy level transitions of an isotope molecule containing the isotope to be separated. The use of the technique for 235 U enrichment is demonstrated. (UK)

  18. Present and prospective situation in laser isotope separation: will the free electron laser be needed

    International Nuclear Information System (INIS)

    Rigny, P.

    1984-09-01

    The need for enriched isotopes, as it appears to day will be recalled for the foreseeable future, this need, in quantitative terms, will be confined to isotopes for nuclear energy. The interest of laser isotope separation will finally depend on our ability to fulfil a number of requirements as to the laser output light characteristics. These will be recalled for the most common laser processes (molecular photodissociation and atomic photoionisation). At this point a comparison with expectations from the FEL can already be attempted. Less common laser isotope separation schemes can gain interest from the possibilities opened by the FEL, especially by access to new wavelengths ranges. Some schemes implying UV or VUV photons will be discussed, as well as some possibilities involving IR photons. Attention will be paid to the problems that arise when considering scaled-up isotope separation installations. A large scale process results in more constraints on the laser parameters. Estimation of FEL capacity in this respect will be attempted

  19. 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)

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

    Directory of Open Access Journals (Sweden)

    Qingcai Xu

    2015-01-01

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

  1. Atlas cross section for scattering of muonic hydrogen atoms on hydrogen isotope molecules

    International Nuclear Information System (INIS)

    Adamczak, A.; Faifman, M.P.; Ponomarev, L.I.

    1996-01-01

    The total cross sections of the elastic, spin-flip, and charge-exchange processes for the scattering of muonic hydrogen isotope atoms (pμ, dμ, tμ) in the ground state on the hydrogen isotope molecules (H 2 , D 2 , T 2 , HD, HT, DT) are calculated. The scattering cross sections of muonic hydrogen isotope atoms on hydrogen isotope nuclei obtained earlier in the multichannel adiabatic approach are used in the calculations. Molecular effects (electron screening, rotational and vibrational excitations of target molecules, etc.) are taken into account. The spin effects of the target molecules and of the incident muonic atoms are included. the cross sections are averaged over the Boltzmann distribution of the molecule rotational states and the Maxwellian distribution of the target molecule kinetic energies for temperatures 30, 100, 300, and 1000 K. The cross sections are given for kinetic energies of the incident muonic atoms ranging from 0.001 to 100 eV in the laboratory frame. 45 refs., 6 tabs

  2. Revised models of interstellar nitrogen isotopic fractionation

    Science.gov (United States)

    Wirström, E. S.; Charnley, S. B.

    2018-03-01

    Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of 15N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised 15N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirström et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included 15N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing 15N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching 14N/15N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the 14N/15N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk 15N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

  3. Metal nanostructures for the enhancement of the Raman response of molecular adsorbates

    Science.gov (United States)

    Giorgetti, Emilia; Giammanco, Francesco; Margheri, Giancarlo; Trigari, Silvana; Muniz-Miranda, Maurizio

    2011-08-01

    Spectroscopic investigation of metallic nanostructures of different size and morphology is presented, with particular focus on the capability of enhancing the Raman response of molecular adsorbates, namely on their SERS properties. In this framework, we describe recent results obtained with Au/Ag nanocages and Au nanostars, which can be used conveniently to shift the extinction spectra and the SERS activity up to the near infrared. In the case of nanostars, we present a synthesis procedure which permits fine tuning of their morphology and extinction, thus allowing preparation of structures with controlled SERS activity from 500 up to 1500 nm.

  4. Isotope ratio monitoring LC/MS (IRM-LC/MS): new applications

    International Nuclear Information System (INIS)

    Juchelka, D; Hilkert, A.; Krummen, M.

    2005-01-01

    With the introduction of compound specific isotope analysis by isotope ratio monitoring GC/ MS (IRM-GC/MS) the immediate demand for similar applications using HPLC was created. Many compounds of biological, medical, pharmaceutical and environmental interest are not volatile or too polar. Consequently, they cannot be directly analyzed by gas chromatography. In IRM-GC/MS the carrier is helium, which does not interfere with the essential combust ion step prior to isotope ratio mass spectrometry (IRMS). In opposite the LC mobile phase has inhibited a similar direct conversion up to now. All earlier IRM-LC/MS approaches were based on the removal of the liquid phase prior to combustion risking fractionation of the isotope ratios of the eluted compounds. To avoid such restrictions we developed a new continuous flow concept for the coupling of an HPLC system to the isotope ratio MS for 13 C/ 12C isotope ratio analysis. In the Finnigan LC IsoLink, the liquid phase is not removed from the sample prior to oxidation. The sample is oxidized still in the mobile phase followed by on-line separation of the CO 2 from the liquid phase and transfer into the isotope ratio MS. Therefore, this strategy is based on water and inorganic buffers as mobile phase. The new approach opens up a whole new world in the application of gas isotope ratio mass spectrometry. The 13 C/ 12 C ratio s of organic acids, amino acids, carbohydrates and nucleotides can now be measured. These components typically within a complex matrix are separated by liquid chromatography followed by on-line determination of the isotope ratios. The draw backs of using derivatization and off-line preparation procedures can now be over come. This new technique allow s studying biochemical cycles, running tracer experiments and determining the origin of components. Applications from different scientific areas such as biogeochemistry, molecular biology, and pharmacy as well as authenticity control o f foods will be presented

  5. Characterization of phenols biodegradation by compound specific stable isotope analysis

    Science.gov (United States)

    Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

    2015-04-01

    Biodegradation of phenol and alkylphenols has been described under both oxic and anoxic conditions. In the absence of molecular oxygen, the degradation of phenolic compounds is initiated by microorganisms through carboxylation, fumarate addition to the methyl moiety or anoxic hydroxylation of the methyl moiety. Comparatively, under aerobic condition, the initiation mechanisms are revealed to be monoxygenation or dihydroxylation for phenol and ring hydroxylation or methyl group oxidation for cresols. While several studies biochemically characterized the enzymes and reaction mechanisms in the relevant degradation pathways, isotope fractionation patterns were rarely reported possibly due to constraints in current analytical methods. In this study, the carbon isotope fractionation patterns upon the degradation of phenol and cresols by several strains were analyzed by using isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). The corresponding enrichment factors for carbon (ƐC) have been obtained. Cresols degradation by various strains showed generally moderate carbon isotope fractionation patterns with notable differences. For p-cresol degradation, five strains were examined. The aerobic strain Acinetobacter calcoaceticus NCIMB8250 exploits ring hydroxylation by molecular oxygen as initial reaction, and a ƐC value of -1.4±0.2‰ was obtained. Pseudomonas pseudoalcaligenes NCIMB 9867, an aerobic strain initiating cresols degradation via oxygen-dependent side chain hydroxylation, yielded a ƐC value of -2.3±0.2‰. Under nitrate-reducing conditions, Geobacter metallireducens DSM 7210 and Azoarcus buckelii DSM 14744 attacks p-cresol at the side chain by monohydroxylation using water as oxygen source; the two strains produced ƐC values of -3.6±0.4‰ and -2±0.1‰, accordingly. The sulfate-reducing Desulfosarcina cetonica DSM 7267 activating cresols by fumarate addition to the methyl moiety yielded ƐC values of -1.9±0.2‰ for p

  6. Isotopic evidence for primordial molecular cloud material in metal-rich carbonaceous chondrites

    DEFF Research Database (Denmark)

    van Kooten, Elishevah M. M. E.; Wielandt, Daniel Kim Peel; Schiller, Martin

    2016-01-01

    product of (26)Al. This correlation is interpreted as reflecting progressive thermal processing of in-falling (26)Al-rich molecular cloud material in the inner Solar System. The thermally unprocessed molecular cloud matter reflecting the nucleosynthetic makeup of the molecular cloud before the last......)Mg*-depleted and (54)Cr-enriched component. This composition is consistent with that expected for thermally unprocessed primordial molecular cloud material before its pollution by stellar-derived (26)Al. The (26)Mg* and (54)Cr compositions of bulk metal-rich chondrites require significant amounts (25......-50%) of primordial molecular cloud matter in their precursor material. Given that such high fractions of primordial molecular cloud material are expected to survive only in the outer Solar System, we infer that, similarly to cometary bodies, metal-rich carbonaceous chondrites are samples of planetesimals...

  7. DNP-enhanced solid-state NMR spectroscopy of active pharmaceutical ingredients.

    Science.gov (United States)

    Zhao, Li; Pinon, Arthur C; Emsley, Lyndon; Rossini, Aaron J

    2017-11-28

    Solid-state NMR spectroscopy has become a valuable tool for the characterization of both pure and formulated active pharmaceutical ingredients (APIs). However, NMR generally suffers from poor sensitivity that often restricts NMR experiments to nuclei with favorable properties, concentrated samples, and acquisition of one-dimensional (1D) NMR spectra. Here, we review how dynamic nuclear polarization (DNP) can be applied to routinely enhance the sensitivity of solid-state NMR experiments by one to two orders of magnitude for both pure and formulated APIs. Sample preparation protocols for relayed DNP experiments and experiments on directly doped APIs are detailed. Numerical spin diffusion models illustrate the dependence of relayed DNP enhancements on the relaxation properties and particle size of the solids and can be used for particle size determination when the other factors are known. We then describe the advanced solid-state NMR experiments that have been enabled by DNP and how they provide unique insight into the molecular and macroscopic structure of APIs. For example, with large sensitivity gains provided by DNP, natural isotopic abundance, 13 C- 13 C double-quantum single-quantum homonuclear correlation NMR spectra of pure APIs can be routinely acquired. DNP also enables solid-state NMR experiments with unreceptive quadrupolar nuclei such as 2 H, 14 N, and 35 Cl that are commonly found in APIs. Applications of DNP-enhanced solid-state NMR spectroscopy for the molecular level characterization of low API load formulations such as commercial tablets and amorphous solid dispersions are described. Future perspectives for DNP-enhanced solid-state NMR experiments on APIs are briefly discussed. Copyright © 2017 John Wiley & Sons, Ltd.

  8. Enhanced mechanical properties of graphene/copper nanocomposites using a molecular-level mixing process.

    Science.gov (United States)

    Hwang, Jaewon; Yoon, Taeshik; Jin, Sung Hwan; Lee, Jinsup; Kim, Taek-Soo; Hong, Soon Hyung; Jeon, Seokwoo

    2013-12-10

    RGO flakes are homogeneously dispersed in a Cu matrix through a molecular-level mixing process. This novel fabrication process prevents the agglomeration of the RGO and enhances adhesion between the RGO and the Cu. The yield strength of the 2.5 vol% RGO/Cu nanocomposite is 1.8 times higher than that of pure Cu. The strengthening mechanism of the RGO is investigated by a double cantilever beam test using the graphene/Cu model structure. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Application of heavy stable isotopes in forensic isotope geochemistry: A review

    International Nuclear Information System (INIS)

    Aggarwal, Jugdeep; Habicht-Mauche, Judith; Juarez, Chelsey

    2008-01-01

    Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers

  10. Application of heavy stable isotopes in forensic isotope geochemistry: A review

    Energy Technology Data Exchange (ETDEWEB)

    Aggarwal, Jugdeep [W.M. Keck Isotope Laboratory, Department of Earth Sciences, University of California, Santa Cruz, CA 95064 (United States)], E-mail: jaggarwal@pmc.ucsc.edu; Habicht-Mauche, Judith; Juarez, Chelsey [Department of Anthropology, University of California, Santa Cruz, CA 95064 (United States)

    2008-09-15

    Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers.

  11. Ejection dynamics of hydrogen molecular ions from methanol in intense laser fields

    International Nuclear Information System (INIS)

    Okino, T; Furukawa, Y; Liu, P; Ichikawa, T; Itakura, R; Hoshina, K; Yamanouchi, K; Nakano, H

    2006-01-01

    The ejection of hydrogen molecular ions from two-body Coulomb explosion processes of methanol (CH 3 OH, CD 3 OH and CH 3 OD) in an intense laser field (800 nm, 60 fs, 0.2 PW cm -2 ) is investigated by a coincidence momentum imaging method. From the coincidence momentum maps, the ejection processes of hydrogen molecular ions, CH 3 OH 2+ → H m + + CH (3-m) OH + (m = 2, 3), CD 3 OH 2+ → D m + + CH (3-m) OH + (m = 2, 3) and CH 3 OD 2+ → H m + + CH (3-m) OD + (m = 2, 3), are identified. Based on the results obtained with isotopically substituted methanol, the isotope effect on the ejection process of hydrogen molecular ions is discussed. Furthermore, the ejection of H/D exchanged hydrogen molecular ions (HD + , HD 2 + and H 2 D + ) is identified, and the timescales for the H/D exchanging processes are estimated from the extent of anisotropy in the ejection directions

  12. The enhanced spin-polarized transport behaviors through cobalt benzene-porphyrin-benzene molecular junctions: the effect of functional groups

    Science.gov (United States)

    Cheng, Jue-Fei; Zhou, Liping; Wen, Zhongqian; Yan, Qiang; Han, Qin; Gao, Lei

    2017-05-01

    The modification effects of the groups amino (NH2) and nitro (NO2) on the spin polarized transport properties of the cobalt benzene-porphyrin-benzene (Co-BPB) molecule coupled to gold (Au) nanowire electrodes are investigated by the nonequilibrium Green’s function method combined with the density functional theory. The calculation results show that functional groups can lead to the significant spin-filter effect, enhanced low-bias negative differential resistance (NDR) behavior and novel reverse rectifying effect in Co-BPB molecular junction. The locations and types of functional groups have distinct influences on spin-polarized transport performances. The configuration with NH2 group substituting H atom in central porphyrin ring has larger spin-down current compared to that with NO2 substitution. And Co-BPB molecule junction with NH2 group substituting H atom in side benzene ring shows reverse rectifying effect. Detailed analyses confirm that NH2 and NO2 group substitution change the spin-polarized transferred charge, which makes the highest occupied molecular orbitals (HOMO) of spin-down channel of Co-BPB closer to the Fermi level. And the shift of HOMO strengthens the spin-polarized coupling between the molecular orbitals and the electrodes, leading to the enhanced spin-polarized behavior. Our findings might be useful in the design of multi-functional molecular devices in the future.

  13. Stable isotope studies. Annual progress report, March 1, 1981-February 28, 1982

    International Nuclear Information System (INIS)

    Ishida, T.

    1981-01-01

    Our studies during the year consisted of cryogenic measurements of vapor pressure isotope effects (VPIE) in CHF 3 , CH 2 F 2 , CH 3 F, and ammonia, interpretations of the results of the VPIE studies of CHF 3 and CH 3 F by means of ab initio molecular orbital calculations and vibrational analyses, studies of nitrogen isotope fractionation by an exchange between nitric oxide and the liquid phase consisting of N 2 O 3 and N 2 O 4 under elevated pressures, an exploration of the concept of closed refluxer system for the Nitrox process for separating 15 N using a Fe(II)/Fe(III) system as reducing agent for nitric acid and the electrolysis for regeneration of Fe(II), and a theoretical study of approximation of the zero-point energy and its isotopic differences developed on the basis of Lanczos' tau-method

  14. Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

    Science.gov (United States)

    Muhammad, Syahidah; Frew, Russell; Hayman, Alan

    2015-02-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

  15. Compound-Specific Isotope Analysis of Diesel Fuels in a Forensic Investigation

    Directory of Open Access Journals (Sweden)

    Syahidah Akmal Muhammad

    2015-02-01

    Full Text Available Compound-specific isotope analysis (CSIA offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ13C and δ2H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin i.e. the very subtle differences in isotopic values between the samples.

  16. Compound-specific isotope analysis of diesel fuels in a forensic investigation.

    Science.gov (United States)

    Muhammad, Syahidah A; Frew, Russell D; Hayman, Alan R

    2015-01-01

    Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ(13)C and δ(2)H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples.

  17. Preliminary review on isotope separation of long life fission products. Application research of laser isotope separation to 135Cs

    International Nuclear Information System (INIS)

    Oshita, Hironori; Ozawa, Masaki; Ishikawa, Makoto; Koyama, Shin'ichi; Akatsuka, Hiroshi

    2007-09-01

    , charge transference, neighboring transition and Doppler effect, 4) the optimization of laser irradiation condition (the degree of vacuum and the temperature), 5) the hyperfine structure of cesium and its relation to selective excitation of 135 Cs, 6) confirmation of the feasibility of selective excitation of 135 Cs and its chemical collection (the hydride formation and its reaction velocity). Hereafter we will research and evaluate the subjects mentioned above and confirming the feasibility of isotope separation of 135 Cs by experiment. LIS can be roughly classified into two ways according to the sample form; atomic laser method and molecular laser method. It is atomic laser method that is in main progress; therefore this document mainly reports the former. (author)

  18. Cryogenic adsorption of low-concentration hydrogen on charcoal, 5A molecular sieve, sodalite, ZSM-5 and Wessalith DAY

    International Nuclear Information System (INIS)

    Willms, R.S.

    1993-01-01

    The separation of low-concentration hydrogen isotopes from helium is a processing step that is required for ceramic lithium breeding blanket processing. Cryogenic adsorption is one method of effecting this separation. In this study live adsorbents were considered for this purpose: charcoal, 5A molecular sieve, UOP S-115, ZSM-5 and Wessalith DAY. The first two adsorbents exhibit good equilibrium loadings and are shown to be quite effective at adsorbing low-concentration hydrogen isotopes. The latter three adsorbents display considerably lower equilibrium loadings. This study concludes that by using either charcoal or 5A molecular sieve, cryogenic adsorption would be an effective means of separating hydrogen isotopes from helium

  19. Process and system for isotope separation using the selective vibrational excitation of molecules

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Keck, J.C.

    1976-01-01

    This invention concerns the separation of isotopes by using the isotopically selective vibrational excitation and the vibration-translation reactions of the excited particles. UF 6 molecular mixed with a carrier gas, such as argon, are directed through a refrigerated chamber lighted by a laser radiation tuned to excite vibrationally the uranium hexafluoride molecules of a particular uranium isotope. The density of the carrier gas is preferably maintained above the density of the uranium hexafluoride to allow a greater collision probability of the vibrationally excited molecules with a carried molecule. In such a case, the vibrationally excited uranium hexafluoride will collide with a carrier gas molecule provoking the conversion of the excitation energy into a translation of the excited molecule, resulting in thermal energy or greater diffusibility than that of the other uranium hexafluoride molecules [fr

  20. The future of producing separated stable isotopes at Oak Ridge National Laboratory for accelerator applications

    International Nuclear Information System (INIS)

    Collins, E.D.

    1994-01-01

    Separated stable isotopes, produced in the calutrons at Oak Ridge National Laboratory, are essential target materials for production of numerous radioisotopes in accelerators and reactors. Recently, separated stable isotope production has been curtailed because government appropriations were discontinued and salts revenues decreased. The calutrons were placed in standby and the operating staff reduced to enable support by sales from existing inventories. Appeals were made to industry and government to preserve this national capability. Methods for providing volume-based price reductions were created to attract support from commercial isotope users. In 1994, the Department of Energy's Isotope Production and Distribution Program was restructured and a strategy produced to seek appropriated funding for the future production of rare, nonprofitable isotopes for research uses. This strategy, together with new demands for medical isotopes, will enable future operation of the calutrons. Moreover, production may be enhanced by complementing calutron capabilities with the Plasma Separation Process

  1. Predictions and Verification of an Isotope Marine Boundary Layer Model

    Science.gov (United States)

    Feng, X.; Posmentier, E. S.; Sonder, L. J.; Fan, N.

    2017-12-01

    A one-dimensional (1D), steady state isotope marine boundary layer (IMBL) model is constructed. The model includes meteorologically important features absent in Craig and Gordon type models, namely height-dependent diffusion/mixing and convergence of subsiding external air. Kinetic isotopic fractionation results from this height-dependent diffusion which starts as pure molecular diffusion at the air-water interface and increases linearly with height due to turbulent mixing. The convergence permits dry, isotopically depleted air subsiding adjacent to the model column to mix into ambient air. In δD-δ18O space, the model results fill a quadrilateral, of which three sides represent 1) vapor in equilibrium with various sea surface temperatures (SSTs) (high d18O boundary of quadrilateral); 2) mixture of vapor in equilibrium with seawater and vapor in the subsiding air (lower boundary depleted in both D and 18O); and 3) vapor that has experienced the maximum possible kinetic fractionation (high δD upper boundary). The results can be plotted in d-excess vs. δ18O space, indicating that these processes all cause variations in d-excess of MBL vapor. In particular, due to relatively high d-excess in the descending air, mixing of this air into the MBL causes an increase in d-excess, even without kinetic isotope fractionation. The model is tested by comparison with seven datasets of marine vapor isotopic ratios, with excellent correspondence; >95% of observational data fall within the quadrilateral area predicted by the model. The distribution of observations also highlights the significant influence of vapor from the nearby converging descending air on isotopic variations in the MBL. At least three factors may explain the affect the isotopic composition of precipitation. The model can be applied to modern as well as paleo- climate conditions.

  2. Raman scattering method and apparatus for measuring isotope ratios and isotopic abundances

    International Nuclear Information System (INIS)

    Harney, R.C.; Bloom, S.D.

    1978-01-01

    Raman scattering is used to measure isotope ratios and/or isotopic abundances. A beam of quasi-monochromatic photons is directed onto the sample to be analyzed, and the resulting Raman-scattered photons are detected and counted for each isotopic species of interest. These photon counts are treated mathematically to yield the desired isotope ratios or isotopic abundances

  3. 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

  4. Isotope separations using chromatographic methods

    International Nuclear Information System (INIS)

    Leseticky, L.

    1985-01-01

    A survey is given of chromatographic separations of compounds only differing in isotope composition. Isotope effects on physical properties which allow chromatographic separation (vapour tension, adsorption heat, partition coefficient) are very small, with the exception of the simplest molecules. Therefore, separation factors only assume the value of several per cent. From this ensues the necessity of using columns which are specially and very carefully prepared and have a separation efficiency of the order of 10 4 theoretical plates. Briefly discussed is liquid chromatography on ion exchangers which with a varied degree of success was used for separating simple inorganic compounds or ions. Ion exchange chromatography of amino acids labelled with tritium, and chromatography of tritium labelled steroids also provided only a certain degree of separation. A detailed analysis is presented of gas chromatography separation of various deuterium and tritium labelled low-molecular compounds, to which a number of studies has been devoted in the literature. Very promising is the method of complexation gas chromatography based on the reversible formation of a complex of the ligand (the compound being separated) and the compound of the (transition) metal as the steady-state phase. (author)

  5. Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

    Science.gov (United States)

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

    2010-01-01

    We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

  6. Isotope separation

    International Nuclear Information System (INIS)

    Bartlett, R.J.; Morrey, J.R.

    1978-01-01

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

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

    Science.gov (United States)

    Jin, Biao; Rolle, Massimo

    2016-04-01

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

  8. Hg stable isotope analysis by the double-spike method.

    Science.gov (United States)

    Mead, Chris; Johnson, Thomas M

    2010-06-01

    Recent publications suggest great potential for analysis of Hg stable isotope abundances to elucidate sources and/or chemical processes that control the environmental impact of mercury. We have developed a new MC-ICP-MS method for analysis of mercury isotope ratios using the double-spike approach, in which a solution containing enriched (196)Hg and (204)Hg is mixed with samples and provides a means to correct for instrumental mass bias and most isotopic fractionation that may occur during sample preparation and introduction into the instrument. Large amounts of isotopic fractionation induced by sample preparation and introduction into the instrument (e.g., by batch reactors) are corrected for. This may greatly enhance various Hg pre-concentration methods by correcting for minor fractionation that may occur during preparation and removing the need to demonstrate 100% recovery. Current precision, when ratios are normalized to the daily average, is 0.06 per thousand, 0.06 per thousand, 0.05 per thousand, and 0.05 per thousand (2sigma) for (202)Hg/(198)Hg, (201)Hg/(198)Hg, (200)Hg/(198)Hg, and (199)Hg/(198)Hg, respectively. This is slightly better than previously published methods. Additionally, this precision was attained despite the presence of large amounts of other Hg isotopes (e.g., 5.0% atom percent (198)Hg) in the spike solution; substantially better precision could be achieved if purer (196)Hg were used.

  9. Isotopic separation

    International Nuclear Information System (INIS)

    Chen, C.L.

    1979-01-01

    Isotopic species in an isotopic mixture including a first species having a first isotope and a second species having a second isotope are separated by selectively exciting the first species in preference to the second species and then reacting the selectively excited first species with an additional preselected radiation, an electron or another chemical species so as to form a product having a mass different from the original species and separating the product from the balance of the mixture in a centrifugal separating device such as centrifuge or aerodynamic nozzle. In the centrifuge the isotopic mixture is passed into a rotor where it is irradiated through a window. Heavier and lighter components can be withdrawn. The irradiated mixture experiences a large centrifugal force and is separated in a deflection area into lighter and heavier components. (UK)

  10. Interference of scalp and skull with dynamic isotope studies of brain

    International Nuclear Information System (INIS)

    Oldendorf, W.H.

    1972-01-01

    The overlying scalp and skull create artifacts in external brain counting measurements in which isotope appears in these tissues. It is much less of a problem in dynamic studies since high levels of superficial isotope are not found in the first few seconds after introduction into the blood by any anatomic route. Diffusible tracers concentrate somewhat less in the scalp and skull than in the brain immediately after injection by any route. Nondiffusible tracers of low molecular weight attain a much higher concentration in the scalp than the brain only after about the first minute because of passage from plasma to scalp extracellular fluid. This equilibration does not occur in brain because of the blood-brain barrier. Scalp and skull thus create much less of a problem with brief dynamic studies than with chronic long-term studies. Some physical considerations of external collimation are discussed, and means are suggested to minimize superficial isotope contributions to brain counts. (U.S.)

  11. Enhanced production and isotope enrichment of recombinant glycoproteins produced in cultured mammalian cells

    Energy Technology Data Exchange (ETDEWEB)

    Skelton, David; Goodyear, Abbey [Florida State University, Department of Chemistry and Biochemistry (United States); Ni, DaQun; Walton, Wendy J.; Rolle, Myron; Hare, Joan T. [Florida State University, Institute of Molecular Biophysics (United States); Logan, Timothy M., E-mail: tlogan@fsu.ed [Florida State University, Department of Chemistry and Biochemistry (United States)

    2010-10-15

    NMR studies of post-translationally modified proteins are complicated by the lack of an efficient method to produce isotope enriched recombinant proteins in cultured mammalian cells. We show that reducing the glucose concentration and substituting glutamate for glutamine in serum-free medium increased cell viability while simultaneously increasing recombinant protein yield and the enrichment of non-essential amino acids compared to culture in unmodified, serum-free medium. Adding dichloroacetate, a pyruvate dehydrogenase kinase inhibitor, further improves cell viability, recombinant protein yield, and isotope enrichment. We demonstrate the method by producing partially enriched recombinant Thy1 glycoprotein from Lec1 Chinese hamster ovary (CHO) cells using U-{sup 13}C-glucose and {sup 15}N-glutamate as labeled precursors. This study suggests that uniformly {sup 15}N,{sup 13}C-labeled recombinant proteins may be produced in cultured mammalian cells starting from a mixture of labeled essential amino acids, glucose, and glutamate.

  12. Enhanced production and isotope enrichment of recombinant glycoproteins produced in cultured mammalian cells

    International Nuclear Information System (INIS)

    Skelton, David; Goodyear, Abbey; Ni, DaQun; Walton, Wendy J.; Rolle, Myron; Hare, Joan T.; Logan, Timothy M.

    2010-01-01

    NMR studies of post-translationally modified proteins are complicated by the lack of an efficient method to produce isotope enriched recombinant proteins in cultured mammalian cells. We show that reducing the glucose concentration and substituting glutamate for glutamine in serum-free medium increased cell viability while simultaneously increasing recombinant protein yield and the enrichment of non-essential amino acids compared to culture in unmodified, serum-free medium. Adding dichloroacetate, a pyruvate dehydrogenase kinase inhibitor, further improves cell viability, recombinant protein yield, and isotope enrichment. We demonstrate the method by producing partially enriched recombinant Thy1 glycoprotein from Lec1 Chinese hamster ovary (CHO) cells using U- 13 C-glucose and 15 N-glutamate as labeled precursors. This study suggests that uniformly 15 N, 13 C-labeled recombinant proteins may be produced in cultured mammalian cells starting from a mixture of labeled essential amino acids, glucose, and glutamate.

  13. Quantifying mercury isotope dynamics in captive Pacific bluefin tuna (Thunnus orientalis

    Directory of Open Access Journals (Sweden)

    Sae Yun Kwon

    2016-02-01

    Full Text Available Abstract Analyses of mercury (Hg isotope ratios in fish tissues are used increasingly to infer sources and biogeochemical processes of Hg in natural aquatic ecosystems. Controlled experiments that can couple internal Hg isotope behavior with traditional isotope tracers (δ13C, δ15N can improve the applicability of Hg isotopes as natural ecological tracers. In this study, we investigated changes in Hg isotope ratios (δ202Hg, Δ199Hg during bioaccumulation of natural diets in the pelagic Pacific bluefin tuna (Thunnus orientalis; PBFT. Juvenile PBFT were fed a mixture of natural prey and a dietary supplement (60% Loligo opalescens, 31% Sardinops sagax, 9% gel supplement in captivity for 2914 days, and white muscle tissues were analyzed for Hg isotope ratios and compared to time in captivity and internal turnover of δ13C and δ15N. PBFT muscle tissues equilibrated to Hg isotope ratios of the dietary mixture within ∼700 days, after which we observed a cessation in further shifts in Δ199Hg, and small but significant negative δ202Hg shifts from the dietary mixture. The internal behavior of Δ199Hg is consistent with previous fish studies, which showed an absence of Δ199Hg fractionation during Hg bioaccumulation. The negative δ202Hg shifts can be attributed to either preferential excretion of Hg with higher δ202Hg values or individual variability in captive PBFT feeding preferences and/or consumption rates. The overall internal behavior of Hg isotopes is similar to that described for δ13C and δ15N, though observed Hg turnover was slower compared to carbon and nitrogen. This improved understanding of internal dynamics of Hg isotopes in relation to δ13C and δ15N enhances the applicability of Hg isotope ratios in fish tissues for tracing Hg sources in natural ecosystems.

  14. Global transcriptomic profiling of aspen trees under elevated [CO2] to identify potential molecular mechanisms responsible for enhanced radial growth.

    Science.gov (United States)

    Wei, Hairong; Gou, Jiqing; Yordanov, Yordan; Zhang, Huaxin; Thakur, Ramesh; Jones, Wendy; Burton, Andrew

    2013-03-01

    Aspen (Populus tremuloides) trees growing under elevated [CO(2)] at a free-air CO(2) enrichment (FACE) site produced significantly more biomass than control trees. We investigated the molecular mechanisms underlying the observed increase in biomass by producing transcriptomic profiles of the vascular cambium zone (VCZ) and leaves, and then performed a comparative study to identify significantly changed genes and pathways after 12 years exposure to elevated [CO(2)]. In leaves, elevated [CO(2)] enhanced expression of genes related to Calvin cycle activity and linked pathways. In the VCZ, the pathways involved in cell growth, cell division, hormone metabolism, and secondary cell wall formation were altered while auxin conjugation, ABA synthesis, and cytokinin glucosylation and degradation were inhibited. Similarly, the genes involved in hemicellulose and pectin biosynthesis were enhanced, but some genes that catalyze important steps in lignin biosynthesis pathway were inhibited. Evidence from systemic analysis supported the functioning of multiple molecular mechanisms that underpin the enhanced radial growth in response to elevated [CO(2)].

  15. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    the δ53Cr value of continental runoff into the ocean. The major findings were that river water is characterised by heavy δ53Cr values (+0.1‰ to +1.6‰), while soils are characterised by light δ53Cr values (-0.3‰), relative to the catchment bedrock (-0.17‰ to -0.21‰), indicating that Cr isotopes......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify......Chromium (Cr) stable isotopes are a useful tracer of changes in redox conditions because changes in its oxidation state are accompanied by an isotopic fractionation. For this reason the Cr isotope system is being developed as a potential tool for paleo-redox reconstruction. Dissolved Cr in seawater...

  16. Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

    Science.gov (United States)

    Pahlevan, K.; Karato, S. I.

    2016-12-01

    Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial

  17. Understanding H isotope adsorption and absorption of Al-alloys using modeling and experiments (LDRD: #165724)

    Energy Technology Data Exchange (ETDEWEB)

    Ward, Donald K. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Zhou, Xiaowang [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Karnesky, Richard A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Kolasinski, Robert [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Thurmer, Konrad [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Chao, Paul [Carnegie Mellon University, Pittsburgh, PA (United States); Epperly, Ethan Nicholas [Livermore Valley Charter Preparatory High School, Livermore, CA (United States); Zimmerman, Jonathan A. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States); Wong, Bryan M. [Univ. of California, Riverside, CA (United States); Sills, Ryan B. [Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

    2015-09-01

    Current austenitic stainless steel storage reservoirs for hydrogen isotopes (e.g. deuterium and tritium) have performance and operational life-limiting interactions (e.g. embrittlement) with H-isotopes. Aluminum alloys (e.g.AA2219), alternatively, have very low H-isotope solubilities, suggesting high resistance towards aging vulnerabilities. This report summarizes the work performed during the life of the Lab Directed Research and Development in the Nuclear Weapons investment area (165724), and provides invaluable modeling and experimental insights into the interactions of H isotopes with surfaces and bulk AlCu-alloys. The modeling work establishes and builds a multi-scale framework which includes: a density functional theory informed bond-order potential for classical molecular dynamics (MD), and subsequent use of MD simulations to inform defect level dislocation dynamics models. Furthermore, low energy ion scattering and thermal desorption spectroscopy experiments are performed to validate these models and add greater physical understanding to them.

  18. Environmental isotope hydrology

    International Nuclear Information System (INIS)

    1973-01-01

    Environmental isotope hydrology is a relatively new field of investigation based on isotopic variations observed in natural waters. These isotopic characteristics have been established over a broad space and time scale. They cannot be controlled by man, but can be observed and interpreted to gain valuable regional information on the origin, turnover and transit time of water in the system which often cannot be obtained by other techniques. The cost of such investigations is usually relatively small in comparison with the cost of classical hydrological studies. The main environmental isotopes of hydrological interest are the stable isotopes deuterium (hydrogen-2), carbon-13, oxygen-18, and the radioactive isotopes tritium (hydrogen-3) and carbon-14. Isotopes of hydrogen and oxygen are ideal geochemical tracers of water because their concentrations are usually not subject to change by interaction with the aquifer material. On the other hand, carbon compounds in groundwater may interact with the aquifer material, complicating the interpretation of carbon-14 data. A few other environmental isotopes such as 32 Si and 238 U/ 234 U have been proposed recently for hydrological purposes but their use has been quite limited until now and they will not be discussed here. (author)

  19. Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

    Science.gov (United States)

    Domagal-Goldman, S.; Kubicki, J. D.

    2006-05-01

    Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the

  20. Stable isotope tracers and exercise physiology: past, present and future.

    Science.gov (United States)

    Wilkinson, Daniel J; Brook, Matthew S; Smith, Kenneth; Atherton, Philip J

    2017-05-01

    Stable isotope tracers have been invaluable assets in physiological research for over 80 years. The application of substrate-specific stable isotope tracers has permitted exquisite insight into amino acid, fatty-acid and carbohydrate metabolic regulation (i.e. incorporation, flux, and oxidation, in a tissue-specific and whole-body fashion) in health, disease and response to acute and chronic exercise. Yet, despite many breakthroughs, there are limitations to 'substrate-specific' stable isotope tracers, which limit physiological insight, e.g. the need for intravenous infusions and restriction to short-term studies (hours) in controlled laboratory settings. In recent years significant interest has developed in alternative stable isotope tracer techniques that overcome these limitations, in particular deuterium oxide (D 2 O or heavy water). The unique properties of this tracer mean that through oral administration, the turnover and flux through a number of different substrates (muscle proteins, lipids, glucose, DNA (satellite cells)) can be monitored simultaneously and flexibly (hours/weeks/months) without the need for restrictive experimental control. This makes it uniquely suited for the study of 'real world' human exercise physiology (amongst many other applications). Moreover, using D 2 O permits evaluation of turnover of plasma and muscle proteins (e.g. dynamic proteomics) in addition to metabolomics (e.g. fluxomics) to seek molecular underpinnings, e.g. of exercise adaptation. Here, we provide insight into the role of stable isotope tracers, from substrate-specific to novel D 2 O approaches, in facilitating our understanding of metabolism. Further novel potential applications of stable isotope tracers are also discussed in the context of integration with the snowballing field of 'omic' technologies. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

  1. 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

  2. Stable isotopes

    International Nuclear Information System (INIS)

    Brazier, J.L.; Guinamant, J.L.

    1995-01-01

    According to the progress which has been realised in the technology of separating and measuring isotopes, the stable isotopes are used as preferable 'labelling elements' for big number of applications. The isotopic composition of natural products shows significant variations as a result of different reasons like the climate, the seasons, or their geographic origins. So, it was proved that the same product has a different isotopic composition of alimentary and agriculture products. It is also important in detecting the pharmacological and medical chemicals. This review article deals with the technology, like chromatography and spectrophotometry, adapted to this aim, and some important applications. 17 refs. 6 figs

  3. Nanoporous materials for hydrogen storage and H2/D2 isotope separation

    International Nuclear Information System (INIS)

    Oh, Hyunchul

    2014-01-01

    This thesis presents a study of hydrogen adsorption properties at RT with noble metal doped porous materials and an efficient separation of hydrogen isotopes with nanoporous materials. Most analysis is performed via thermal desorption spectra (TDS) and Sieverts-type apparatus. The result and discussion is presented in two parts; Chapter 4 focuses on metal doped nanoporous materials for hydrogen storage. Cryogenic hydrogen storage by physisorption on porous materials has the advantage of high reversibility and fast refuelling times with low heat evolution at modest pressures. At room temperature, however, the physisorption mechanism is not abEle to achieve enough capacity for practical application due to the weak van der Waals interaction, i.e., low isosteric heats for hydrogen sorption. Recently, the ''spillover'' effect has been proposed by R. Yang et al. to enhance the room temperature hydrogen storage capacity. However, the mechanism of this storage enhancement by decoration of noble metal particles inside high surface area supports is not yet fully understood and still under debate. In this chapter, noble metal (Pt / Pd) doped nanoporous materials (i.e. porous carbon, COFs) have been investigated for room temperature hydrogen storage. Their textural properties and hydrogen storage capacity are characterized by various analytic techniques (e.g. SEM, HRTEM, XRD, BET, ICP-OES, Thermal desorption spectra, Sievert's apparatus and Raman spectroscopy). Firstly, Pt-doped and un-doped templated carbons possessing almost identical textural properties were successfully synthesized via a single step wet impregnation method. This enables the study of Pt catalytic activities and hydrogen adsorption kinetics on porous carbons at ambient temperature by TDS after H 2 /D 2 gas exposure and PCT measurement, respectively. While the H 2 adsorption kinetics in the microporous structure is enhanced by Pt catalytic activities (spillover), only a small enhancement of the hydrogen

  4. Optical isotope shifts for unstable samarium isotopes

    International Nuclear Information System (INIS)

    Eastham, D.A.; Walker, P.M.; Griffith, J.A.R.; Evans, D.E.; Grant, I.S.; England, J.G.; Fawcett, M.J.

    1984-01-01

    Using a tunable dye laser beam intersecting a thermal atomic beam, optical isotope shifts and hyperfine splittings have been measured for the four unstable samarium isotopes between 144 Sm and 154 Sm, covering the well known transition region from spherical to deformed shapes. (orig.)

  5. Magnetically enhanced triode etching of large area silicon membranes in a molecular bromine plasma

    International Nuclear Information System (INIS)

    Wolfe, J.C.; Sen, S.; Pendharkar, S.V.; Mauger, P.; Shimkunas, A.R.

    1992-01-01

    The optimization of a process for etching 125 mm silicon membranes formed on 150 mm wafers and bonded to Pyrex rings is discussed. A magnetically enhanced triode etching system was designed to provide an intense, remote plasma surrounding the membrane while, at the same time, suppressing the discharge over the membrane itself. For the optimized molecular bromine process, the silicon etch rate is 40 nm/min and the selectivity relative to SiO 2 is 160:1. 14 refs., 6 figs

  6. Applications of Isotope Ratio Mass Spectrometry in Sports Drug Testing Accounting for Isotope Fractionation in Analysis of Biological Samples.

    Science.gov (United States)

    Piper, Thomas; Thevis, Mario

    2017-01-01

    The misuse of anabolic-androgenic steroids (AAS) in sports aiming at enhancing athletic performance has been a challenging matter for doping control laboratories for decades. While the presence of a xenobiotic AAS or its metabolite(s) in human urine immediately represents an antidoping rule violation, the detection of the misuse of endogenous steroids such as testosterone necessitates comparably complex procedures. Concentration thresholds and diagnostic analyte ratios computed from urinary steroid concentrations of, e.g., testosterone and epitestosterone have aided identifying suspicious doping control samples in the past. These ratios can however also be affected by confounding factors and are therefore not sufficient to prove illicit steroid administrations. Here, carbon and, in rare cases, hydrogen isotope ratio mass spectrometry (IRMS) has become an indispensable tool. Importantly, the isotopic signatures of pharmaceutical steroid preparations commonly differ slightly but significantly from those found with endogenously produced steroids. By comparing the isotope ratios of endogenous reference compounds like pregnanediol to that of testosterone and its metabolites, the unambiguous identification of the urinary steroids' origin is accomplished. Due to the complex urinary matrix, several steps in sample preparation are inevitable as pure analyte peaks are a prerequisite for valid IRMS determinations. The sample cleanup encompasses steps such as solid phase or liquid-liquid extraction that are presumably not accompanied by isotopic fractionation processes, as well as more critical steps like enzymatic hydrolysis, high-performance liquid chromatography fractionation, and derivatization of analytes. In order to exclude any bias of the analytical results, each step of the analytical procedure is optimized and validated to exclude, or at least result in constant, isotopic fractionation. These efforts are explained in detail. © 2017 Elsevier Inc. All rights reserved.

  7. Isotopes in the Arctic atmospheric water cycle

    Science.gov (United States)

    Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen Larsen, Hans Christian; Masson-Delmotte, Valérie

    2016-04-01

    measurements highlighted significant synoptic variations in summer in both sites. In Samoylov, the premises of a seasonal cycle have been observed during the summer-fall transition, with a fast humidity level and isotopic decrease. The latitudinal gradient is also highly visible on the Polarstern record. Complementing simulations of the water vapour isotopic composition by the ECHAM5-wiso model reproduce the Polarstern synoptic variability and spatial patterns with a good accuracy. In the near future, our records will be combined with simultaneous water isotope measurements in Iceland (by Hans Christian Steen-Larsen, CIC), Svalbard (by Valérie-Masson Delmotte, LSCE) and paired with complementing climate simulations enhanced by water isotope diagnostics. These data sets, covering an approx. 6,000 km transect of Northern Eurasia will allow for a quantitative assessment of the isotopic variations of the Arctic water cycle. The results of these analyses will also be of relevance for the interpretation of isotope signals found in ice cores and on terrestrial Arctic sites in terms of past climate change.

  8. Site-specific and multielement approach to the determination of liquid-vapor isotope fractionation parameters. The case of alcohols

    International Nuclear Information System (INIS)

    Moussa, I.; Naulet, N.; Martin, M.L.; Martin, G.J.

    1990-01-01

    Isotope fractionation phenomena occurring at the natural abundance level in the course of liquid-vapor transformation have been investigated by using the SNIF-NMR method (site-specific natural isotope fractionation studied by NMR) which has a unique capability of providing simultaneous access to fractionation parameters associated with different molecular isotopomers. This new approach has been combined with the determination of overall carbon and hydrogen fractionation effects by isotope ratio mass spectrometry (IRMS). The results of distillation and evaporation experiments of alcohols performed in technical conditions of practical interest have been analyzed according to the Rayleigh-type model. In order to check the performance of the column, unit fractionation factors were measured beforehand for water and for the hydroxylic sites of methanol and ethanol for which liquid-vapor equilibrium constants were already known. Inverse isotope effects are determined in distillation experiments for the overall carbon isotope ratio and for the site-specific hydrogen isotope ratios associated with the methyl and methylene sites of methanol and ethanol. In contrast, normal isotope effects are produced by distillation for the hydroxylic sites and by evaporation for all the isotopic ratios

  9. Electron linac for medical isotope production with improved energy efficiency and isotope recovery

    Science.gov (United States)

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

    2015-09-08

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

  10. In silico modelling of permeation enhancement potency in Caco-2 monolayers based on molecular descriptors and random forest

    DEFF Research Database (Denmark)

    Welling, Søren Havelund; Clemmensen, Line Katrine Harder; Buckley, Stephen T.

    2015-01-01

    has been developed.The random forest-QSAR model was based upon Caco-2 data for 41 surfactant-like permeation enhancers from Whitehead et al. (2008) and molecular descriptors calculated from their structure.The QSAR model was validated by two test-sets: (i) an eleven compound experimental set with Caco......-2 data and (ii) nine compounds with Caco-2 data from literature. Feature contributions, a recent developed diagnostic tool, was applied to elucidate the contribution of individual molecular descriptors to the predicted potency. Feature contributions provided easy interpretable suggestions...

  11. Correlation of zero-point energy with molecular structure and molecular forces. 3. Approximation for H/D isotope shifts and linear frequency sum rule

    International Nuclear Information System (INIS)

    Oi, T.; Ishida, T.

    1984-01-01

    The approximation methods for the zero-point energy (ZPE) previously developed using the Lanczo's tau method have been applied to the shifts in ZPE due to hydrogen isotope substitutions. Six types of approximation methods have been compared and analyzed on the basis of a weighing function Ω(lambda) varies as lambda/sup k/ and the actual eigenvalue shift spectra. The method generated by the most general optimzation treatment yields a predictable and generally satisfactory precision of the order of 1% or better. A linear frequency sum rule has been derived, which approximately holds for the sets of isotopic molecules which satisfy the second-order frequency sum rule. 19 references, 3 figures, 3 tables

  12. The National Institute of Research and Development for Isotopic and Molecular Technologies at Cluj - Napoca - Fifty Years of Experience

    International Nuclear Information System (INIS)

    Vasaru, Gh.

    2000-01-01

    The life of an institute represents knitting of tens and hundreds of threads of professional achievements, human striving, aspirations, enthusiast endeavouring sparks and often enough defeats. The history of an institute can be narrated from different angles of view but perhaps the most beautiful and correct presentation would be that the institute itself would narrate if it could be able to do that. In 1950 the Physics Division of the Institut for Physics at Bucharest - Magurele created at Cluj - Napoca a subsidiary section later operating under the aegis of Cluj - Napoca subsidiary of Romanian Academy. The research programs were mainly addressing at that time applicative items as required by the local industry. A new technology for obtaining acetylene by cracking methane under electric arc discharge was obtained and it became basic for producing row material for synthetic rubber industry. In order to perform measurements in isotope separation procedures a series of analytical methods for gas mixtures was developed as well as the analytic equipment for both laboratory and industrial uses. Starting from 1956 the Cluj - Napoca Division of the Atomic Physics Institute in Bucharest focused its research programs on stable isotope physics and chemistry. These programs aimed at solving in Romania the deuterium related problems, namely, the deuterium separation and analysis and heavy water preparation, the nuclear ingredients of major importance for CANDU type nuclear power reactors, moderated and cooled with heavy water. Initial research for deuterium analysis developed new densitometric, optical and gas-chromatographic methods. Another direction of research was the problem of light element separation. A new method based on thermal diffusion was work out and studies were conducted, relating to separation factors and equilibrium time establishing for different gaseous isotopic mixtures (H/D, 12 C / 13 C, 14 N / 15 N, 16 O / 18 O). In 1967-1968 the heavy nitrogen isotope

  13. Radiative width of molecular-cluster states

    International Nuclear Information System (INIS)

    Alhassid, Y.; Gai, M.; Bertsch, G.F.

    1982-01-01

    Molecular states are characterized by enhanced electromagnetic deexcitations of many different multipolarities. The expected enhancement of E1, E2, and E3 transitions is examined by deriving molecular sum rules for radiative deexcitation widths and via a dimensionality approach. The enhancement of the E1 transitions is the most striking

  14. Assessing diet in savanna herbivores using stable carbon isotope ratios of faeces

    Directory of Open Access Journals (Sweden)

    D. Codron

    2005-06-01

    Full Text Available In African savannas, browse-based resources (@3 plants are isotopically distinct from grasses (@4 plants. The carbon isotopic composition of the basic plant diet is recorded in animal tissues. Mammal faeces are a readily accessible, non-invasive, sample material for temporally resolved dietary reconstructions. Faeces, however, include both undigested plant matter and waste, hence accuracy of dietary calculations could potentially be compromised by shifts in plant isotopic values related to seasonal or spatial differences, or by variability in the isotopic differences between faeces and diet. A controlled feeding study of four ungulate species showed a small, consistent difference between diet and faeces of-0.9 o, irrespective of whether the diet was @3 or C4-based. Results from faeces oftaxa known to be pure grazers, pure browsers, and mixed-feeders from the Kruger National Park were entirely consistent with their diets, but the accuracy of dietary reconstructions is enhanced with data from local plant communities.

  15. Progresses in the stable isotope studies of microbial processes associated with wetland methane production

    International Nuclear Information System (INIS)

    Li Qing; Lin Guanghui

    2013-01-01

    Methane emissions from wetlands play a key role in regulating global atmospheric methane concentration, so better understanding of microbial processes for the methane emission in wetlands is critical for developing process models and reducing uncertainty in global methane emission inventory. In this review, we describe basic microbial processes for wetland methane production and then demonstrate how stable isotope fractionation and stable isotope probing can be used to investigate the mechanisms underlying different methanogenic pathways and to quantify microbial species involved in wetland methane production. When applying stable isotope technique to calculate contributions of different pathways to the total methane production in various wetlands, the technical challenge is how to determine isotopic fractionation factors for the acetate derived methane production and carbon dioxide derived methane production. Although the application of stable isotope probing techniques to study the actual functions of different microbial organisms to methane production process is significantly superior to the traditional molecular biology method, the combination of these two technologies will be crucial for direct linking of the microbial community and functional structure with the corresponding metabolic functions, and provide new ideas for future studies. (authors)

  16. 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)

  17. Structural properties of hydrogen isotopes in solid phase in the context of inertial confinement fusion

    Directory of Open Access Journals (Sweden)

    Guerrero Carlo

    2013-11-01

    Full Text Available Quality of Deuterium-Tritium capsules is a critical aspect in Inertial Confinement Fusion. In this work, we present a Quantum Molecular Dynamics methodology able to model hydrogen isotopes and their structural molecular organisation at extreme pressures and cryogenic temperatures (< 15 K. Our study sets up the basis for a future analysis on the mechanical and structural properties of DT-ice in inertial confinement fusion (ICF target manufacturing conditions.

  18. 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?

  19. 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.

  20. 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

  1. 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.

  2. Adsorption of hydrogen and deuterium on modified molecular sieves

    International Nuclear Information System (INIS)

    Li Jing; Shi Jinsong; Wu Erdong; Li Xiongwei; Peng Lixia

    2013-01-01

    The adsorption characteristics of hydrogen isotopes on 5A, ZSM-5 and their modified molecular sieves were studied at liquid nitrogen temperature with volumetric method. The effects of modification methods such as transition metal salt loading and ball milling on the adsorption behavior were discussed. It is observed that the adsorption amounts on the modified molecular sieves are reduced. but some modifications contribute to the separation between H 2 and D 2 . (authors)

  3. Isotope exchange reaction in Li2ZrO3 packed bed

    International Nuclear Information System (INIS)

    Kawamura, Y.; Enoeda, M.; Okuno, K.

    1998-01-01

    To understand the release behavior of bred tritium in a solid breeder blanket, the tritium transfer rate and tritium inventory for various mass transfer processes should be investigated. The contribution of the surface reactions (adsorption, desorption and two kinds of isotope exchange reactions) to the release process cannot be ignored. It is believed that two kinds of isotope exchange reactions (gaseous hydrogen-tritiated water and water vapor-tritiated water) occur on the surface of the solid breeder materials when hydrogen is added to the sweep gas to enhance the tritium release rate. The isotope exchange reaction study in H-D systems was carried out using a Li 2 ZrO 3 packed bed. The exchange reaction between gaseous hydrogen and water was the rate controlling step among the two kinds of exchange reactions. The reaction rate constants were quantified, and experimental equations were proposed. The equilibrium constant of the isotope exchange reaction in the H-D system was obtained from experimental data and was found to be 1.17. (orig.)

  4. Oxygen isotope partitioning between rhyolitic glass/melt and CO2: An experimental study at 550-950 degrees C and 1 bar

    International Nuclear Information System (INIS)

    Palin, J.M.; Epstein, S.; Stolper, E.M.

    1996-01-01

    Oxygen isotope partitioning between gaseous CO 2 and a natural rhyolitic glass and melt (77.7 wt% SiO 2 , 0.16 wt% H 2 O total ) has been measured at 550-950 degrees C and approximately 1 bar. Equilibrium oxygen isotope fractionation factors (α CO2-rhyolite = ( 18 O/ 16 O) rhyolite ) determined in exchange experiments of 100-255 day duration. These values agree well with predictions based on experimentally determined oxygen isotope fractionation factors for CO 2 -silica glass and CO 2 -albitic glass/melt, if the rhyolitic glass is taken to be a simple mixture of normative silica and alkali feldspar components. The results indicate that oxygen isotope partitioning in felsic glasses and melts can be modeled by linear combinations of endmember silicate constituents. Rates of oxygen isotope exchange observed in the partitioning experiments are consistent with control by diffusion of molecular H 2 O dissolved in the glass/melt and are three orders of magnitude faster than predicted for rate control solely by diffusion of dissolved molecular CO 2 under the experimental conditions. Additional experiments using untreated and dehydrated (0.09 wt% H 2 O total ) rhyolitic glass quantatively support these interpretations. We conclude that diffusive oxygen isotope exchange in rhyolitic glass/melt, and probably other polymerized silicate materials, it controlled by the concentrations and diffusivities of dissolved oxygen-bearing volatile species rather than diffusion of network oxygen under all but the most volatile-poor conditions. 25 refs., 6 figs., 1 tab

  5. Studies on separation of lithium isotopes by solvent extraction: Pt. 2

    International Nuclear Information System (INIS)

    Chen Yaohuan; Yan Jinying; Li Yongkun

    1987-01-01

    The effect of the struture of chelating agent and synergetic agent on the extraction separation of lithium isotopes by Sudan I-neutral ligand synergetic extraction systems were discussed in this paper. In order to obtain higher isotopic effect, the chelating agent must possess weaker acidity (pK a > 11), stronger intramolecular hydrogen bonding and a greater tendency to form a six-membered chelating ring. In the synergetic agent, there must be a functional group possessing strong coordination ability without steric hindrance. The separation effect (α) increased with the increase in the basicity of the coordinating group. The increase of the number of chelating rings in the extractable complex was of benefit to the enhancement of α. Further discussions are also made on the enrichment direction of extraction systems and the prospects of different systems to be used for isotope separation

  6. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

  8. Raman microspectroscopy, surface-enhanced Raman scattering microspectroscopy, and stable-isotope Raman microspectroscopy for biofilm characterization.

    Science.gov (United States)

    Ivleva, Natalia P; Kubryk, Patrick; Niessner, Reinhard

    2017-07-01

    Biofilms represent the predominant form of microbial life on our planet. These aggregates of microorganisms, which are embedded in a matrix formed by extracellular polymeric substances, may colonize nearly all interfaces. Detailed knowledge of microorganisms enclosed in biofilms as well as of the chemical composition, structure, and functions of the complex biofilm matrix and their changes at different stages of the biofilm formation and under various physical and chemical conditions is relevant in different fields. Important research topics include the development and improvement of antibiotics and medical devices and the optimization of biocides, antifouling strategies, and biological wastewater treatment. Raman microspectroscopy is a capable and nondestructive tool that can provide detailed two-dimensional and three-dimensional chemical information about biofilm constituents with the spatial resolution of an optical microscope and without interference from water. However, the sensitivity of Raman microspectroscopy is rather limited, which hampers the applicability of Raman microspectroscopy especially at low biomass concentrations. Fortunately, the resonance Raman effect as well as surface-enhanced Raman scattering can help to overcome this drawback. Furthermore, the combination of Raman microspectroscopy with other microscopic techniques, mass spectrometry techniques, or particularly with stable-isotope techniques can provide comprehensive information on monospecies and multispecies biofilms. Here, an overview of different Raman microspectroscopic techniques, including resonance Raman microspectroscopy and surface-enhanced Raman scattering microspectroscopy, for in situ detection, visualization, identification, and chemical characterization of biofilms is given, and the main feasibilities and limitations of these techniques in biofilm research are presented. Future possibilities of and challenges for Raman microspectroscopy alone and in combination with other

  9. Trapping of hydrogen isotopes in molybdenum and niobium predamaged by ion implantation

    International Nuclear Information System (INIS)

    Bottiger, J.; Picraux, S.T.; Rud, N.; Laursen, T.

    1977-01-01

    The trapping of hydrogen isotopes at defects in Mo and Nb have been studied. Ion beams of 11- and 18-keV He + , 55-keV O + and Ne + , and 500-keV Bi + were used to create defects. Subsequently H or D was injected at room temperature by use of molecular beams of 16-keV H + 2 and D + 2 . Appreciable enhancements were observed in the amount of H and D retained within the near-surface region of predamaged samples compared to samples with no prior damage. The total amount of D retained within the near-surface region was measured by means of the nuclear reaction D( 3 He,p) 4 He, and H depth profiles were measured via a resonance in the nuclear reaction 1 H( 19 F,αγ) 16 O. The H profiles correlate with the predicted predamaging ion profiles; however, appreciable tails to deeper depths for the hydrogen profiles are observed for the heavier predamaging ions. For a given predamage ion fluence, the amount of trapped deuterium increases linearly with incident deuterium fluence until a saturation in the enhancement is reached. The amount of deuterium trapped when saturation occurs increases with increasing predamage fluence. The experiments indicate that lighter ions, which create fewer primary displacements, are more effective per displacement in trapping hydrogen. An appreciable release of hydrogen is obtained upon annealing at 200 and 300 degreeC, and a preannealing experiment indicates this is due to detrapping rather than to any loss of traps. These temperatures suggest a much higher binding energy for the trapped hydrogen isotopes (approx.1.5 eV) than the available evidence gives for simple H-defect binding energies (approximately-less-than0.3 eV). The detailed trapping mechanism is not known. However, it is suggested on the basis of the high binding energies and the high concentrations of hydrogen which can be trapped that clusters of hydrogen may be formed

  10. Quality assurance programme for isotope diagnostic laboratories

    International Nuclear Information System (INIS)

    Krasznai, Istvan

    1987-01-01

    Quality assurance systems are suggested to be introduced in laboratories, in accordance with the recommendations of IAEA and WHO, taking local circumstances into consideration. It is emphasized that a quantitative enhancement of work must not endanger its quality; diagnostic information must be undistorted, reproducible, and gathered with the minimum of radiation burden. National authorities are requested to strengthen their supervision. Recommendations for quality assurance methods are given for medical isotope diagnostic laboratories. (author)

  11. 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

  12. An unusual isotope effect in a high-transition-temperature superconductor

    International Nuclear Information System (INIS)

    Gweon, G.-H.; Sasagawa, T.; Zhou, S.Y.; Graf, J.; Takagi, H.; Lee, D.-H.; Lanzara, A.

    2004-01-01

    In conventional superconductors, the electron pairing that allows superconductivity is caused by exchange of virtual phonons, which are quanta of lattice vibration. For high-transition-temperature (high-Tc) superconductors, it is far from clear that phonons are involved in the pairing at all. For example, the negligible change in Tc of optimally doped Bi2Sr2CaCu2O8 (Bi2212) upon oxygen isotope substitution (16O to 18O leads to Tc decreasing from 92 to 91 K) has often been taken to mean that phonons play an insignificant role in this material. Here we provide a detailed comparison of the electron dynamics of Bi2212 samples containing different oxygen isotopes, using angle-resolved photoemission spectroscopy. Our data show definite and strong isotope effects. Surprisingly, the effects mainly appear in broad high-energy humps, commonly referred to as ''incoherent peaks''. As a function of temperature and electron momentum, the magnitude of the isotope effect closely correlates with the superconducting gap--that is, the pair binding energy. We suggest that these results can be explained in a dynamic spin-Peierls picture, where the singlet pairing of electrons and the electron-lattice coupling mutually enhance each other

  13. Canada's ongoing role in global medical isotope supply

    International Nuclear Information System (INIS)

    Wiens, R.A.

    2014-01-01

    Canada has been a leader in the production of medical isotopes, most notably Molybednum-99 (Mo-99) and Cobalt-60 (Co-60) used for diagnosis, prevention and treatment of disease, since the inception of the technology in the 1950s. These products have become critical components of healthcare, impacting the daily lives of millions of people around the world. The technological, political, social and commercial climate for production of these isotopes has changed dramatically over the many decades since their use began. Canada's role in assuring long-term stability of supply continues to evolve, and at Nordion we are identifying ways to meet the new and significant challenges associated with these changes. As a supplier to this global industry, Canada is presented with not only high expectations, but also unique opportunities for advancement of policy, science and technology in support of the longevity of the medical isotope and gamma sterilization industries. This paper will examine the current drivers for change in the global medical isotope supply chain, provide an overview of new and enhanced technology options, and identify the steps necessary for Canada to maintain and expand its strong position in this critical industry. (author)

  14. Multiple isotopes (O, C, Li, Sr) as tracers of CO2 and brine leakage from CO2-enhanced oil recovery activities in Permian Basin, Texas, USA

    Science.gov (United States)

    Phan, T. T.; Sharma, S.; Gardiner, J. B.; Thomas, R. B.; Stuckman, M.; Spaulding, R.; Lopano, C. L.; Hakala, A.

    2017-12-01

    Potential CO2 and brine migration or leakage into shallow groundwater is a critical issue associated with CO2 injection at both enhanced oil recovery (EOR) and carbon sequestration sites. The effectiveness of multiple isotope systems (δ18OH2O, δ13C, δ7Li, 87Sr/86Sr) in monitoring CO2 and brine leakage at a CO2-EOR site located within the Permian basin (Seminole, Texas, USA) was studied. Water samples collected from an oil producing formation (San Andres), a deep groundwater formation (Santa Rosa), and a shallow groundwater aquifer (Ogallala) over a four-year period were analyzed for elemental and isotopic compositions. The absence of any change in δ18OH2O or δ13CDIC values of water in the overlying Ogallala aquifer after CO2 injection indicates that injected CO2 did not leak into this aquifer. The range of Ogallala water δ7Li (13-17‰) overlaps the San Andres water δ7Li (13-15‰) whereas 87Sr/86Sr of Ogallala (0.70792±0.00005) significantly differs from San Andres water (0.70865±0.00003). This observation demonstrates that Sr isotopes are much more sensitive than Li isotopes in tracking brine leakage into shallow groundwater at the studied site. In contrast, deep groundwater δ7Li (21-25‰) is isotopically distinct from San Andres produced water; thus, monitoring this intermitted formation water can provide an early indication of CO2 injection-induced brine migration from the underlying oil producing formation. During water alternating with gas (WAG) operations, a significant shift towards more positive δ13CDIC values was observed in the produced water from several of the San Andres formation wells. The carbon isotope trend suggests that the 13C enriched injected CO2 and formation carbonates became the primary sources of dissolved inorganic carbon in the area surrounding the injection wells. Moreover, one-way ANOVA statistical analysis shows that the differences in δ7Li (F(1,16) = 2.09, p = 0.17) and 87Sr/86Sr (F(1,18) = 4.47, p = 0.05) values of

  15. Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectrometry Modelling Under Saturated Absorption

    Science.gov (United States)

    Dupré, Patrick

    2015-06-01

    The Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectrometry (NICE-OHMS) is a modern technique renowned for its ultimate sensitivity, because it combines long equivalent absorption length provided by a high finesse cavity, and a detection theoretically limited by the sole photon-shot-noise. One fallout of the high finesse is the possibility to accumulating strong intracavity electromagnetic fields (EMF). Under this condition, molecular transitions can be easy saturated giving rise to the usual Lamb dips (or hole burning). However, the unusual shape of the basically trichromatic EMF (due to the RF lateral sidebands) induces nonlinear couplings, i.e., new crossover transitions. An analytical methodology will be presented to calculate spectra provided by NICE-OHMS experiments. It is based on the solutions of the equations of motion of an open two-blocked-level system performed in the frequency-domain (optically thin medium). Knowing the transition dipole moment, the NICE-OHMS signals (``absorption-like'' and ``dispersion-like'') can be simulated by integration over the Doppler shifts and by paying attention to the molecular Zeeman sublevels and to the EMF polarization The approach has been validated by discussion experimental data obtained on two transitions of {C2H2} in the near-infrared under moderated saturation. One of the applications of the saturated absorption is to be able to simultaneously determine the transition intensity and the density number while only one these 2 quantities can only be assessed in nonlinear absorption. J. Opt. Soc. Am. B 32, 838 (2015) Optics Express 16, 14689 (2008)

  16. Method for separating isotopes

    International Nuclear Information System (INIS)

    Schlenker, R.F.

    1978-01-01

    A vortex tube for separating isotopes is described. A gas mixture containing the isotopic molecules enters the vortex tube under pressure and is separated into a hot discharge flow stream and a cold discharge flow stream. The hot discharge is enriched in lighter isotopic molecules whereas the cold discharge flow stream is enriched in the heavier isotopic molecules. The vortex tube can be used in a single stage or multistage isotope separation apparatus

  17. Method for separating isotopes

    International Nuclear Information System (INIS)

    Jepson, B.E.

    1975-01-01

    Isotopes are separated by contacting a feed solution containing the isotopes with a cyclic polyether wherein a complex of one isotope is formed with the cyclic polyether, the cyclic polyether complex is extracted from the feed solution, and the isotope is thereafter separated from the cyclic polyether

  18. Lifetimes of organic photovoltaics: Using TOF-SIMS and 18O2 isotopic labelling to characterise chemical degradation mechanisms

    DEFF Research Database (Denmark)

    Norrman, K.; Krebs, Frederik C

    2006-01-01

    The lifetimes of organic photovoltaic cells based on conjugated polymer materials were studied. The device geometry was glass:ITO:PEDOT:PSS:C-12-PSV:C-60:aluminium. To characterise and elucidate the parts of the degradation mechanisms induced by molecular oxygen, 1802 isotopic labelling was emplo......The lifetimes of organic photovoltaic cells based on conjugated polymer materials were studied. The device geometry was glass:ITO:PEDOT:PSS:C-12-PSV:C-60:aluminium. To characterise and elucidate the parts of the degradation mechanisms induced by molecular oxygen, 1802 isotopic labelling...

  19. Recent progress of hydrogen isotope behavior studies for neutron or heavy ion damaged W

    International Nuclear Information System (INIS)

    Oya, Yasuhisa; Hatano, Yuji; Shimada, Masashi; Buchenauer, Dean; Kolasinski, Robert; Merrill, Brad; Kondo, Sosuke; Hinoki, Tatsuya; Alimov, Vladimir Kh.

    2016-01-01

    Highlights: • This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. • Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. • The distribution of defects throughout the sample also changes the shape of TDS spectrum. • Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed. - Abstract: This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. In particular, the desorption temperature shifts higher as the defect concentration increases. In addition, the distribution of defects throughout the sample also changes the shape of TDS spectrum. Even if low energy traps were distributed in the bulk region, the D diffusion toward the surface requires additional time for trapping/detrapping during surface-to-bulk transport, contributing to a shift of desorption peaks toward higher temperatures. It can be said that both of distribution of damage (e.g. hydrogen isotope trapping sites) and their stabilities would have a large impact on desorption. In addition, transmutation effects should be also considered for an actual fusion environment. Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed.

  20. Recent progress of hydrogen isotope behavior studies for neutron or heavy ion damaged W

    Energy Technology Data Exchange (ETDEWEB)

    Oya, Yasuhisa, E-mail: syoya@ipc.shizuoka.ac.jp [Shizuoka University, 836 Ohya, Suruga-ku Shizuoka 422-8529 (Japan); Hatano, Yuji [University of Toyama, 3190 Gofuku, Toyama 939-8555 (Japan); Shimada, Masashi [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Buchenauer, Dean; Kolasinski, Robert [Sandia National Laboratories, Livermore, CA 94551 (United States); Merrill, Brad [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Kondo, Sosuke; Hinoki, Tatsuya [Kyoto University, Gokasho, Uji 611-0011 (Japan); Alimov, Vladimir Kh. [University of Toyama, 3190 Gofuku, Toyama 939-8555 (Japan)

    2016-12-15

    Highlights: • This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. • Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. • The distribution of defects throughout the sample also changes the shape of TDS spectrum. • Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed. - Abstract: This paper reviews recent results pertaining to hydrogen isotope behavior in neutron and heavy ion damaged W. Accumulation of damage in W creates stable trapping sites for hydrogen isotopes, thereby changing the observed desorption behavior. In particular, the desorption temperature shifts higher as the defect concentration increases. In addition, the distribution of defects throughout the sample also changes the shape of TDS spectrum. Even if low energy traps were distributed in the bulk region, the D diffusion toward the surface requires additional time for trapping/detrapping during surface-to-bulk transport, contributing to a shift of desorption peaks toward higher temperatures. It can be said that both of distribution of damage (e.g. hydrogen isotope trapping sites) and their stabilities would have a large impact on desorption. In addition, transmutation effects should be also considered for an actual fusion environment. Experimental results show that production of Re by nuclear reaction of W with neutrons reduces the density of trapping sites, though no remarkable retention enhancement is observed.

  1. Isotopic clusters

    International Nuclear Information System (INIS)

    Geraedts, J.M.P.

    1983-01-01

    Spectra of isotopically mixed clusters (dimers of SF 6 ) are calculated as well as transition frequencies. The result leads to speculations about the suitability of the laser-cluster fragmentation process for isotope separation. (Auth.)

  2. Method for separating isotopes

    International Nuclear Information System (INIS)

    Jepson, B.E.

    1976-01-01

    The invention comprises a method for separating different isotopes of elements from each other by contacting a feed solution containing the different isotopes with a macrocyclic polyether to preferentially form a macrocyclic polyether complex with the lighter of the different isotopes. The macrocyclic polyether complex is then separated from the lighter isotope depleted feed solution. A chemical separation of isotopes is carried out in which a constant refluxing system permits a continuous countercurrent liquid-liquid extraction. (LL)

  3. SU-F-T-666: Molecular-Targeted Gold Nanorods Enhances the RBE of Proton Therapy

    Energy Technology Data Exchange (ETDEWEB)

    Khoo, A; Sahoo, N; Krishnan, S; Diagaradjane, P [UT MD Anderson Cancer Center, Houston, TX (United States)

    2016-06-15

    Purpose: In recent years, proton beam radiation therapy (PBRT) has gained significant attention in the treatment of tumors in anatomically complex locations. However, the therapeutic benefit of PBRT is limited by a relative biological effectiveness (RBE) of just 1.1. The purpose of this study is to evaluate whether this limitation can be overcome by artificially enhancing the RBE using molecular-targeted gold nanorods (GNRs). Methods: Molecular-targeting of GNRs was accomplished using Cetuximab (antibody specific to epidermal growth factor receptor that is over-expressed in tumors) conjugated GNRs (cGNRs) and their binding affinity to Head and Neck cancer cells was confirmed using dark field microscopy and Transmission Electron Microscopy (TEM). The radiosensitization potential of cGNRs when irradiated with photon (6MV) and proton (100 and 160 MeV) beams was determined using clonogenic assays. The RBE at 10% surviving fraction (RBE{sub 10}) for proton therapies at central and distal locations of SOBP was calculated with respect to 6 MV photons. IgGconjugated GNRs (iGNRs) were used as controls in all experiments. Results: cGNRs demonstrated significant radiosensitization when compared to iGNRs for 6MV photons (1.14 vs 1.04), 100 MeV protons (1.19 vs 1.04), and 160 MeV protons (1.17 vs 1.04). While RBE10 for proton beams at the center of SOBP revealed similar effects for both 100 and 160 MeV (RBE{sup 10}=1.39 vs 1.38; p>0.05), enhanced radiosensitization was observed at the distal SOBP with 100 MeV beams demonstrating greater effect than 160 MeV beams (RBE{sup 10}=1.79 vs 1.6; p<0.05). Conclusion: EGFR-targeting GNRs significantly enhance the RBE of protons well above the accepted 1.1 value. The enhanced RBE observed for lower energy protons (100 MeV) and at the distal SOBP suggests that low energy components may play a role in the observed radiosensitization effect. This strategy holds promise for clinical translation and could evolve as a paradigm-changing approach

  4. Determining CO2 storage potential during miscible CO2 enhanced oil recovery: Noble gas and stable isotope tracers

    Science.gov (United States)

    Shelton, Jenna L.; McIntosh, Jennifer C.; Hunt, Andrew; Beebe, Thomas L; Parker, Andrew D; Warwick, Peter D.; Drake, Ronald; McCray, John E.

    2016-01-01

    Rising atmospheric carbon dioxide (CO2) concentrations are fueling anthropogenic climate change. Geologic sequestration of anthropogenic CO2 in depleted oil reservoirs is one option for reducing CO2 emissions to the atmosphere while enhancing oil recovery. In order to evaluate the feasibility of using enhanced oil recovery (EOR) sites in the United States for permanent CO2 storage, an active multi-stage miscible CO2flooding project in the Permian Basin (North Ward Estes Field, near Wickett, Texas) was investigated. In addition, two major natural CO2 reservoirs in the southeastern Paradox Basin (McElmo Dome and Doe Canyon) were also investigated as they provide CO2 for EOR operations in the Permian Basin. Produced gas and water were collected from three different CO2 flooding phases (with different start dates) within the North Ward Estes Field to evaluate possible CO2 storage mechanisms and amounts of total CO2retention. McElmo Dome and Doe Canyon were sampled for produced gas to determine the noble gas and stable isotope signature of the original injected EOR gas and to confirm the source of this naturally-occurring CO2. As expected, the natural CO2produced from McElmo Dome and Doe Canyon is a mix of mantle and crustal sources. When comparing CO2 injection and production rates for the CO2 floods in the North Ward Estes Field, it appears that CO2 retention in the reservoir decreased over the course of the three injections, retaining 39%, 49% and 61% of the injected CO2 for the 2008, 2010, and 2013 projects, respectively, characteristic of maturing CO2 miscible flood projects. Noble gas isotopic composition of the injected and produced gas for the flood projects suggest no active fractionation, while δ13CCO2 values suggest no active CO2dissolution into formation water, or mineralization. CO2 volumes capable of dissolving in residual formation fluids were also estimated along with the potential to store pure-phase supercritical CO2. Using a combination

  5. Speciated Elemental and Isotopic Characterization of Atmospheric Aerosols - Recent Advances

    Science.gov (United States)

    Shafer, M.; Majestic, B.; Schauer, J.

    2007-12-01

    Detailed elemental, isotopic, and chemical speciation analysis of aerosol particulate matter (PM) can provide valuable information on PM sources, atmospheric processing, and climate forcing. Certain PM sources may best be resolved using trace metal signatures, and elemental and isotopic fingerprints can supplement and enhance molecular maker analysis of PM for source apportionment modeling. In the search for toxicologically relevant components of PM, health studies are increasingly demanding more comprehensive characterization schemes. It is also clear that total metal analysis is at best a poor surrogate for the bioavailable component, and analytical techniques that address the labile component or specific chemical species are needed. Recent sampling and analytical developments advanced by the project team have facilitated comprehensive characterization of even very small masses of atmospheric PM. Historically; this level of detail was rarely achieved due to limitations in analytical sensitivity and a lack of awareness concerning the potential for contamination. These advances have enabled the coupling of advanced chemical characterization to vital field sampling approaches that typically supply only very limited PM mass; e.g. (1) particle size-resolved sampling; (2) personal sampler collections; and (3) fine temporal scale sampling. The analytical tools that our research group is applying include: (1) sector field (high-resolution-HR) ICP-MS, (2) liquid waveguide long-path spectrophotometry (LWG-LPS), and (3) synchrotron x-ray absorption spectroscopy (sXAS). When coupled with an efficient and validated solubilization method, the HR-ICP-MS can provide quantitative elemental information on over 50 elements in microgram quantities of PM. The high mass resolution and enhanced signal-to-noise of HR-ICP-MS significantly advance data quality and quantity over that possible with traditional quadrupole ICP-MS. The LWG-LPS system enables an assessment of the soluble

  6. Isotope effects on nuclear shielding

    International Nuclear Information System (INIS)

    Hansen, P.E.

    1983-01-01

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

  7. 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

  8. Monitoring Isotopes in Rivers: Creation of the Global Network of Isotopes in Rivers (GNIR). Results of a Coordinated Research Project 2002-2006

    International Nuclear Information System (INIS)

    2012-03-01

    to contribute to the enhancement of our understanding of hydrological processes at the catchment scale. This publication presents several isotope datasets compiled for major rivers covering all continents as well as preliminary conclusions obtained from available isotope results. All isotope data compiled as part of the CRP have been included in IAEA isotope databases and are available on-line. The principal outcome of the CRP was to show the importance of maintaining and strengthening GNIR operation under the auspices of the IAEA. Additionally, isotope information collected as part of the CRP provided evidence of the importance of groundwater contribution to the baseflow of rivers. As a result, a follow-up CRP was launched by the IAEA dealing with the use of isotope and tracer tools to better characterize the magnitude and transit time of groundwater contribution to the baseflow of rivers.

  9. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

    Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

    1977-01-01

    A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

  10. Radiochemical search for neutron-rich isotopes of nielsbohrium in the (16)O + (254)Es reaction

    International Nuclear Information System (INIS)

    Schaedel, M.; Jaeger, E.; Bruechle, W.; Suemmerer, K.; Hulet, E.K.; Wild, J.F.; Lougheed, R.W.; Dougan, R.J.; Moody, K.J.

    1994-09-01

    We have used on-line gas chromatography to search for new isotopes of element 107 near the deformed sub-shell at N = 162 and Z = 108. Enhanced nuclear stability is predicted for this region. 254g Es was irradiated with 16 O at barrier energies to minimize the fusion hindrance in the entrance channel and to reduce the excitation energy of the compound nucleus to a minimum value. For half-lives between roughly two seconds and two minutes no signal for a positive identification of a new isotope of element 107 was detected. Consequently, only an upper cross-section limit of a few nanobarns was obtained. While this cross-section limit was too high to probe the influence of the predicted enhanced nuclear ground-state stability on the survival probability in the fission/evaporation competition, a very large cross-section enhancement would have been detectable. (orig.)

  11. Applications of isotopes

    International Nuclear Information System (INIS)

    Kirby-Smith, J.S.

    1976-01-01

    Current and potential applications of stable isotopes as tracers in a number of biomedical and environmental areas are discussed. It is pointed out that a wide variety of problems exist in these fields whose solutions in principle are amenable to the isotopic approach. The number and diversity of these problems as well as the unique role stable isotopes can play in their solution illustrate the importance of achieving and maintaining a broad inventory of isotopic species. Experience has demonstrated unequivocally an additional overriding requirement for widespread exploration of stable isotopes by the scientific and technical community, i.e., the need for low cost availability of the materials in quantity. Some representative applications of 12 C, 13 C, 14 N, 15 N, 16 O, 17 O, and 18 O are discussed

  12. The H{sup +}{sub 3} + H{sub 2} isotopic system. Origin of deuterium astrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Hugo, Edouard Jean-Marie

    2008-07-01

    Dense cold molecular clouds reckoned to be stellar nurseries are the scene of an extreme molecular deuteration. Despite the cosmic D/H ratio of {proportional_to}10{sup -5}, molecular species in prestellar cores are observed to contain nearly as much deuterium as hydrogen. This astonishing deuterium enrichment promoted by low temperatures is the work of H{sup +}{sub 3}. It is the key species which unlocks the deuterium from its HD reservoir via reactions like H{sup +}{sub 3}+HD {r_reversible} H{sub 2}D{sup +}+H{sub 2} and drags it further to other species in successive reactions. For this reason, the H{sup +}{sub 3}+H{sub 2} isotopic system is outstandingly critical for the astrochemistry of cold environments. However, its understanding is yet incomplete and insufficient. This thesis thus focuses on the H{sup +}{sub 3}+H{sub 2} isotopic system from a theoretical, experimental and astronomical point of view giving a particular look into the role of nuclear spins. As a first step, the stringent nuclear spin selection rules in associative, dissociative and reactive collisions are investigated. This purely theoretical study zooms into the details of the nuclear spin wavefunctions and shows that their permutation symmetry representation is necessary and sufficient, contrary to their angular momentum representation. Additionally, a new deterministic interpretation of nuclear spins in chemical reactions is proposed. Based on these considerations, a complete set of state-to-state rate coefficients for all H{sup +}{sub 3} + H{sub 2} isotopic variants is calculated using a microcanonical model leaned on phase space theory. An experimental study is conducted in parallel with a 22-pole ion trap apparatus in order to inspect the influences of temperature and H{sub 2} ortho-to-para ratio. The good overall agreement between experimental and theoretical results supports the validity and utility of the calculated set of rate coefficients. Furthermore, the potentiality of the 22-pole

  13. Computer automated mass spectrometer for isotope analysis on gas samples

    International Nuclear Information System (INIS)

    Pamula, A.; Kaucsar, M.; Fatu, C.; Ursu, D.; Vonica, D.; Bendea, D.; Muntean, F.

    1998-01-01

    A low resolution, high precision instrument was designed and realized in the mass spectrometry laboratory of the Institute of Isotopic and Molecular Technology, Cluj-Napoca. The paper presents the vacuum system, the sample inlet system, the ion source, the magnetic analyzer and the ion collector. The instrument is almost completely automated. There are described the analog-to-digital conversion circuits, the local control microcomputer, the automation systems and the performance checking. (authors)

  14. Supramolecular Nanoparticles for Molecular Diagnostics and Therapeutics

    Science.gov (United States)

    Chen, Kuan-Ju

    Over the past decades, significant efforts have been devoted to explore the use of various nanoparticle-based systems in the field of nanomedicine, including molecular imaging and therapy. Supramolecular synthetic approaches have attracted lots of attention due to their flexibility, convenience, and modularity for producing nanoparticles. In this dissertation, the developmental story of our size-controllable supramolecular nanoparticles (SNPs) will be discussed, as well as their use in specific biomedical applications. To achieve the self-assembly of SNPs, the well-characterized molecular recognition system (i.e., cyclodextrin/adamantane recognition) was employed. The resulting SNPs, which were assembled from three molecular building blocks, possess incredible stability in various physiological conditions, reversible size-controllability and dynamic disassembly that were exploited for various in vitro and in vivo applications. An advantage of using the supramolecular approach is that it enables the convenient incorporation of functional ligands onto SNP surface that confers functionality ( e.g., targeting, cell penetration) to SNPs. We utilized SNPs for molecular imaging such as magnetic resonance imaging (MRI) and positron emission tomography (PET) by introducing reporter systems (i.e., radio-isotopes, MR contrast agents, and fluorophores) into SNPs. On the other hand, the incorporation of various payloads, including drugs, genes and proteins, into SNPs showed improved delivery performance and enhanced therapeutic efficacy for these therapeutic agents. Leveraging the powers of (i) a combinatorial synthetic approach based on supramolecular assembly and (ii) a digital microreactor, a rapid developmental pathway was developed that is capable of screening SNP candidates for the ideal structural and functional properties that deliver optimal performance. Moreover, SNP-based theranostic delivery systems that combine reporter systems and therapeutic payloads into a

  15. Isotope reversals in hydrocarbon gases of natural shale systems and well head production data

    Energy Technology Data Exchange (ETDEWEB)

    Berner, U.; Schloemer, S.; Stiller, E. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany); Marquardt, D. [Rijksuniversiteit Utrecht (Netherlands)

    2013-08-01

    Relationships between gas geochemical signatures and the thermal maturity of source rocks containing aquatic organic matter are based on on pyrolysis experiments and have been successfully used in conventional hydrocarbon exploration since long. We demonstrate how these models can be applied to the evaluation of unconventional shale resources. For this purpose hydrocarbon gases have been extracted from low and high mature source rocks (type II kerogens) using laboratory desorption techniques. We determined the molecular composition of the gases as well as the carbon isotope ratios of methane to propane. In the extracted gases we observe an increase of {sup 13}C content in methane with increasing dry gas ratio (C1/{Sigma}C1-6). The carbon isotope ratios of ethane and propane initially increase with increasing dryness but start to become isotopically lighter above a dry gas ratio of 0.8. We show that oil-to-gas cracking explains the observed gas geochemical data, and that mixing between gases from different processes is a key factor to describe natural hydrocarbon systems of shales. However, data from published case studies using well head gases which show 'isotope roll-over' effects indicate that the isotopic reversal observed in well head samples deviate from those observed in natural shale systems in a fundamental way. We show that isotope reversals related to well head gases are best explained by an additional isotope fractionation effect induced through hydraulic fracturing and gas migration from the shale to the well head. Although, this induced isotope fractionation is an artifact which obscures isotopic information of natural systems to a large extend, we suggest a simple classification scheme which allows distinguishing between hot and cool spot areas using well head or mud line gas data. (orig.)

  16. 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

  17. Molecular biological enhancement of coal biodesulfurization. Seventh quarter report, May--July 1990

    Energy Technology Data Exchange (ETDEWEB)

    Kilbane, J.J.; Bielaga, B.A.

    1990-07-01

    The overall objective of this project is to sue molecular genetics to develop strains of bacteria with enhanced ability to remove sulfur from coal and to obtain data that will allow the performance and economics of a coal biodesulfurization process to be predicted. The work planned for the current quarter (May 1990 to July 1990) includes the following activities: (1) Construct a cloning vector that can be used in Rhodococcus rhodochrous IGTS8 from the small cryptic plasmid found in Rhodococcus rhodochrous ATCC 190607; (2) Develop techniques for the genetic analysis of IGTS8; (3) Continue biochemical experiments, particularly those that may allow the identification of desulfurization-related enzymes; (4) Continue experiments with coal to determine the kinetics of organic sulfur removal.

  18. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ

    2006-01-01

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

  19. Geochemistry of silicon isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Tiping; Li, Yanhe; Gao, Jianfei; Hu, Bin [Chinese Academy of Geological Science, Beijing (China). Inst. of Mineral Resources; Jiang, Shaoyong [China Univ. of Geosciences, Wuhan (China).

    2018-04-01

    Silicon is one of the most abundant elements in the Earth and silicon isotope geochemistry is important in identifying the silicon source for various geological bodies and in studying the behavior of silicon in different geological processes. This book starts with an introduction on the development of silicon isotope geochemistry. Various analytical methods are described and compared with each other in detail. The mechanisms of silicon isotope fractionation are discussed, and silicon isotope distributions in various extraterrestrial and terrestrial reservoirs are updated. Besides, the applications of silicon isotopes in several important fields are presented.

  20. Enhanced treatment of osteoid osteoma by intraoperative isotopic marking: a case report

    International Nuclear Information System (INIS)

    Haddam, A.; Bsiss, A.; Ech charraq, I.; BenRais, N.; Bakriga, B.; Moustain, M.R.; Hamama, J.

    2009-01-01

    Osteoid osteomas are small-sized benign painful bony tumours. Their complete surgical ablation consists in the proper treatment. The use of a portable Gamma probe allows to accurately localize the osteoid osteoma after radiolabelling and to reduce the size of incision and the bony ablation. We report the case of a patient having benefited from an isotopic intraoperative localization of an osteoid osteoma in the left tibia. Discussion chapter includes a comprehensive review of literature. (authors)

  1. Analysis of the differentially expressed low molecular weight peptides in human serum via an N-terminal isotope labeling technique combining nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

    Science.gov (United States)

    Leng, Jiapeng; Zhu, Dong; Wu, Duojiao; Zhu, Tongyu; Zhao, Ningwei; Guo, Yinlong

    2012-11-15

    Peptidomics analysis of human serum is challenging due to the low abundance of serum peptides and interference from the complex matrix. This study analyzed the differentially expressed (DE) low molecular weight peptides in human serum integrating a DMPITC-based N-terminal isotope labeling technique with nano-liquid chromatography and matrix-assisted laser desorption/ionization mass spectrometry (nano-LC/MALDI-MS). The workflow introduced a [d(6)]-4,6-dimethoxypyrimidine-2-isothiocyanate (DMPITC)-labeled mixture of aliquots from test samples as the internal standard. The spiked [d(0)]-DMPITC-labeled samples were separated by nano-LC then spotted on the MALDI target. Both quantitative and qualitative studies for serum peptides were achieved based on the isotope-labeled peaks. The DMPITC labeling technique combined with nano-LC/MALDI-MS not only minimized the errors in peptide quantitation, but also allowed convenient recognition of the labeled peptides due to the 6 Da mass difference. The data showed that the entire research procedure as well as the subsequent data analysis method were effective, reproducible, and sensitive for the analysis of DE serum peptides. This study successfully established a research model for DE serum peptides using DMPITC-based N-terminal isotope labeling and nano-LC/MALDI-MS. Application of the DMPITC-based N-terminal labeling technique is expected to provide a promising tool for the investigation of peptides in vivo, especially for the analysis of DE peptides under different biological conditions. Copyright © 2012 John Wiley & Sons, Ltd.

  2. Pico-CSIA: Picomolar Scale Compound-Specific Isotope Analyses

    Science.gov (United States)

    Baczynski, A. A.; Polissar, P. J.; Juchelka, D.; Schwieters, J. B.; Hilkert, A.; Freeman, K. H.

    2016-12-01

    The basic approach to analyzing molecular isotopes has remained largely unchanged since the late 1990s. Conventional compound-specific isotope analyses (CSIA) are conducted using capillary gas chromatography (GC), a combustion interface, and an isotope-ratio mass spectrometer (IRMS). Commercially available GC-IRMS systems are comprised of components with inner diameters ≥0.25 mm and employ helium flow rates of 1-4 mL/min. These flow rates are an order of magnitude larger than what the IRMS can accept. Consequently, ≥90% of the sample is lost through the open split, and 1-10s of nanomoles of carbon are required for analysis. These sample requirements are prohibitive for many biomarkers, which are often present in picomolar concentrations. We utilize the resolving power and low flows of narrow-bore capillary GC to improve the sensitivity of CSIA. Narrow bore capillary columns (<0.25 mm ID) allow low helium flow rates of ≤0.5mL/min for more efficient sample transfer to the ion source of the IRMS while maintaining the high linear flow rates necessary to preserve narrow peak widths ( 250 ms). The IRMS has been fitted with collector amplifiers configured to 25 ms response times for rapid data acquisition across narrow peaks. Previous authors (e.g., Sacks et al., 2007) successfully demonstrated improved sensitivity afforded by narrow-bore GC columns. They reported an accuracy and precision of 1.4‰ for peaks with an average width at half maximum of 720 ms for 100 picomoles of carbon on column. Our method builds on their advances and further reduces peak widths ( 600 ms) and the amount of sample lost prior to isotopic analysis. Preliminary experiments with 100 picomoles of carbon on column show an accuracy and standard deviation <1‰. With further improvement, we hope to demonstrate robust isotopic analysis of 10s of picomoles of carbon, more than 2 orders of magnitude lower than commercial systems. The pico-CSIA method affords high-precision isotopic analyses for

  3. Light induced drift: a possible mechanism of separation of isotopes by laser excitation

    International Nuclear Information System (INIS)

    Biswas, D.J.; Nilaya, J.P.; Venkatramani, N.

    2003-02-01

    A comprehensive review of the literature on the effect of light induced drift and its exploitation in the separation of isotopes, both in atomic and molecular forms, is presented. An experimental scheme based on this effect to separate S 33 , with a natural abundance of ∼0.76%, from SF 6 has also been worked out. (author)

  4. Developing Potential New Reference Materials for Light Isotopes in Foodstuffs

    Science.gov (United States)

    Frew, Russell; Van Hale, Robert; Clarke, Dianne; Abrahim, Aiman; Resch, Christian; Mayr, Leopold; Cannavan, Andrew; Gröning, Manfred

    2013-04-01

    Measurements of subtle variations in stable isotope ratios provide the means for verifying food integrity in numerous ways. Adulterants usually have different isotopic composition so their presence in a food is readily detectable. Stable isotope measurements can also be used to determine the region of production of the food. In most cases the ability of stable isotope measurements to verify, or otherwise reject, the authenticity of the food is greatly enhanced by comparison of a result to a reference database. The more high-quality data in the database, the more statistical power is afforded by the comparison. A serious weakness at present is the lack of reference materials in food matrices available to the community. Thus researchers have to rely on in-house standards for calibration and quality assurance. The result is that there are numerous datasets published that may be internally consistent but it is exceedingly difficult to combine these datasets into a cohesive database. This is particularly important for measurements of the hydrogen isotopes. Here we present a survey of the stable isotope (^2H, ^13C and ^15N) composition of 12 Reference Materials from the International Atomic Energy Agency catalogue. All but one of these materials are plant matter and have been developed as reference materials for other applications such as radionuclide or trace element measurements. Thus they have been verified as suitable materials in terms of stability and homogeneity for those tests. The purpose of this work is to ascertain if they are similarly suitable as stable isotope reference materials. The results from our survey show that there is a wide range in elemental and isotopic composition among these materials. For example, the ^15N values range from-13.5‰ to +18.6‰ and the nitrogen elemental composition range is from 0.7% to 9.7%. The ^13C values range from -20‰ to -40‰ and the carbon elemental composition ranges from 15% to 47%. We are now in the process of

  5. Automatic isotope gas analysis of tritium labelled organic materials Pt. 3

    International Nuclear Information System (INIS)

    Gacs, I.; Mlinko, S.; Payer, K.; Otvos, L.; Banfi, D.; Palagyi, T.

    1978-01-01

    An isotope analytical procedure and an automatic instrument developed for the determination of tritium in organic compounds and biological materials by internal gas counting are described. The sample is burnt in a stream of oxygen and the combustion products including water vapour carrying the tritium are led onto a column of molecular sieve-5A heated to 550 deg C. Tritium is retained temporarily on the column, then transferred into a stream of hydrogen by isotope exchange. After addition of butane, the tritiated hydrogen is led into an internal detector and enclosed there for radioactivity measurement. The procedure, providing quantitative recovery, is completed in five minutes. It is free of memory effect and suitable for the determination of tritium in a wide range of organic compounds and samples of biological origin. (author)

  6. Source tracing of natural organic matter bound mercury in boreal forest runoff with mercury stable isotopes.

    Science.gov (United States)

    Jiskra, Martin; Wiederhold, Jan G; Skyllberg, Ulf; Kronberg, Rose-Marie; Kretzschmar, Ruben

    2017-10-18

    Terrestrial runoff represents a major source of mercury (Hg) to aquatic ecosystems. In boreal forest catchments, such as the one in northern Sweden studied here, mercury bound to natural organic matter (NOM) represents a large fraction of mercury in the runoff. We present a method to measure Hg stable isotope signatures of colloidal Hg, mainly complexed by high molecular weight or colloidal natural organic matter (NOM) in natural waters based on pre-enrichment by ultrafiltration, followed by freeze-drying and combustion. We report that Hg associated with high molecular weight NOM in the boreal forest runoff has very similar Hg isotope signatures as compared to the organic soil horizons of the catchment area. The mass-independent fractionation (MIF) signatures (Δ 199 Hg and Δ 200 Hg) measured in soils and runoff were in agreement with typical values reported for atmospheric gaseous elemental mercury (Hg 0 ) and distinctly different from reported Hg isotope signatures in precipitation. We therefore suggest that most Hg in the boreal terrestrial ecosystem originated from the deposition of Hg 0 through foliar uptake rather than precipitation. Using a mixing model we calculated the contribution of soil horizons to the Hg in the runoff. At moderate to high flow runoff conditions, that prevailed during sampling, the uppermost part of the organic horizon (Oe/He) contributed 50-70% of the Hg in the runoff, while the underlying more humified organic Oa/Ha and the mineral soil horizons displayed a lower mobility of Hg. The good agreement of the Hg isotope results with other source tracing approaches using radiocarbon signatures and Hg : C ratios provides additional support for the strong coupling between Hg and NOM. The exploratory results from this study illustrate the potential of Hg stable isotopes to trace the source of Hg from atmospheric deposition through the terrestrial ecosystem to soil runoff, and provide a basis for more in-depth studies investigating the

  7. Development of a new method for hydrogen isotope analysis of trace hydrocarbons in natural gas samples

    Directory of Open Access Journals (Sweden)

    Xibin Wang

    2016-12-01

    Full Text Available A new method had been developed for the analysis of hydrogen isotopic composition of trace hydrocarbons in natural gas samples by using solid phase microextraction (SPME combined with gas chromatography-isotope ratio mass spectrometry (GC/IRMS. In this study, the SPME technique had been initially introduced to achieve the enrichment of trace content of hydrocarbons with low abundance and coupled to GC/IRMS for hydrogen isotopic analysis. The main parameters, including the equilibration time, extraction temperature, and the fiber type, were systematically optimized. The results not only demonstrated that high extraction yield was true but also shows that the hydrogen isotopic fractionation was not observed during the extraction process, when the SPME device fitted with polydimethylsiloxane/divinylbenzene/carbon molecular sieve (PDMS/DVB/CAR fiber. The applications of SPME-GC/IRMS method were evaluated by using natural gas samples collected from different sedimentary basins; the standard deviation (SD was better than 4‰ for reproducible measurements; and also, the hydrogen isotope values from C1 to C9 can be obtained with satisfying repeatability. The SPME-GC/IRMS method fitted with PDMS/DVB/CAR fiber is well suited for the preconcentration of trace hydrocarbons, and provides a reliable hydrogen isotopic analysis for trace hydrocarbons in natural gas samples.

  8. Isotope labeling for NMR studies of macromolecular structure and interactions

    International Nuclear Information System (INIS)

    Wright, P.E.

    1994-01-01

    Implementation of biosynthetic methods for uniform or specific isotope labeling of proteins, coupled with the recent development of powerful heteronuclear multidimensional NMR methods, has led to a dramatic increase in the size and complexity of macromolecular systems that are now amenable to NMR structural analysis. In recent years, a new technology has emerged that combines uniform 13 C, 15 N labeling with heteronuclear multidimensional NMR methods to allow NMR structural studies of systems approaching 25 to 30 kDa in molecular weight. In addition, with the introduction of specific 13 C and 15 N labels into ligands, meaningful NMR studies of complexes of even higher molecular weight have become feasible. These advances usher in a new era in which the earlier, rather stringent molecular weight limitations have been greatly surpassed and NMR can begin to address many central biological problems that involve macromolecular structure, dynamics, and interactions

  9. Isotope labeling for NMR studies of macromolecular structure and interactions

    Energy Technology Data Exchange (ETDEWEB)

    Wright, P.E. [Scripps Research Institute, La Jolla, CA (United States)

    1994-12-01

    Implementation of biosynthetic methods for uniform or specific isotope labeling of proteins, coupled with the recent development of powerful heteronuclear multidimensional NMR methods, has led to a dramatic increase in the size and complexity of macromolecular systems that are now amenable to NMR structural analysis. In recent years, a new technology has emerged that combines uniform {sup 13}C, {sup 15}N labeling with heteronuclear multidimensional NMR methods to allow NMR structural studies of systems approaching 25 to 30 kDa in molecular weight. In addition, with the introduction of specific {sup 13}C and {sup 15}N labels into ligands, meaningful NMR studies of complexes of even higher molecular weight have become feasible. These advances usher in a new era in which the earlier, rather stringent molecular weight limitations have been greatly surpassed and NMR can begin to address many central biological problems that involve macromolecular structure, dynamics, and interactions.

  10. Microscopic cascading of second-order molecular nonlinearity: New design principles for enhancing third-order nonlinearity.

    Science.gov (United States)

    Baev, Alexander; Autschbach, Jochen; Boyd, Robert W; Prasad, Paras N

    2010-04-12

    Herein, we develop a phenomenological model for microscopic cascading and substantiate it with ab initio calculations. It is shown that the concept of local microscopic cascading of a second-order nonlinearity can lead to a third-order nonlinearity, without introducing any new loss mechanisms that could limit the usefulness of our approach. This approach provides a new molecular design protocol, in which the current great successes achieved in producing molecules with extremely large second-order nonlinearity can be used in a supra molecular organization in a preferred orientation to generate very large third-order response magnitudes. The results of density functional calculations for a well-known second-order molecule, (para)nitroaniline, show that a head-to-tail dimer configuration exhibits enhanced third-order nonlinearity, in agreement with the phenomenological model which suggests that such an arrangement will produce cascading due to local field effects.

  11. ICT: isotope correction toolbox.

    Science.gov (United States)

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

    2016-01-01

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

  12. 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)

  13. Molecular enhancement of Balmer emissions following foil-induced dissociation of fast H2+ and H3+ ions

    International Nuclear Information System (INIS)

    Kobayashi, H.; Oda, N.

    1984-01-01

    Relative emission yields of Balmer lines as functions of the dwell time (t/sub D/ = 0.97--54.1 fs) in thin carbon foils (2--68 μg/cm 2 ) have been measured with (0.2--0.8)-MeV/amu H + , H 2 + , and H 3 + incident on thin carbon foils. Large molecular effects for emission yields of Balmer lines have been observed for H 2 + and H 3 + , where the molecular effect for H 3 + is larger than that for H 2 + . The molecular effects for H 2 + and H 3 + depend on the principal quantum number (n = 3--6), but this n dependence disappears at the largest t/sub D/ ( = 54.1 fs). The molecular effects rapidly decrease with increasing t/sub D/ in the small-t/sub D/ ( or approx. =2 fs) region. The magnitudes of the molecular effects at the largest t/sub D/ ( = 54.1 fs) are in good agreement with those by Andresen et al. [Phys. Scr. 19, 335 (1979)]. Relative populations of n-state hydrogens in the large-t/sub D/ (> or approx. =2 fs) region have been derived from the relative yields of Balmer lines as functions of n and t/sub D/. The molecular enhancement for relative populations of n-state hydrogens for H 2 + depends on n and t/sub D/, and decreases with increasing t/sub D/ and increases with increasing n

  14. Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

    Science.gov (United States)

    Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

    2012-01-01

    Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

  15. Lead isotope measurements on aerosol samples with ICP-MS

    International Nuclear Information System (INIS)

    Widmer, C.R.; Kraehenbuehl, U.; Kramers, J.; Tobler, L.

    2000-01-01

    Size fractionated aerosols were collected with low pressure Berner impactors on a radio/TV tower 110 m above ground on a hill 10 km east of Bern at a total elevation of 1060 m asl. Two different wind sectors were chosen with the goal of assessing any differences in lead concentration and the 3 radiogenic lead isotopes (206,207,208) for east and west wind, respectively. A leaching technique was used to extract the lead quantitatively from the surface of the impaction foils. This method has been proven to be better suited for airborne particles than complete microwave digestion because it is less time consuming and contamination risk is smaller. Blank considerations played a major role in choosing all the chemicals, tubes, beakers and selecting the analytical method. Lead concentrations were determined with GF-AAS and lead isotopes with two different ICP-MS systems, one being a multicollector system. Precision of the simultaneous multicollector system was found to be at least a factor of 3 better than that of the sequentially operating ICP-MS. The small variations in isotope ratios from the two wind sectors can be distinctly seen with this enhanced precision. The observed relative difference in isotope ratios between east- and westwind was ∝0.6% for 207 Pb/ 206 Pb and ∝0.5% for 208 Pb/ 206 Pb. (orig.)

  16. Intracellular Cadmium Isotope Fractionation

    Science.gov (United States)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  17. Fluoride sample matrices and reaction cells — new capabilities for isotope measurements in accelerator mass spectrometry

    Directory of Open Access Journals (Sweden)

    Eliades J.

    2012-04-01

    Full Text Available Two new techniques, which extend the range of elements that can be analyzed by Accelerator Mass Spectrometry (AMS, and which increase its isobar selection capabilities, have been recently introduced. The first consists of embedding the sample material in a fluoride matrix (e.g. PbF2, which facilitates the production, in the ion source, of fluoride molecular anions that include the isotope of interest. In addition to forming anions with large electron binding energies and thereby increasing the range of analysable elements, in many cases by selection of a molecular form with a particular number of fluorine atoms, some isobar discrimination can be obtained. The second technique, for the significant reduction of atomic isobar interferences, is used following mass selection of the rare isotope. It consists of the deceleration, cooling and reaction of the rare mass beam with a gas, selected so that unwanted isobars are greatly attenuated in comparison with the isotope of interest. Proof of principle measurements for the analysis of 36C1 and 41Ca have provided encouraging results and work is proceeding on the integration of these techniques in a new AMS system planned for installation in late 2012 at the University of Ottawa.

  18. Method to make accurate concentration and isotopic measurements for small gas samples

    Science.gov (United States)

    Palmer, M. R.; Wahl, E.; Cunningham, K. L.

    2013-12-01

    Carbon isotopic ratio measurements of CO2 and CH4 provide valuable insight into carbon cycle processes. However, many of these studies, like soil gas, soil flux, and water head space experiments, provide very small gas sample volumes, too small for direct measurement by current constant-flow Cavity Ring-Down (CRDS) isotopic analyzers. Previously, we addressed this issue by developing a sample introduction module which enabled the isotopic ratio measurement of 40ml samples or smaller. However, the system, called the Small Sample Isotope Module (SSIM), does dilute the sample during the delivery with inert carrier gas which causes a ~5% reduction in concentration. The isotopic ratio measurements are not affected by this small dilution, but researchers are naturally interested accurate concentration measurements. We present the accuracy and precision of a new method of using this delivery module which we call 'double injection.' Two portions of the 40ml of the sample (20ml each) are introduced to the analyzer, the first injection of which flushes out the diluting gas and the second injection is measured. The accuracy of this new method is demonstrated by comparing the concentration and isotopic ratio measurements for a gas sampled directly and that same gas measured through the SSIM. The data show that the CO2 concentration measurements were the same within instrument precision. The isotopic ratio precision (1σ) of repeated measurements was 0.16 permil for CO2 and 1.15 permil for CH4 at ambient concentrations. This new method provides a significant enhancement in the information provided by small samples.

  19. Applications of stable isotopes

    International Nuclear Information System (INIS)

    Letolle, R.; Mariotti, A.; Bariac, T.

    1991-06-01

    This report reviews the historical background and the properties of stable isotopes, the methods used for their measurement (mass spectrometry and others), the present technics for isotope enrichment and separation, and at last the various present and foreseeable application (in nuclear energy, physical and chemical research, materials industry and research; tracing in industrial, medical and agronomical tests; the use of natural isotope variations for environmental studies, agronomy, natural resources appraising: water, minerals, energy). Some new possibilities in the use of stable isotope are offered. A last chapter gives the present state and forecast development of stable isotope uses in France and Europe

  20. Stable isotope-resolved metabolomics and applications for drug development

    Science.gov (United States)

    Fan, Teresa W-M.; Lorkiewicz, Pawel; Sellers, Katherine; Moseley, Hunter N.B.; Higashi, Richard M.; Lane, Andrew N.

    2012-01-01

    Advances in analytical methodologies, principally nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS), during the last decade have made large-scale analysis of the human metabolome a reality. This is leading to the reawakening of the importance of metabolism in human diseases, particularly cancer. The metabolome is the functional readout of the genome, functional genome, and proteome; it is also an integral partner in molecular regulations for homeostasis. The interrogation of the metabolome, or metabolomics, is now being applied to numerous diseases, largely by metabolite profiling for biomarker discovery, but also in pharmacology and therapeutics. Recent advances in stable isotope tracer-based metabolomic approaches enable unambiguous tracking of individual atoms through compartmentalized metabolic networks directly in human subjects, which promises to decipher the complexity of the human metabolome at an unprecedented pace. This knowledge will revolutionize our understanding of complex human diseases, clinical diagnostics, as well as individualized therapeutics and drug response. In this review, we focus on the use of stable isotope tracers with metabolomics technologies for understanding metabolic network dynamics in both model systems and in clinical applications. Atom-resolved isotope tracing via the two major analytical platforms, NMR and MS, has the power to determine novel metabolic reprogramming in diseases, discover new drug targets, and facilitates ADME studies. We also illustrate new metabolic tracer-based imaging technologies, which enable direct visualization of metabolic processes in vivo. We further outline current practices and future requirements for biochemoinformatics development, which is an integral part of translating stable isotope-resolved metabolomics into clinical reality. PMID:22212615

  1. High mass isotope separation arrangement

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1976-01-01

    An isotope separation arrangement for separating a preselected isotope from a mixture of chemically-identical but isotopically-different molecules by either photon-induced pure revibrational or vibronic selective excitation of the molecules containing the atoms of the isotope to be separated from a lower to a higher energy state, and a chemical reaction of the higher energy state molecules with a chemically-reactive agent to form a chemical compound containing primarily the atoms of the isotope to be separated in a physicochemical state different from the physicochemical state of the mixture of chemically-identical but isotopically-different molecules. The chemical compound containing the atoms of the isotope to be separated may be subsequently processed to obtain the isotope. The laser configuration used to generate the photon beam is fully described

  2. Isotope separation process

    International Nuclear Information System (INIS)

    Lyon, R.K.

    1976-01-01

    The instant invention relates to a process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same material in said material. In one embodiment, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by selective dissociation of said excited molecules by the absorption of a single photon of visible or ultraviolet light. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium. 11 Claims, 2 Drawing Figures

  3. Integrating stomach content and stable isotope analyses to quantify the diets of pygoscelid penguins.

    Directory of Open Access Journals (Sweden)

    Michael J Polito

    Full Text Available Stomach content analysis (SCA and more recently stable isotope analysis (SIA integrated with isotopic mixing models have become common methods for dietary studies and provide insight into the foraging ecology of seabirds. However, both methods have drawbacks and biases that may result in difficulties in quantifying inter-annual and species-specific differences in diets. We used these two methods to simultaneously quantify the chick-rearing diet of Chinstrap (Pygoscelis antarctica and Gentoo (P. papua penguins and highlight methods of integrating SCA data to increase accuracy of diet composition estimates using SIA. SCA biomass estimates were highly variable and underestimated the importance of soft-bodied prey such as fish. Two-source, isotopic mixing model predictions were less variable and identified inter-annual and species-specific differences in the relative amounts of fish and krill in penguin diets not readily apparent using SCA. In contrast, multi-source isotopic mixing models had difficulty estimating the dietary contribution of fish species occupying similar trophic levels without refinement using SCA-derived otolith data. Overall, our ability to track inter-annual and species-specific differences in penguin diets using SIA was enhanced by integrating SCA data to isotopic mixing modes in three ways: 1 selecting appropriate prey sources, 2 weighting combinations of isotopically similar prey in two-source mixing models and 3 refining predicted contributions of isotopically similar prey in multi-source models.

  4. Separation of molecular hydrogen isotope mixtures using zeolite NaX-3M

    International Nuclear Information System (INIS)

    Polevoj, A.S.; Yudin, I.P.

    1984-01-01

    The components of transfer unit height (TUH) at separation of the H 2 -D 2 mixture using zeolite NaX-3M in the countercurrent column are determined. It is shown that the interphase isotopic exchange in the column is limited by gaseous diffusion in sorbent primary pores. On the basis of the TUH dependence the value of the hydrogen diffusion coefficient in primary pores of NaX-3M zeolite equal at 77 K and 87.3 K, respectively, approximately 1.09x10 -15 and approximately 1.69x10 -15 m 2 /s is calculated

  5. The application of inductively coupled plasma dynamic reaction cell mass spectrometry for measurement of selenium isotopes, isotope ratios and chromatographic detection of selenoamino acids

    DEFF Research Database (Denmark)

    Sloth, Jens Jørgen; Larsen, Erik Huusfeldt

    2000-01-01

    orders of magnitude by using methane as reactive cell gas in the DRC. By using 3% v/v methanol in water for carbon-enhanced ionisation of selenium, the sensitivity of Se-80 was 10(4) counts s(-1) per ng ml(-1) of selenium, and the estimated limit of detection was 6 pg ml(-1). The precision of the isotope...

  6. Observations of molecular hydrogen mixing ratio and stable isotopic composition at the Cabauw tall tower in the Netherlands

    Science.gov (United States)

    Batenburg, A. M.; Popa, M. E.; Vermeulen, A. T.; van den Bulk, W. C. M.; Jongejan, P. A. C.; Fisher, R. E.; Lowry, D.; Nisbet, E. G.; Röckmann, T.

    2016-12-01

    Measurements of the stable isotopic composition (δD(H2) or δD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (χ(H2)) measurements for understanding the atmospheric H2 cycle. δD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by χ(H2) values that reach up to ≈1 ppm and low δD values. An isotopic source signature analysis yields an apparent source signature below -400‰, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (≈-340‰), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in χ(H2) at lower sampling levels (20 and 60 m) with respect to higher sampling levels (120 and 200 m). There was a significant shift to lower median δD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising

  7. Isotope laboratories

    International Nuclear Information System (INIS)

    1978-01-01

    This report from the Dutch Ministry of Health is an advisory document concerned with isotope laboratories in hospitals, in connection with the Dutch laws for hospitals. It discusses which hospitals should have isotope laboratories and concludes that as many hospitals as possible should have small laboratories so that emergency cases can be dealt with. It divides the Netherlands into regions and suggests which hospitals should have these facilities. The questions of how big each lab. is to be, what equipment each has, how each lab. is organised, what therapeutic and diagnostic work should be carried out by each, etc. are discussed. The answers are provided by reports from working groups for in vivo diagnostics, in vitro diagnostics, therapy, and safety and their results form the criteria for the licences of isotope labs. The results of a questionnaire for isotope labs. already in the Netherlands are presented, and their activities outlined. (C.F.)

  8. Isotope exchange study of the dissociation of metal-humic substance complexes

    International Nuclear Information System (INIS)

    Mizera, J.; Jansova, A.; Hvozdova, I.; Benes, P.; Novak, F.

    2003-01-01

    Isotope exchange was employed to study dissociation of metal cations from their complexes with humic substances (HS). Dissociation of cation from HS controls the rate of isotope exchange between two identical metal-HS solutions (but for the presence of a radiotracer) divided by a dialysis membrane. The rate of isotope exchange of Eu/ 152 Eu and Co/ 60 Co in the systems with various HS was monitored as a function of pH, ionic strength, and the degree of HS loading with metal. The apparent rate of Eu-HS dissociation was found to be enhanced by decreasing pH, increasing ionic strength, and increasing metal loading. Co-HS dissociation was too fast to be followed by the method. For interpretation of the experimental kinetic data, the multiple first order law has been applied. Based on the results, a concept of HS as a mixture of two types of binding sites is discussed. (author)

  9. 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.

  10. Process for isotope separation

    International Nuclear Information System (INIS)

    Emile, B.F.M.

    1983-11-01

    A process is claimed for isotopic separation applied to isotopes of elements that can be placed in at least a physicochemical form in which the isotopic atoms or the molecules containing these atoms can be easily displaced and for which there are selective radiations preferentially absorbed by the isotopes of a certain type or by the molecules containing them, said absorption substantially increasing the probability of ionization of said atoms or molecules relative to the atoms or molecules that did not absorb the radiation. The process consists of placing the isotopic mixture in such a form, subjecting it in a separation zone to selective radiations and to an electrical field that produces migration of positive ions toward the negative electrodes and negative ions toward the positive electrodes, and withdrawing from certain such zones the fractions thus enriched in certain isotopes

  11. Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

    Science.gov (United States)

    Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

    2017-11-01

    Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Molecular design of high performance zwitterionic liquids for enhanced heavy-oil recovery processes.

    Science.gov (United States)

    Martínez-Magadán, J M; Cartas-Rosado, A R; Oviedo-Roa, R; Cisneros-Dévora, R; Pons-Jiménez, M; Hernández-Altamirano, R; Zamudio-Rivera, L S

    2018-03-01

    Branched gemini zwitterionic liquids, which contain two zwitterionic moieties of linked quaternary-ammonium and carboxylate groups, are proposed as chemicals to be applied in the Enhanced Oil Recovery (EOR) from fractured carbonate reservoirs. The zwitterionic moieties are bridged between them through an alkyl chain containing 12 ether groups, and each zwitterionic moiety has attached a long alkyl tail including a CC double bond. A theoretical molecular mechanism over which EOR could rest, consisting on both the disaggregation of heavy oil and the reservoir-rock wettability alteration, was suggested. Results show that chemicals can both reduce the viscosity and remove heavy-oil molecules from the rock surface. Copyright © 2018. Published by Elsevier Inc.

  13. Stable isotope enrichment by thermal diffusion

    International Nuclear Information System (INIS)

    Vasaru, Gheorghe

    2003-01-01

    Thermal diffusion (TD) in both gaseous and liquid phase has been the subject of extensive experimental and theoretical investigations, especially after the invention by K. Clusius and G. Dickel of the thermal diffusion column, sixty years ago. This paper gives a brief overview of the most important applications and developments of this transport phenomenon for enrichment of 13 C and of some noble gases isotopes in our institute. The results of calculations of the transport coefficients H and K for a concentric tube type TD column, operated with methane as process gas, are presented. Static separation factor at equilibrium vs gas pressure has been calculated for various molecular models. The experimental separation factors for different gas pressure were found to be consistent with those calculated for the inverse power repulsion model and the Lennard-Jones model. The most important characteristics of a seven-stage cascade consisting of 19 TD columns of concentric tube type are given. This system has been constructed and successfully operated at a temperature of 673 K and produces an enrichment of methane of natural isotopic 13 C abundance, up to the concentration of 25% 13 CH 4 . Enrichment of the noble gases isotopes implies: - a . Enrichment of 20 Ne and 22 Ne in a eight-stage cascade consisting of 8 TD columns; - b. enrichment of 46 Ar in a seven-stage cascade consisting of TD columns and finally; - c. enrichment of 78 Kr and 86 Kr in a fifteen-stage cascade, consisting of 35 TD columns. For all these installations we have adopted TD columns of hot wire type (4 m in length), operated at a temperature of 1073 K. (author)

  14. Isotope separation process

    International Nuclear Information System (INIS)

    Cabicar, J.; Stamberg, K.; Katzer, J.

    1983-01-01

    A process for separating isotopes by the method of controlled distribution is claimed. A first phase is either a solution of isotopic components and a ligand (from 10 - 6 M to a saturated solution), or a gaseous mixture of isotopic components, or a gaseous mixture of isotopic components and an inert gas. The isotopes are in the starting mixture in molar ratio from 1:10 5 to 1:10 - 5 . The second phase is a solid sorbent such as styrene-divinylbenzene ion exchangers, or bio-sorbents on the basis of mycelium of lower fungi and sorbents on the basis of cellulose, or an extraction agent such as tributyl phosphate and trioctyl amine, if need be, kept by a carrier such as teflon, silica gel and cellulose. The two-phase system exhibits non-linear equilibrium isotherm for sorption and/or desorption or for extraction and/or re-extraction. After bringing both phases into contact the rate of transport of isotopic components from one phase into another is not equal. Retardation of isotopic exchange takes place by complexation of isotopes with ligands such as cabonate, sulphate, citrate, chloride and ethylenediamine tetraacetate ions, or by using sorbents and extraction agents with chelating functional groups such as carboxyl and hyroxyl groups, groups on the basis of phosphorus, nitrogen and sulphur and/or by operating in darkness, or in the light having wave length between 2.5x10 2 and 10 9 nm. The contact time is between 10 - 2 and 10 6 s, temperature between 10 2 and 10 3 K, the number of stirrer revolutions between 10 - 2 and 10 4 revolutions per s, flow rate at column arrangement between 10 - 6 and 10 - 1 m/s and the size of particles of sorbent between 10 - 6 and 10 - 2 m

  15. Isotope separation process

    International Nuclear Information System (INIS)

    Thomas, W.R.L.

    1979-01-01

    The instant invention relates to an improved process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same element in said material. More particularly, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by a step wherein more of the excited molecules than non-excited molecules are converted to a chemically different form which may be separated by means known in the art. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium

  16. Isotope separation process

    International Nuclear Information System (INIS)

    Lyon, R.K.

    1977-01-01

    The instant invention relates to a process for separating a material into two or more parts in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same material in said material. More particularly, the invention relates to a method for the isotopically selective excitation of gas phase molecules by multiple infrared photon absorption followed by a step wherein more of the excited molecules than nonexcited molecules are converted to a chemically different form which may be separated by means known in the art. This invention is useful for, but not limited to, the separation of the principal isotopes of uranium. 15 claims, 1 figure

  17. Isotope separation method and apparatus

    International Nuclear Information System (INIS)

    Lyon, R.K.; Eisner, P.N.; Thomas, W.R.L.

    1980-01-01

    A method and apparatus are specified for separating a mixture of isotopes present in a compound, preferably a gaseous compound, into two or more parts in each of which the abundances of the isotopes differ from the natural abundances of the isotopes in the compound. The invention particularly relates to carrying out a laser induced, isotopically selective conversion of gaseous molecules in such a manner as to achieve more than one stage of isotope separation along the length of the laser beam. As an example, the invention is applied to the separation of the isotopes of uranium in UF 6 , in which either the U-235 or U-238 isotope is selectively excited by means of irradiation from an infrared laser, and the selectively excited isotope converted into a product that can be recovered from UF 6 by one of a variety of methods that are described. (U.K.)

  18. Enhancement of molecular sensitivity in positron emission tomography with quantum correlation of γ-ray photons

    Science.gov (United States)

    Sato, K.; Kobayashi, Y.

    2015-05-01

    Enhancement of molecular sensitivity in positron emission tomography (PET) has long been discussed with respect to imaging instrumentation and algorithms for data treatment. Here, the molecular sensitivity in PET is discussed on the basis of 2-dimensional coincident measurements of 511 keV γ ray photons resultant from two-photon annihilation. Introduction of an additional selection window based on the energy sum and difference of the coincidently measured γ ray photons, without any significant instrumental and algorithmic changes, showed an improvement in the signal-to-noise ratio (SNR) by an order of magnitude. Improvement of performance characteristics in the PET imaging system was demonstrated by an increase in the noise equivalent count rate (NECR) which takes both the SNR and the detection efficiency into consideration. A further improvement of both the SNR and the NECR is expected for the present system in real clinical and in-vivo environments, where much stronger positron sources are employed.

  19. Enhancement of molecular sensitivity in positron emission tomography with quantum correlation of γ-ray photons

    International Nuclear Information System (INIS)

    Sato, K.; Kobayashi, Y.

    2015-01-01

    Enhancement of molecular sensitivity in positron emission tomography (PET) has long been discussed with respect to imaging instrumentation and algorithms for data treatment. Here, the molecular sensitivity in PET is discussed on the basis of 2-dimensional coincident measurements of 511 keV γ ray photons resultant from two-photon annihilation. Introduction of an additional selection window based on the energy sum and difference of the coincidently measured γ ray photons, without any significant instrumental and algorithmic changes, showed an improvement in the signal-to-noise ratio (SNR) by an order of magnitude. Improvement of performance characteristics in the PET imaging system was demonstrated by an increase in the noise equivalent count rate (NECR) which takes both the SNR and the detection efficiency into consideration. A further improvement of both the SNR and the NECR is expected for the present system in real clinical and in-vivo environments, where much stronger positron sources are employed

  20. Isotope angiocardiography

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  1. International Isotopes Markets

    Directory of Open Access Journals (Sweden)

    Stanislaw Z. Zhiznin

    2016-01-01

    Full Text Available The paper studies world markets of stable and radioactive isotopes. Isotopes have found various applications in science, industry, agriculture and other sectors of the economy, but especially - in medicine. Nuclear medicine is developing intensively all over the world thanks to the success in the treatment of various diseases with the help of radioactive pharmaceuticals (radiopharmaceuticals. The article uses empirical data from a forecast study of the global radiopharmaceuticals market made in 2015 by a research company «Markets and Markets» for the European, North American and global markets. The paper also analyzes the statistical data on the global export and import of natural uranium, enriched and depleted uranium, plutonium, thorium and some stable isotopes of non-medical purposes, presented by a company «Trend economy» in 2014. Despite a unique industrial base for the production of isotopes created in the Soviet Union Russia occupies a modest position on the world market of nuclear medicine except for certain areas. More than 80% of isotopes, produced in USSR were consumed domestically, the export of the stable and radioactive isotopes was in equal proportions. Now the country's domestic radiopharmaceuticals market is poorly developed. To radically change the situation, it is necessary to carry out reforms that stimulate the development of nuclear medicine.

  2. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

    Science.gov (United States)

    Nuth, J. A.; Paquette, J. A.; Farquhar, A.; Johnson, N. M.

    2011-01-01

    The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

  3. Laser-cooled atomic ions as probes of molecular ions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Kenneth R.; Viteri, C. Ricardo; Clark, Craig R.; Goeders, James E.; Khanyile, Ncamiso B.; Vittorini, Grahame D. [Schools of Chemistry and Biochemistry, Computational Science and Engineering and Physics, Georgia Institute of Technology, Atlanta, GA 30332 (United States)

    2015-01-22

    Trapped laser-cooled atomic ions are a new tool for understanding cold molecular ions. The atomic ions not only sympathetically cool the molecular ions to millikelvin temperatures, but the bright atomic ion fluorescence can also serve as a detector of both molecular reactions and molecular spectra. We are working towards the detection of single molecular ion spectra by sympathetic heating spectroscopy. Sympathetic heating spectroscopy uses the coupled motion of two trapped ions to measure the spectra of one ion by observing changes in the fluorescence of the other ion. Sympathetic heating spectroscopy is a generalization of quantum logic spectroscopy, but does not require ions in the motional ground state or coherent control of the ion internal states. We have recently demonstrated this technique using two isotopes of Ca{sup +} [Phys. Rev. A, 81, 043428 (2010)]. Limits of the method and potential applications for molecular spectroscopy are discussed.

  4. Osmium isotope perturbations during the Pliensbachian-Toarcian (Early Jurassic): Relationships between volcanism, weathering, and climate change

    Science.gov (United States)

    Percival, Lawrence; Cohen, Anthony; Davies, Marc; Dickson, Alexander; Jenkyns, Hugh; Hesselbo, Stephen; Mather, Tamsin; Xu, Weimu; Storm, Marisa

    2016-04-01

    The Mesozoic Era marked a time of greenhouse conditions on Earth, punctuated by a number of abrupt perturbations to the carbon cycle, such as Ocean Anoxic Events (OAEs). OAEs are typically marked in the stratigraphic record by the appearance of organic-rich shales, and excursions in carbon-isotope ratios registered in carbonates and organic matter. A range of geochemical evidence indicates changes to global temperatures, typically featuring abrupt warming possibly caused by CO2 emissions resulting from Large Igneous Province (LIP) volcanism. A warmer atmosphere is thought to have led to changes in the global hydrological cycle, which would likely have enhanced global weathering rates. The Toarcian OAE (T-OAE) is inferred, from osmium isotope ratios in organic-rich mudrocks from Yorkshire and western North America, to have been a time of such increased weathering rates. However, it is likely that the sediments at these locations were deposited in relatively hydrographically restricted environments, potentially more susceptible to the influence of local input; consequently, they may not offer the best representation of the global seawater Os-isotope composition at that time. In this study, we have measured the osmium isotope composition of siciliclastic mudrocks in a core from the Mochras borehole (Llanbedr Farm, Cardigan Bay Basin, Wales), which constitutes a sedimentary record for a fully open-marine seaway that connected Tethys to the Boreal ocean during the Toarcian. We analysed samples from strata including both the T-OAE and preceding Pliensbachian-Toarcian boundary (Pl-To), both of which record multiple geochemical excursions and records of elevated extinction amongst benthic fauna. We find that the latest Pliensbachian records seawater 187Os/188Os of ~0.35-0.4, rising to ~0.5 at the Pl-To boundary, before a further rise to ~0.7 during the T-OAE. We conclude that such increases in radiogenic Os flux to the ocean system resulted from enhanced continental

  5. Electrochemically controlled iron isotope fractionation

    Science.gov (United States)

    Black, Jay R.; Young, Edward D.; Kavner, Abby

    2010-02-01

    Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

  6. Uranium isotopes in groundwaters from Tubarao Group, Parana Basin, Brazil

    International Nuclear Information System (INIS)

    Bonotto, D.M.; Caprioglio, L.

    1999-01-01

    The purpose of this work is to characterize the uranium isotopes 238-U and 234-U in some important deep tubular wells drilled at Tubarao Group, with the aim of verifying if the dissolution processes that are taking place within the aquifer can generate enhanced 234-U/238-U activity ratios like those found at the Botucatu-Piramboia aquifer. (author)

  7. Three New Offset {delta}{sup 11}B Isotope Reference Materials for Environmental Boron Isotope Studies

    Energy Technology Data Exchange (ETDEWEB)

    Rosner, M. [BAM Federal Institute for Materials Research and Testing, Berlin (Germany); IsoAnalysis UG, Berlin (Germany); Vogl, J. [BAM Federal Institute for Materials Research and Testing, Berlin (Germany)

    2013-07-15

    The isotopic composition of boron is a well established tool in various areas of science and industry. Boron isotope compositions are typically reported as {delta}{sup 11}B values which indicate the isotopic difference of a sample relative to the isotope reference material NIST SRM 951. A significant drawback of all of the available boron isotope reference materials is that none of them covers a natural boron isotope composition apart from NIST SRM 951. To fill this gap of required {delta}{sup 11}B reference materials three new solution boric acid reference materials were produced, which cover 60 per mille of the natural boron isotope variation (-20 to 40 per mille {delta}{sup 11}B) of about 100 per mille . The new reference materials are certified for their {delta}{sup 11}B values and are commercially available through European Reference Materials (http://www.erm-crm.org). The newly produced and certified boron isotope reference materials will allow straightforward method validation and quality control of boron isotope data. (author)

  8. An isotope-enrichment unit and a process for isotope separation

    International Nuclear Information System (INIS)

    1981-01-01

    A process and equipment for isotope enrichment using gas-centrifuge cascades are described. The method is described as applied to the separation of uranium isotopes, using natural-abundance uranium hexafluoride as the gaseous-mixture feedstock. (U.K.)

  9. Assembled microneedle arrays enhance the transport of compounds varying over a large range of molecular weight across human dermatomed skin

    NARCIS (Netherlands)

    Verbaan, F.J.; Bal, S.M.; van den Berg, D.J.; Groenink, W.H.H.; Verpoorten, H.; Lüttge, Regina; Bouwstra, J.A.

    2007-01-01

    In this study, we demonstrate the feasibility to use microneedle arrays manufactured from commercially available 30G hypodermal needles to enhance the transport of compounds up to a molecular weight of 72 kDa. Piercing of human dermatomed skin with microneedle arrays was studied by Trypan Blue

  10. Studies of carbon--isotope fractionation. Annual progress report, December 1, 1974--November 30, 1975

    International Nuclear Information System (INIS)

    Ishida, T.

    1975-01-01

    The vapor pressure isotope effect of 13 C/ 12 C-substitution in CClF 3 was measured at temperatures between 169 0 and 206 0 K by means of cryogenic distillation. The 13 C/ 12 C-vapor pressure isotope effect in CHF 3 was also studied at temperatures between 161 0 and 205 0 K by a similar method. The construction of a cryostat has progressed as scheduled. The investigation of carbon isotope exchange equilibria between carbon dioxide and various carbamates dissolved in various organic solvents has continued. The five-stage system of Taylor-Ghate design was improved to shorten the transient time. A single stage apparatus was designed, built, and tested. These systems are used to measure the equilibrium constants and various phase equilibria involved in the carbon dioxide--carbamate system. The investigation of the explicit method of total isotope effect has made progress. A satisfactory approximation was found for the classical partition function of a Morse oscillator. The method gives a reasonable result at rho identical with 1 / 2 √(u/sub e//x/sub e/) greater than 1.5. The medium cluster approach was applied to isotopic methanes to investigate the effects of intermolecular distance and mutual orientations of molecules in the liquid upon vapor pressure isotope effect. It was found that all geometrical effects studied tend to vanish as the size of clusters is increased. Isotope effect in the zero-point energy shifts on condensation was calculated on the basis of London dispersion forces in liquid and a semi-empirical molecular orbital theory, and was favorably compared with experimental results

  11. 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.

  12. Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

    International Nuclear Information System (INIS)

    Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

    1985-01-01

    The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

  13. 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.

  14. RAF/7/013: Enhancing the Use of Isotope Hydrology in Planning, Management and Development of Water Resources (AFRA)

    International Nuclear Information System (INIS)

    Opiyo, A.N.

    2017-01-01

    The project is a follow-up of RAF/8/048. Building capacity on isotope studies in Africa. It also relates IAEA KEN 7005 project on Evaluation of Surface and Groundwater Interaction of the Kilimanjaro Aquifer applying Isotope Techniques. The main aim of the project is to carry out Hydrological, Hydrogeological and geological, hydrogeo-chemical and geochemical studies and Water resources risks and vulnerability studies. AfriWatSan Project Relates to RAF/7/013 and it contribute to the overall objective

  15. 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

  16. High mass isotope separation arrangement

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1980-01-01

    This invention relates to the isotope separation art and, more particularly, to a selectively photon-induced energy level transition of an isotopic molecule containing the isotope to be separated and a chemical reaction with a chemically reactive agent to provide a chemical compound containing atoms of the isotope desired. In particular a description is given of a method of laser isotope separation applied to the separation of 235 UF 6 from 238 UF 6 . (U.K.)

  17. 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

  18. Variations in the stable isotope ratios of specific aromatic and aliphatic hydrocarbons from coal conversion processes

    Energy Technology Data Exchange (ETDEWEB)

    McRae, C.; Snape, C.E.; Fallick, A.E. [University of Strathclyde, Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

    1998-07-01

    To establish the scope for applying gas chromatography-isotope ratio mass spectrometry ({sup {delta}-13}C GC-IRMS) to molecular recognition problems in coal utilisation, {sup 13}C/{sup 12}C isotope ratios were determined for n-alkanes and polycyclic aromatic hydrocarbons (PAHs) as a function of coal rank and process conditions. Six coals ranging from a lignite to a low volatile bituminous coal were subjected to chloroform extraction, fixed-bed pyrolysis under hydrogen pressure (hydropyrolysis) and fluidised-bed (flash) pyrolysis. No significant variations in the stable isotope ratios of n-alkanes were evident as a function of either rank or conversion regime. In contrast, the isotope ratios of PAHs show large variations with those for hydropyrolysis (-23 to -25 parts per thousand) being similar to the bulk values of the initial coals and being isotopically heavier (less negative) than their fluidised-bed pyrolysis counterparts by 2-3 parts per thousand. However, the PAHs from fluidised-bed pyrolysis, which resemble closely those obtained from high temperature coal carbonization, are still heavier (by 2-3 parts per thousand) than those from diesel particulates and coal gasification and combustion residues. This provides a firm basis for the source apportionment of airborne PAHs in the proximity of coking plants, particularly with no major variations in the PAH isotope ratios being found as a function of rank.

  19. Inductively coupled plasma-mass spectrometry for elemental analysis and isotope ratio determinations in individual organic compounds separated by gas chromatography

    International Nuclear Information System (INIS)

    Chong, N.S.; Houk, R.S.

    1987-01-01

    A gas chromatograph (GC) with a packed column was interfaced to an inductively coupled plasma-mass spectrometer (ICP-MS) to yield atomic mass spectra from volatile organic compounds. Atomization of injected compounds was nearly complete and independent of molecular structure, so that elemental ratios could be determined. Detection limits were in the range 0.001 to 400 ng s -1 , depending on the ionization energy of the element and its abundance in the background spectrum. The relative standard deviation of measured isotope ratios varied from 0.4% for Br (i.e., a ratio close to unity) to 18% for N (a very large ratio). Thus, GC-ICP-MS provides elemental and isotope ratio information that is complementary to the molecular information derived from GC-MS with conventional ionization methods

  20. Isotope production

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Dewi M.

    1995-07-15

    Some 2 0% of patients using radiopharmaceuticals receive injections of materials produced by cyclotrons. There are over 200 cyclotrons worldwide; around 35 are operated by commercial companies solely for the production of radio-pharmaceuticals with another 25 accelerators producing medically useful isotopes. These neutron-deficient isotopes are usually produced by proton bombardment. All commonly used medical isotopes can be generated by 'compact' cyclotrons with energies up to 40 MeV and beam intensities in the range 50 to 400 microamps. Specially designed target systems contain gram-quantities of highly enriched stable isotopes as starting materials. The targets can accommodate the high power densities of the proton beams and are designed for automated remote handling. The complete manufacturing cycle includes large-scale target production, isotope generation by cyclotron beam bombardment, radio-chemical extraction, pharmaceutical dispensing, raw material recovery, and labelling/packaging prior to the rapid delivery of these short-lived products. All these manufacturing steps adhere to the pharmaceutical industry standards of Good Manufacturing Practice (GMP). Unlike research accelerators, commercial cyclotrons are customized 'compact' machines usually supplied by specialist companies such as IBA (Belgium), EBCO (Canada) or Scanditronix (Sweden). The design criteria for these commercial cyclotrons are - small magnet dimensions, power-efficient operation of magnet and radiofrequency systems, high intensity extracted proton beams, well defined beam size and automated computer control. Performance requirements include rapid startup and shutdown, high reliability to support the daily production of short-lived isotopes and low maintenance to minimize the radiation dose to personnel. In 1987 a major step forward in meeting these exacting industrial requirements came when IBA, together with the University of Louvain-La-Neuve in Belgium, developed the Cyclone-30

  1. Nitrogen and carbon isotope variability in the green-algal lichen Xanthoria parietina and their implications on mycobiont–photobiont interactions

    Science.gov (United States)

    Beck, Andreas; Mayr, Christoph

    2012-01-01

    Stable isotope patterns in lichens are known to vary largely, but effects of substrate on carbon and nitrogen stable isotope signatures of lichens were previously not investigated systematically. N and C contents and stable isotope (δ15N, δ13C) patterns have been measured in 92 lichen specimens of Xanthoria parietina from southern Bavaria growing on different substrates (bark and stone). Photobiont and mycobiont were isolated from selected populations and isotopically analyzed. Molecular investigations of the internal transcribed spacer of the nuclear ribosomal DNA (ITS nrDNA) region have been conducted on a subset of the specimens of X. parietina. Phylogenetic analysis showed no correlation between the symbionts X. parietina and Trebouxia decolorans and the substrate, isotope composition, or geographic origin. Instead specimens grown on organic substrate significantly differ in isotope values from those on minerogenic substrate. This study documents that the lichens growing on bark use additional or different N sources than the lichens growing on stone. δ15N variation of X. parietina apparently is controlled predominantly by the mass fraction of the mycobiont and its nitrogen isotope composition. In contrast with mycobionts, photobionts of X. parietina are much more 15N-depleted and show less isotopic variability than mycobionts, probably indicating a mycobiont-independent nitrogen acquisition by uptake of atmospheric ammonia. PMID:23301178

  2. Stable isotopes in barnacles as a tool to understand green sea turtle (Chelonia mydas) regional movement patterns

    Science.gov (United States)

    Detjen, M.; Sterling, E.; Gómez, A.

    2015-12-01

    Sea turtles are migratory animals that travel long distances between their feeding and breeding grounds. Traditional methods for researching sea turtle migratory behavior have important disadvantages, and the development of alternatives would enhance our ability to monitor and manage these globally endangered species. Here we report on the isotope signatures in green sea-turtle (Chelonia mydas) barnacles (Platylepas sp.) and discuss their potential relevance as tools with which to study green sea turtle migration and habitat use patterns. We analyzed oxygen (δ18O) and carbon (δ13C) isotope ratios in barnacle calcite layers from specimens collected from green turtles captured at the Palmyra Atoll National Wildlife Refuge (PANWR) in the central Pacific. Carbon isotopes were not informative in this study. However, the oxygen isotope results suggest likely regional movement patterns when mapped onto a predictive oxygen isotope map of the Pacific. Barnacle proxies could therefore complement other methods in understanding regional movement patterns, informing more effective conservation policy that takes into account connectivity between populations.

  3. C-13 isotopic studies of the surface catalysed reactions of methane

    International Nuclear Information System (INIS)

    Long, M.A.; He, S.J.X.; Adebajo, M.

    1997-01-01

    The ability of methane to methylate aromatic compounds, which are considered to be models for coal, is being studied. Related to this reaction, but at higher temperatures, is the direct formation of benzene from methane in the presence of these catalysts. Controversy exists in the literature on the former reaction, and 13 C isotope studies are being used to resolve the question. The interest in this reaction arises because the utilisation of methane, in the form of natural gas, in place of hydrogen for direct coal liquefaction would have major economic advantage. For this reason Isotope studies in this area have contributed significantly to an understanding of the methylation reactions. The paper describes experiments utilising methane 13 C, which show that methylation of aromatics such as naphthalene by the methane 13 C is catalysed by microporous, Cu-exchanged SAPO-5, at elevated pressures (6.8 MPa) and temperatures around 400 degree C. The mass spectrometric analysis and n.m.r. study of the isotopic composition of the products of the methylation reaction demonstrate unequivocally that methane provides the additional carbon atom for the methylated products. Thermodynamic calculations predict that the reaction is favourable at high methane pressures under these experimental conditions. The mechanism as suggested by the isotope study is discussed. The catalysts which show activity for the activation of methane for direct methylation of organic compounds, such as naphthalene, toluene, phenol and pyrene, are substituted aluminophosphate molecular sieves, EIAPO-5 (where El=Pb, Cu, Ni and Si) and a number of metal substituted zeolites. Our earlier tritium studies had shown that these catalysts will activate alkanes, at least as far as isotope hydrogen exchange reactions are concerned

  4. Replica Exchange Gaussian Accelerated Molecular Dynamics: Improved Enhanced Sampling and Free Energy Calculation.

    Science.gov (United States)

    Huang, Yu-Ming M; McCammon, J Andrew; Miao, Yinglong

    2018-04-10

    Through adding a harmonic boost potential to smooth the system potential energy surface, Gaussian accelerated molecular dynamics (GaMD) provides enhanced sampling and free energy calculation of biomolecules without the need of predefined reaction coordinates. This work continues to improve the acceleration power and energy reweighting of the GaMD by combining the GaMD with replica exchange algorithms. Two versions of replica exchange GaMD (rex-GaMD) are presented: force constant rex-GaMD and threshold energy rex-GaMD. During simulations of force constant rex-GaMD, the boost potential can be exchanged between replicas of different harmonic force constants with fixed threshold energy. However, the algorithm of threshold energy rex-GaMD tends to switch the threshold energy between lower and upper bounds for generating different levels of boost potential. Testing simulations on three model systems, including the alanine dipeptide, chignolin, and HIV protease, demonstrate that through continuous exchanges of the boost potential, the rex-GaMD simulations not only enhance the conformational transitions of the systems but also narrow down the distribution width of the applied boost potential for accurate energetic reweighting to recover biomolecular free energy profiles.

  5. The combined use of micro-hydropyrolysis and compound-specific isotope analysis (CSIA) as a novel technique to identify coal-derived biodegraded PAH flux in the complex environment

    Energy Technology Data Exchange (ETDEWEB)

    Cheng-Gong Sun; Gbolagade Olalere; Wisdom Ivwurie; Mick Cooper; Colin Snape [University of Nottingham, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre

    2007-07-01

    A novel analytical methodology combining CSIA and micro-hydropyrolysis (CSIA/micro-HyPy) has been developed to aid unambiguous source apportionment of PAHs in the complex environment where PAH matrices have been heavily biodegraded and/or their isotopic signatures are overlapping for some sources. Asphaltenes retain useful information of biogeochemical significance, which can be accessed via hydropyrolysis. The PAHs released from hydropyrolysis of asphaltenes, the bound PAHs, from different primary sources (e.g. crude oils, low and high temperature coal tars) were characterized and compared to free aromatics in regard to their molecular and 13C-isotopic profiles. It was found that hydropyrolysis of asphaltenes can generate molecular and isotopic profiles highly representative of their primary sources. For both low and high temperature coal tar, the bound aromatics have broadly similar molecular distributions to their free aromatic counterparts and have {sup 13}C-isotopic values almost identical to those of UK bituminous coals(-23{per_thousand}), indicating that the asphaltenes are actually released as representative fragments of coal structures during carbonization. As expected, the bound aromatics are more 13C-enriched by 1-3 {per_thousand} (-21 to -23{per_thousand}) compared to free aromatics (-24 to -26{per_thousand}). No significant isotopic difference was observed between free and bound aromatics for a North Sea crude oil, all having similar {sup 13}C-isotopic values (-27.2-30.2 {per_thousand}) that are significantly lighter than those for coal-derived aromatics. Applications of this novel methodological CSIA/micro-HyPy technique to samples previously examined from an area around a former carbonization plant have been successfully demonstrated where unambiguous source apportionment could not be achieved previously for the PAHs due to likely environmental alternation. 3 refs., 2 figs., 2 tabs.

  6. International symposium on isotope hydrology and integrated water resources management. Book of extended synopses

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-07-01

    Scarcity of freshwater, degradation of its quality, and increasing demand has motivated ongoing concern in the international community for more effective utilization of freshwater resources. The IAEA's symposia on the use of isotope techniques in water resources development and management have become a recurrent event held every four years. They have provided an international forum for a comprehensive review of the present state-of-the-art and recent advances made in this specific field as well as a basis for delineation of further research and development needs. The year 2003 marks the 40th anniversary of the first IAEA water resources symposium. Increasing use of isotope techniques over the past four decades, in part due to efforts of IAEA, has enhanced availability and effective use of isotopes to address water resources management issues. The Symposium covers a multi-disciplinary spectrum of research and applications of isotope techniques. The participation of isotope specialists, hydrologists, hydrogeologists, geochemists, environmental scientists and water managers is welcomed. The Organizers further encourage the participation and contribution of graduate students in these fields. The major areas covered include: Water cycle processes in the atmosphere and hydrosphere, including surface water, groundwater, and watershed-based studies, age dating of young groundwaters, water, carbon and nutrient cycling processes at the land-ocean-atmosphere interface, recent advances in analytical techniques for isotope hydrology and field applications of isotopes in groundwater or surface water resources management. This book of synopses covers oral presentations and poster sessions.

  7. Sensing site-specific structural characteristics and chirality using vibrational circular dichroism of isotope labeled peptides.

    Science.gov (United States)

    Keiderling, Timothy A

    2017-12-01

    Isotope labeling has a long history in chemistry as a tool for probing structure, offering enhanced sensitivity, or enabling site selection with a wide range of spectroscopic tools. Chirality sensitive methods such as electronic circular dichroism are global structural tools and have intrinsically low resolution. Consequently, they are generally insensitive to modifications to enhance site selectivity. The use of isotope labeling to modify vibrational spectra with unique resolvable frequency shifts can provide useful site-specific sensitivity, and these methods have been recently more widely expanded in biopolymer studies. While the spectral shifts resulting from changes in isotopic mass can provide resolution of modes from specific parts of the molecule and can allow detection of local change in structure with perturbation, these shifts alone do not directly indicate structure or chirality. With vibrational circular dichroism (VCD), the shifted bands and their resultant sign patterns can be used to indicate local conformations in labeled biopolymers, particularly if multiple labels are used and if their coupling is theoretically modeled. This mini-review discusses selected examples of the use of labeling specific amides in peptides to develop local structural insight with VCD spectra. © 2017 Wiley Periodicals, Inc.

  8. Isotope separation apparatus

    International Nuclear Information System (INIS)

    Lyon, R.K.; Eisner, P.N.; Thomas, W.R.I.

    1983-01-01

    This application discloses a method for and an apparatus in which isotopes of an element in a compared are separated from each other while that compound, i.e., including a mixture of such isotopes, flows along a predetermined path. The apparatus includes a flow tube having a beginning and an end. The mixture of isotopes is introduced into the flow tube at a first introduction point between the beginning and the end thereof to flow the mixture toward the end thereof. A laser irradiates the flow tube dissociating compounds of a preselected one of said isotopes thereby converting the mixture in an isotopically selective manner. The dissociation products are removed from the tube at a first removal point between the first introduction point and the end. The dissociation product removed at the the first removal point are reconverted back into the comound thereby providing a first stage enriched compound. This first stage enriched compound is reintroduced into the flow tube at a second introduction point between the beginning thereof and the first introduction point. Further product is removed from the flow tube at a second removal point between the second introduction point and the first introduction point. The second introduction point is chosen so that the isotope composition of the first stage enriched compound is approximately the same as that of the compound in the flow tube

  9. Molecular detection of drug resistance in microbes by isotopic techniques: The IAEA experience

    International Nuclear Information System (INIS)

    Dar, L.; Boussaha, A.; Padhy, A.K.; Khan, B.

    2003-01-01

    The International Atomic Energy Agency (IAEA) supports various programmes on the uses of radionuclide techniques in the management of human communicable diseases. An important issue, being addressed through several technology transfer projects, is the detection of drug resistance in microbes by radioisotope based molecular-biology diagnostic procedures. The techniques employed include dot blot hybridisation with P-32 labelled oligonucleotide probes to detect point mutations, associated with drug resistance, in microbial genes amplified by the polymerase chain reaction (PCR). Molecular methods have been used for the detection of drug resistance in the malarial parasite, Plasmodium falciparum, and in Mycobacterium tuberculosis. Radioisotope based molecular-biology methods have been demonstrated to have comparative advantages in being sensitive, specific, cost-effective, and suitable for application to large-scale molecular surveillance for drug resistance. (author)

  10. 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.

  11. Radionuclide measurements using resonantly enhanced collisional ionization

    International Nuclear Information System (INIS)

    Whitaker, T.J.; Bushaw, B.A.; Gerke, G.K.

    1987-01-01

    This report describes development of a laser-enhanced collisional ionization method for direct radionuclide measurements that are independent of radioactive decay. The technique uses two nitrogen-laser-pumped dye lasers to selectively excite the target isotope to an electronic state near the ionization threshold. The excited actinide atoms then undergo collisions with a buffer gas and are efficiently ionized. The resulting ions can be detected by conventional methods. The attributes of this approach include highly sensitive isotope analysis with relatively inexpensive lasers and a simple vacuum system. 9 refs., 3 figs

  12. Molecular effects in ion-electron emission from clean metal surfaces

    International Nuclear Information System (INIS)

    Baragiola, R.A.; Alonso, E.V.; Auciello, O.; Ferron, J.; Lantschner, G.; Oliva Florio, A.

    1978-01-01

    The authors have measured electron emission yields from clean Al, Cu and Ag under 2-50 keV H + , D + , H 2 + impact. It is found that molecular ion yields are lower than twice the yield of atomic ions. No isotope effects are observed for equal-velocity ions. (Auth.)

  13. The method for production of high purity carrier free ortophosphoric acid labeled with isotopes Phosphorus-32 and Phosphorus-33

    International Nuclear Information System (INIS)

    Abdukayumov, M.N.; Abdusalyamov, A.N.; Chistyakov, P.G.; Yuldashev, B.S.

    2001-01-01

    Extensive application for various radioactive isotopes was found in an extremity of the 20-Th century in a science and production. Labeled compounds are used with growing effectiveness in a molecular biology, gene engineering, medicine and other areas. Phosphorus-32 and Phosphorus-33 isotopes as a different labeled compounds that are used mainly in molecular biology are produced at the Radiopreparat enterprise of the Institute of Nuclear Physics of Academy of Sciences of Uzbekistan Republic. The quality of labeled preparations is very high. The specifications for above mentioned preparations corresponds to demands most of customers in different countries. P-32 or P-33 labeled orthophosphoric acid has high radiochemical purity (more than 99 %) and specific radioactivity close to theoretical. Orthophosphoric acid prepared by the described above method has radiochemical purity about 95 % and output of the target product 99%

  14. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Liang; Xie, Yun [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Du, Liang [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); School of Radiation Medicine and Protection (SRMP), School for Radiological and Interdisciplinary Sciences (RAD-X), Suzhou 215000 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Tan, Zhaoyi, E-mail: zhyitan@126.com [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-04-28

    Highlights: • This is the first theoretical investigation about T–H exchange in vacuum oil. • T–H isotope exchange is accomplished through two different change mechanisms. • Isotope exchange is selective, molecules with −OH and −COOH exchange more easily. • The methyl and methylene radicals in waste oil were observed by {sup 1}HNMR. - Abstract: The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium–hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T–H exchange mechanism and the hyrogenation–dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation–dehydrogenation exchange mechanism, the T–H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with −OH and −COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T–H isotope exchange can be determined by the hydrogenation of T{sub 2} or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products.

  15. A molecular dynamics study of liquid layering and thermal conductivity enhancement in nanoparticle suspensions

    Science.gov (United States)

    Paul, J.; Madhu, A. K.; Jayadeep, U. B.; Sobhan, C. B.; Peterson, G. P.

    2018-03-01

    Liquid layering is considered to be one of the factors contributing to the often anomalous enhancement in thermal conductivity of nanoparticle suspensions. The extent of this layering was found to be significant at lower particle sizes, as reported in an earlier work by the authors. In continuation to that work, an investigation was conducted to better understand the fundamental parameters impacting the reported anomalous enhancement in thermal conductivity of nanoparticle suspensions (nanofluids), utilizing equilibrium molecular dynamics simulations in a copper-argon system. Nanofluids containing nanoparticles of size less than 6 nm were investigated and studied analytically. The heat current auto-correlation function in the Green-Kubo formulation for thermal conductivity was decomposed into self-correlations and cross-correlations of different species and the kinetic, potential, collision and enthalpy terms of the dominant portion of the heat current vector. The presence of liquid layering around the nanoparticle was firmly established through simulations that show the dominant contribution of Ar-Ar self-correlation and the trend displayed by the kinetic-potential cross-correlation within the argon species.

  16. Isotopically exchangeable phosphorus

    International Nuclear Information System (INIS)

    Barbaro, N.O.

    1984-01-01

    A critique revision of isotope dilution is presented. The concepts and use of exchangeable phosphorus, the phosphate adsorption, the kinetics of isotopic exchange and the equilibrium time in soils are discussed. (M.A.C.) [pt

  17. Structure-based molecular simulations reveal the enhancement of biased Brownian motions in single-headed kinesin.

    Science.gov (United States)

    Kanada, Ryo; Kuwata, Takeshi; Kenzaki, Hiroo; Takada, Shoji

    2013-01-01

    Kinesin is a family of molecular motors that move unidirectionally along microtubules (MT) using ATP hydrolysis free energy. In the family, the conventional two-headed kinesin was experimentally characterized to move unidirectionally through "walking" in a hand-over-hand fashion by coordinated motions of the two heads. Interestingly a single-headed kinesin, a truncated KIF1A, still can generate a biased Brownian movement along MT, as observed by in vitro single molecule experiments. Thus, KIF1A must use a different mechanism from the conventional kinesin to achieve the unidirectional motions. Based on the energy landscape view of proteins, for the first time, we conducted a set of molecular simulations of the truncated KIF1A movements over an ATP hydrolysis cycle and found a mechanism exhibiting and enhancing stochastic forward-biased movements in a similar way to those in experiments. First, simulating stand-alone KIF1A, we did not find any biased movements, while we found that KIF1A with a large friction cargo-analog attached to the C-terminus can generate clearly biased Brownian movements upon an ATP hydrolysis cycle. The linked cargo-analog enhanced the detachment of the KIF1A from MT. Once detached, diffusion of the KIF1A head was restricted around the large cargo which was located in front of the head at the time of detachment, thus generating a forward bias of the diffusion. The cargo plays the role of a diffusional anchor, or cane, in KIF1A "walking."

  18. Structure-based molecular simulations reveal the enhancement of biased Brownian motions in single-headed kinesin.

    Directory of Open Access Journals (Sweden)

    Ryo Kanada

    Full Text Available Kinesin is a family of molecular motors that move unidirectionally along microtubules (MT using ATP hydrolysis free energy. In the family, the conventional two-headed kinesin was experimentally characterized to move unidirectionally through "walking" in a hand-over-hand fashion by coordinated motions of the two heads. Interestingly a single-headed kinesin, a truncated KIF1A, still can generate a biased Brownian movement along MT, as observed by in vitro single molecule experiments. Thus, KIF1A must use a different mechanism from the conventional kinesin to achieve the unidirectional motions. Based on the energy landscape view of proteins, for the first time, we conducted a set of molecular simulations of the truncated KIF1A movements over an ATP hydrolysis cycle and found a mechanism exhibiting and enhancing stochastic forward-biased movements in a similar way to those in experiments. First, simulating stand-alone KIF1A, we did not find any biased movements, while we found that KIF1A with a large friction cargo-analog attached to the C-terminus can generate clearly biased Brownian movements upon an ATP hydrolysis cycle. The linked cargo-analog enhanced the detachment of the KIF1A from MT. Once detached, diffusion of the KIF1A head was restricted around the large cargo which was located in front of the head at the time of detachment, thus generating a forward bias of the diffusion. The cargo plays the role of a diffusional anchor, or cane, in KIF1A "walking."

  19. Enhanced decomposition of dimethyl phthalate via molecular oxygen activated by Fe-Fe{sub 2}O{sub 3}/AC under microwave irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yiling [Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 (China); Ai, Zhihui, E-mail: jennifer.ai@mail.ccnu.edu.cn [Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 (China); Zhang, Lizhi [Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079 (China)

    2012-10-15

    Highlights: Black-Right-Pointing-Pointer Microwave irradiation induces the electrons transferring from AC to Fe-Fe{sub 2}O{sub 3} and reacts with molecular oxygen. Black-Right-Pointing-Pointer Microwave heating accelerates the electron transferring from AC to Fe-Fe{sub 2}O{sub 3} to generate reactive oxygen species. Black-Right-Pointing-Pointer This environmental remediation method is feasible for aqueous organic pollutants treatment. - Abstract: In this study, we demonstrate that the decomposition of dimethyl phthalate under microwave irradiation could be greatly enhanced over Fe-Fe{sub 2}O{sub 3} nanowires supported on activated carbon (Fe-Fe{sub 2}O{sub 3}/AC). The great enhanced decomposition of dimethyl phthalate could be attributed to a unique microwave induced molecular oxygen activation process. Upon microwave irradiation, electrons could be transferred from activated carbon to zero-valent iron, and then react with molecular oxygen to form O{sub 2}{center_dot}{sup -} and {center_dot}OH radicals for the decomposition of dimethyl phthalate. The deactivation and the regeneration of Fe-Fe{sub 2}O{sub 3}/AC catalyst were systematically studied. We also found that microwave heating could accelerate the electron transferring from AC to Fe-Fe{sub 2}O{sub 3} to generate more reactive oxygen species for the decomposition of DMP than conventional oil bath heating. This novel molecular oxygen activation approach may find applications for wastewater treatment and drinking water purification.

  20. Quadrupole and octupole collectivity and cluster structures in neon isotopes

    Science.gov (United States)

    Marević, P.; Ebran, J.-P.; Khan, E.; Nikšić, T.; Vretenar, D.

    2018-02-01

    The lowest positive- and negative-parity bands of 20Ne and neutron-rich even-even Ne isotopes are investigated using a theoretical framework based on energy density functionals. Starting from a self-consistent relativistic Hartree-Bogoliubov calculation of axially symmetric and reflection-asymmetric deformation energy surfaces, the collective symmetry-conserving states are built using projection techniques and the generator coordinate method. Overall a good agreement with the experimental excitation energies and transition rates is obtained. In particular, the model provides an accurate description of the excitation spectra and transition probabilities in 20Ne. The contribution of cluster configurations to the low-energy states is discussed, as well as the transitional character of the ground state. The analysis is extended to 22Ne and the shape-coexisting isotope 24Ne, and to the drip-line nuclei 32Ne and 34Ne. The role of valence neutrons in the formation of molecular-type bonds between clusters is discussed.

  1. 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

  2. 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

  3. Isotopes Project

    International Nuclear Information System (INIS)

    Dairiki, J.M.; Browne, E.; Firestone, R.B.; Lederer, C.M.; Shirley, V.S.

    1984-01-01

    The Isotopes Project compiles and evaluates nuclear structure and decay data and disseminates these data to the scientific community. From 1940-1978 the Project had as its main objective the production of the Table of Isotopes. Since publication of the seventh (and last) edition in 1978, the group now coordinates its nuclear data evaluation efforts with those of other data centers via national and international nuclear data networks. The group is currently responsible for the evaluation of mass chains A = 167-194. All evaluated data are entered into the International Evaluated Nuclear Structure Data File (ENSDF) and are published in Nuclear Data Sheets. In addition to the evaluation effort, the Isotopes Project is responsible for production of the Radioactivity Handbook

  4. Evaluating the skills of isotope-enabled general circulation models against in situ atmospheric water vapor isotope observations

    DEFF Research Database (Denmark)

    Steen-Larsen, Hans Christian; Risi, C.; Werner, M.

    2017-01-01

    The skills of isotope-enabled general circulation models are evaluated against atmospheric water vapor isotopes. We have combined in situ observations of surface water vapor isotopes spanning multiple field seasons (2010, 2011, and 2012) from the top of the Greenland Ice Sheet (NEEM site: 77.45°N......: 2014). This allows us to benchmark the ability to simulate the daily water vapor isotope variations from five different simulations using isotope-enabled general circulation models. Our model-data comparison documents clear isotope biases both on top of the Greenland Ice Sheet (1-11% for δ18O and 4...... boundary layer water vapor isotopes of the Baffin Bay region show strong influence on the water vapor isotopes at the NEEM deep ice core-drilling site in northwest Greenland. Our evaluation of the simulations using isotope-enabled general circulation models also documents wide intermodel spatial...

  5. Stable isotope enrichment: Current and future potential

    International Nuclear Information System (INIS)

    Tracy, J.G.; Aaron, W.S.

    1992-01-01

    Oak Ridge National Laboratory (ORNL) operates the Isotope Enrichment Facility for the purpose of providing enriched stable isotopes, selected radioactive isotopes (including the actinides), and isotope-related materials and services for use in various research applications. ORNL is responsible for isotope enrichment and the distribution of approximately 225 nongaseous stable isotopes from 50 multi-isotopic elements. Many enriched isotope products are of prime importance in the fabrication of nuclear targets and the subsequent production of special radionuclides. State-of-the-art techniques to achieve special isotopic, chemical, and physical requirements are performed at ORNL This report describes the status and capabilities of the Isotope Enrichment Facility and the Isotope Research Materials Laboratory as well as emphasizing potential advancements in enrichment capabilities

  6. Stable isotope enrichment - current and future potential

    International Nuclear Information System (INIS)

    Tracy, J.G.; Aaron, W.S.

    1993-01-01

    Oak Ridge National Laboratory (ORNL) operates the Isotope Enrichment Facility for the purpose of providing enriched stable isotopes, selected radioactive isotopes (including the actinides), and isotope-related materials and services for use in various research applications. ORNL is responsible for isotope enrichment and the distribution of approximately 225 nongaseous stable isotopes from 50 multi-isotopic elements. Many enriched isotope products are of prime importance in the fabrication of nuclear targets and the subsequent production of special radionuclides. State-of-the-art techniques to achieve special isotopic, chemical, and physical requirements are performed at ORNL. This report describes the status and capabilities of the Isotope Enrichment Facility and the Isotope Research Materials Laboratory as well as emphasizing potential advancements in enrichment capabilities. (orig.)

  7. Stable Isotope Group 1982 progress report

    International Nuclear Information System (INIS)

    Stewart, M.K.

    1983-06-01

    The work of the Stable Isotope Group of the Institute of Nuclear Sciences during 1982, in the fields of isotope geology, isotope hydrology, geochronology, isotope biology and mass spectrometer instrumentation, is described

  8. Design of a compact permanent magnet Cyclotron Mass Spectrometer for the detection and measurement of trace isotopes

    International Nuclear Information System (INIS)

    Young, A.T.; Bertsche, K.J.; Clark, D.J.; Halbach, K.; Kunkel, W.B.; Leung, K.N.; Li, C.Y.

    1992-07-01

    A technique for the detection of trace amounts of rare isotopes, Cyclotron mass Spectrometry (CMS), is described. This technique uses the relationships between particle mass, charge, magnetic field strength and cyclotron orbital frequency to provide high mass resolution. The instrument also has high sensitivity and is capable of measuring isotopes with abundances of - 12 . Improvements now being implemented will lead to further increases in the sensitivity and enhance operating parameters such as cost, portability, and sample throughput

  9. Isotopic marking and tracers

    International Nuclear Information System (INIS)

    Morel, F.

    1997-01-01

    The use of radioactive isotopes as tracers in biology has been developed thanks to the economic generation of the required isotopes in accelerators and nuclear reactors, and to the multiple applications of tracers in the life domain; the most usual isotopes employed in biology are carbon, hydrogen, phosphorus and sulfur isotopes, because these elements are present in most of organic molecules. Most of the life science knowledge appears to be dependent to the extensive use of nuclear tools and radioactive tracers; the example of the utilization of radioactive phosphorus marked ATP to study the multiple reactions with proteins, nucleic acids, etc., is given

  10. Boron isotopes in geothermal systems

    International Nuclear Information System (INIS)

    Aggarwal, J.

    1997-01-01

    Boron is a highly mobile element and during water-rock reactions, boron is leached out of rocks with no apparent fractionation. In geothermal systems where the water recharging the systems are meteoric in origin, the B isotope ratio of the geothermal fluid reflects the B isotope ratio of the rocks. Seawater has a distinctive B isotope ratio and where seawater recharges the geothermal system, the B isotope ratio of the geothermal system reflects the mixing of rock derived B and seawater derived B. Any deviations of the actual B isotope ratio of a mixture reflects subtle differences in the water-rock ratios in the cold downwelling limb of the hydrothermal system. This paper will present data from a variety of different geothermal systems, including New Zealand; Iceland; Yellowston, USA; Ibusuki, Japan to show the range in B isotope ratios in active geothermal systems. Some of these systems show well defined mixing trends between seawater and the host rocks, whilst others show the boron isotope ratios of the host rock only. In geothermal systems containing high amounts of CO 2 boron isotope ratios from a volatile B source can also be inferred. (auth)

  11. Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

    Science.gov (United States)

    Pribil, Michael; Ridley, William I.; Emsbo, Poul

    2015-01-01

    Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  13. Isotopes in Greenland Precipitation

    DEFF Research Database (Denmark)

    Faber, Anne-Katrine

    Greenland ice cores offer a unique opportunity to investigate the climate system behaviour. The objective of this PhD project is to investigate isotope modelling of present- day conditions and conduct model-data comparison using Greenland ice cores. Thus this thesis investigates how the integration...... of model and data can be used to improve the understanding of climate changes. This is done through analysis of isotope modelling, observations and ice core measurements. This dissertation comprises three projects: (1) Modelling the isotopic response to changes in Arctic sea surface conditions, (2......) Constructing a new Greenland database of observations and present-day ice core measurements, and (3) Performance test of isotope-enabled CAM5 for Greenland. The recent decades of rapid Arctic sea ice decline are used as a basis for an observational-based model experiment using the isotope-enabled CAM model 3...

  14. Isotope separation process

    International Nuclear Information System (INIS)

    1976-01-01

    The invention relates to a process for separating a given material into two or more parts, in each of which the abundances of the isotopes of a given element differ from the abundances of the isotopes of the same material in the said material. More particularly, the invention relates to a method for the isotopically selective excitation of gas phase UF 6 by infrared photon absorption followed by selective reaction of said excited UF 6 with atomic chlorine, bromine, or iodine to form a product which may be separated by means known in the art

  15. Pb isotopes of Gorgona Island (Colombia): Isotopic variations correlated with magma type

    International Nuclear Information System (INIS)

    Dupre, B.; Echeverria, L.M.

    1984-01-01

    Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8x2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206 Pb/ 204 Pbproportional19.75) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle sourbe regions, and by mixing or contamination between them. (orig.)

  16. Pb isotopes of Gorgona Island (Colombia): isotopic variations correlated with magma type

    Science.gov (United States)

    Dupré, B.; Echeverría, L. M.

    1984-02-01

    Lead isotopic results obtained on komatiites and basalts from Gorgona Island provide evidence of large isotopic variations within a restricted area (8 × 2.5 km). The variations are correlated with differences in volcanic rock type. The highest isotopic ratios ( 206Pb/ 204Pb˜ 19.75 ) correspond to tholeiites which make up most of the island. The lowest ratios (18.3) correspond to the komatiites of the west coast of the island. Other rock types (komatiites of the east coast, K-tholeiites, picrites and tuffs) have isotopic characteristics intermediate between these two extreme values. These results are explained by the existence of two distinct mantle source regions, and by mixing or contamination between them.

  17. Interactive effects of elevated CO2 and nitrogen deposition on fatty acid molecular and isotope composition of above- and belowground tree biomass and forest soil fractions.

    Science.gov (United States)

    Griepentrog, Marco; Eglinton, Timothy I; Hagedorn, Frank; Schmidt, Michael W I; Wiesenberg, Guido L B

    2015-01-01

    Atmospheric carbon dioxide (CO2) and reactive nitrogen (N) concentrations have been increasing due to human activities and impact the global carbon (C) cycle by affecting plant photosynthesis and decomposition processes in soil. Large amounts of C are stored in plants and soils, but the mechanisms behind the stabilization of plant- and microbial-derived organic matter (OM) in soils are still under debate and it is not clear how N deposition affects soil OM dynamics. Here, we studied the effects of 4 years of elevated (13C-depleted) CO2 and N deposition in forest ecosystems established in open-top chambers on composition and turnover of fatty acids (FAs) in plants and soils. FAs served as biomarkers for plant- and microbial-derived OM in soil density fractions. We analyzed above- and belowground plant biomass of beech and spruce trees as well as soil density fractions for the total organic C and FA molecular and isotope (δ13C) composition. FAs did not accumulate relative to total organic C in fine mineral fractions, showing that FAs are not effectively stabilized by association with soil minerals. The δ13C values of FAs in plant biomass increased under high N deposition. However, the N effect was only apparent under elevated CO2 suggesting a N limitation of the system. In soil fractions, only isotope compositions of short-chain FAs (C16+18) were affected. Fractions of 'new' (experimental-derived) FAs were calculated using isotope depletion in elevated CO2 plots and decreased from free light to fine mineral fractions. 'New' FAs were higher in short-chain compared to long-chain FAs (C20-30), indicating a faster turnover of short-chain compared to long-chain FAs. Increased N deposition did not significantly affect the quantity of 'new' FAs in soil fractions, but showed a tendency of increased amounts of 'old' (pre-experimental) C suggesting that decomposition of 'old' C is retarded by high N inputs. © 2014 John Wiley & Sons Ltd.

  18. 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)

  19. Molecular dynamics simulation based on the multi-component molecular orbital method: Application to H5O2+,D5O2+,andT5O2+

    International Nuclear Information System (INIS)

    Ishimoto, Takayoshi; Koyama, Michihisa

    2012-01-01

    Graphical abstract: Molecular dynamics method based on multi-component molecular orbital method was applied to basic hydrogen bonding systems, H 5 O 2 + , and its isotopomers (D 5 O 2 + andT 5 O 2 + ). Highlights: ► Molecular dynamics method with nuclear quantum effect was developed. ► Multi-component molecular orbital method was used as ab initio MO calculation. ► Developed method applied to basic hydrogen bonding system, H 5 O 2 + , and isotopomers. ► O ⋯ O vibrational stretching reflected to the distribution of protonic wavefunctions. ► H/D/T isotope effect was also analyzed. - Abstract: We propose a molecular dynamics (MD) method based on the multi-component molecular orbital (MC M O) method, which takes into account the quantum effect of proton directly, for the detailed analyses of proton transfer in hydrogen bonding system. The MC M O based MD (MC M O-MD) method is applied to the basic structures, H 5 O 2 + (called “Zundel ion”), and its isotopomers (D 5 O 2 + andT 5 O 2 + ). We clearly demonstrate the geometrical difference of hydrogen bonded O ⋯ O distance induced by H/D/T isotope effect because the O ⋯ O in H-compound was longer than that in D- or T-compound. We also find the strong relation between stretching vibration of O ⋯ O and the distribution of hydrogen bonded protonic wavefunction because the protonic wavefunction tends to delocalize when the O ⋯ O distance becomes short during the dynamics. Our proposed MC M O-MD simulation is expected as a powerful tool to analyze the proton dynamics in hydrogen bonding systems.

  20. Stable Isotope Group 1983 progress report

    International Nuclear Information System (INIS)

    Stewart, M.K.

    1984-06-01

    The work of the Stable Isotope Group of the Institute of Nuclear Sciences in the fields of isotope geology, isotope hydrology, geochronology, isotope biology and related fields, and mass spectrometer instrumentation, during 1983, is described