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Sample records for chemical isotope exchange

  1. Mass-independent isotope effects in chemical exchange reaction

    International Nuclear Information System (INIS)

    Nishizawa, Kazushige

    2000-01-01

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

  2. Isotope separation by chemical exchange process: Final technical report

    International Nuclear Information System (INIS)

    Schneider, A.

    1987-02-01

    The feasibility of a chemical exchange method for the separation of the isotopes of europium was demonstrated in the system EuCl 2 -EuCl 3 . The single stage separation factor, α, in this system is 1.001 or 1.0005 per mass unit. This value of α is comparable to the separation factors reported for the U 4+ - U 6 and U 3+ - Y 4+ systems. The separation of the ionic species was done by precipitation of the Eu 2+ ions or by extraction of the Eu 3+ ions with HDEHP. Conceptual schemes were developed for a countercurrent reflux cascades consisting of solvent extraction contractors. A regenerative electrocel, combining simultaneous europium reduction, europium oxidation with energy generation, and europium stripping from the organic phase is described. 32 refs., 22 figs., 6 tabs

  3. Chemical exchange equilibria in isotope separation. Part I : Evaluation of separation factors

    International Nuclear Information System (INIS)

    Dave, S.M.

    1980-01-01

    The theory of chemical exchange equilibria as applied to the isotope separation processes and the isotope effects on equilibrium constants of different exchange reactions has come a long way since its inception by Urey and Rittenberg. An attempt has been made to bring relevant information together and present a unified approach to isotopic chemical exchange equilibrium constant evaluation and its implications to separation processes. (auth.)

  4. Early history of chemical exchange isotope enrichment and lessons we learn

    International Nuclear Information System (INIS)

    Ishida, Takanobu; Ono, Yuriko

    2006-01-01

    The chemical exchange isotope enrichment process has an advantage over other isotope separation methods in that it involves two chemicals rather than one and, consequently, relatively large separation factors can be obtained. However, the chemical exchange method requires a chemical conversion of the substance enriched in the target isotope into the second substance. The idiosyncrasies of the isotope separation process by this method are pointed out using McCabe-Thiele diagram and, from them, the difficulties involved in the chemical exchange methods are itemized. Examples of the points being made are taken from the pioneering works of this field carried out by Harold C. Urey, his contemporaries, the students and the students' students. Lessons we learn from these works are discussed. (author)

  5. Enrichment of {sup 15}N and {sup 10}B isotopes by chemical exchange process

    Energy Technology Data Exchange (ETDEWEB)

    D` Souza, A B; Sonwalkar, A S; Subrahmanyam, B V; Valladares, B A [Chemical Engineering Division, Bhabha Atomic Research Centre, Mumbai (India)

    1994-06-01

    Many processes are available for separation of stable isotopes like distillation, chemical exchange, thermal diffusion, gaseous diffusion, centrifuge etc. Chemical exchange process is eminently suitable for separation of isotopes of light elements. Work done on separation and enrichment of two of the stable isotopes viz. {sup 15}N and {sup 10}B in Chemical Engineering Division is presented. {sup 15}N is widely used as a tracer in agricultural research and {sup 10}B is used in nuclear industry as control rod material, soluble reactor poison, neutron detector etc. The work on {sup 15}N isotope resulted in a pilot plant, which was the only source of this material in the country for many years and later it was translated into a production plant as M/s. RCF Ltd. The work done on the ion-exchange process for enrichment of {sup 10}B isotope which is basically a chemical exchange process, is now being updated into a pilot plant to produce enriched {sup 10}B to be used as soluble reactor poison. (author). 5 refs., 2 figs., 3 tabs.

  6. Enrichment of 15N and 10B isotopes by chemical exchange process

    International Nuclear Information System (INIS)

    D'Souza, A.B.; Sonwalkar, A.S.; Subrahmanyam, B.V.; Valladares, B.A.

    1994-01-01

    Many processes are available for separation of stable isotopes like distillation, chemical exchange, thermal diffusion, gaseous diffusion, centrifuge etc. Chemical exchange process is eminently suitable for separation of isotopes of light elements. Work done on separation and enrichment of two of the stable isotopes viz. 15 N and 10 B in Chemical Engineering Division is presented. 15 N is widely used as a tracer in agricultural research and 10 B is used in nuclear industry as control rod material, soluble reactor poison, neutron detector etc. The work on 15 N isotope resulted in a pilot plant, which was the only source of this material in the country for many years and later it was translated into a production plant as M/s. RCF Ltd. The work done on the ion-exchange process for enrichment of 10 B isotope which is basically a chemical exchange process, is now being updated into a pilot plant to produce enriched 10 B to be used as soluble reactor poison. (author)

  7. A new cascade method for studying isotope effect in chemical exchange system without valance change

    International Nuclear Information System (INIS)

    Wen Xiaoning; Luo Wenzong

    1987-01-01

    A new cascade method for studying isotope effect in chemical exchange system without valance change is developed and described. This method is simple to use and consumes less extractant as compared with the commonly used Woodward method. It is also convenient for unstable systems

  8. Non-equilibrium mass transfer absorption model for the design of boron isotopes chemical exchange column

    International Nuclear Information System (INIS)

    Bai, Peng; Fan, Kaigong; Guo, Xianghai; Zhang, Haocui

    2016-01-01

    Highlights: • We propose a non-equilibrium mass transfer absorption model instead of a distillation equilibrium model to calculate boron isotopes separation. • We apply the model to calculate the needed column height to meet prescribed separation requirements. - Abstract: To interpret the phenomenon of chemical exchange in boron isotopes separation accurately, the process is specified as an absorption–reaction–desorption hybrid process instead of a distillation equilibrium model, the non-equilibrium mass transfer absorption model is put forward and a mass transfer enhancement factor E is introduced to find the packing height needed to meet the specified separation requirements with MATLAB.

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

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  10. 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

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

    International Nuclear Information System (INIS)

    Xuelei Chu; Ohmoto, Hiroshi

    1991-01-01

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

  12. Isothermal and non-isothermal conditions of isotope separation by chemical exchange method

    International Nuclear Information System (INIS)

    Khoroshilov, A.V.; Andreev, B.M.; Katalnikov, S.G.

    1992-01-01

    The published data about the effect of temperature on thermodynamic and mass transfer parameters of isotope separation by the chemical exchange method were used to examine the influence of iso- and non-isothermal conditions on the effectiveness of the separation process. It has been shown that simultaneous fulfillment of several optimization criteria is impossible in optimization of the isothermal process. If the limitation that temperature must be constant in the whole range of concentrational changes for an isolated isotope is removed, then it is possible to solve the problem of optimization with simultaneous fulfillment of several optimization criteria. When the separation process is carried out with non-isothermal conditions, that is, in temperature cascade, then the maximum concentration change takes place at every theoretical separation plate, and whole cascade is characterised by maximum throughput, minimum height and volume, and minimum cost for the stream reflux. From the results of our study, it was concluded that in the optimum temperature cascade, the cost of production of unity quantity of isotope can be decreased at least by a factor of two as compared with the optimal isothermal version of the separation process. (author)

  13. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

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

  14. Magnetic isotope effect and theory of atomic orbital hybridization to predict a mechanism of chemical exchange reactions.

    Science.gov (United States)

    Epov, Vladimir N

    2011-08-07

    A novel approach is suggested to investigate the mechanisms of chemical complexation reactions based on the results of Fujii with co-workers; they have experimentally observed that several metals and metalloids demonstrate mass-independent isotope fractionation during the reactions with the DC18C6 crown ether using solvent-solvent extraction. In this manuscript, the isotope fractionation caused by the magnetic isotope effect is used to understand the mechanisms of chemical exchange reactions. Due to the rule that reactions are allowed for certain electron spin states, and forbidden for others, magnetic isotopes show chemical anomalies during these reactions. Mass-independent fractionation is suggested to take place due to the hyperfine interaction of the nuclear spin with the electron spin of the intermediate product. Moreover, the sign of the mass-independent fractionation is found to be dependent on the element and its species, which is also explained by the magnetic isotope effect. For example, highly negative mass-independent isotope fractionation of magnetic isotopes was observed for reactions of DC18C6 with SnCl(2) species and with several Ru(III) chloro-species, and highly positive for reactions of this ether with TeCl(6)(2-), and with several Cd(II) and Pd(II) species. The atomic radius of an element is also a critical parameter for the reaction with crown ether, particularly the element ions with [Kr]4d(n)5s(m) electron shell fits the best with the DC18C6 crown ring. It is demonstrated that the magnetic isotope effect in combination with the theory of orbital hybridization can help to understand the mechanism of complexation reactions. The suggested approach is also applied to explain previously published mass-independent fractionation of Hg isotopes in other types of chemical exchange reactions. This journal is © the Owner Societies 2011

  15. Separation and sampling technique of light element isotopes by chemical exchange process

    International Nuclear Information System (INIS)

    Kato, Shunsaku; Oi, Kenta; Takagi, Norio; Hirotsu, Takafumi; Kano, Hirofumi; Sonoda, Akinari; Makita, Yoji

    2000-01-01

    Lithium and boron isotope separation technique were studied. Granulation of lithium isotope separation agent was carried out by cure covering in solution. Separation of lithium isotope was stepped up by ammonium carbonate used as elusion agent. Styrene and ester resin derived three kinds of agents such as 2-amino-1, 3-propanediol (1, 3-PD), 2-amino-2-methyl-1, 3-propanediol (Me-1,3-PD) and tris(2-hydroxyethyl)amine (Tris) were used as absorbent.The ester resin with Tris showed larger amount of adsorption (1.4 mmol/g) than other resins. However, all resins with agent indicated more large adsorption volume of boron than the objective value (0.5 mmol/g). Large isotope shift was shown by the unsymmetrical vibration mode of lithium ion on the basis of quantum chemical calculation of isotope effect on dehydration of hydrated lithium ion. (S.Y.)

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

    International Nuclear Information System (INIS)

    Knoechel, A.; Wilken, R.D.

    1981-01-01

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

  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. Physico-Chemical Study of the Separation of Calcium Isotopes by Chemical Exchange Between Amalgam and Salt Solutions

    International Nuclear Information System (INIS)

    Duie, P.; Dirian, G.

    1962-01-01

    In a preliminary study of the isotopic exchange between Ca amalgam and aqueous or organic solutions of Ca salts, the main parameters governing the feasibility of a separation process based on these systems such as separation factor, exchange kinetics, rate of decomposition of the amalgam were investigated. The separation factor between 40 Ca and 46 Ca was found to be of the order of 1.02. The rate of the exchange reaction is rather low for aqueous solutions, extremely low for organic solutions. The amalgam seems not to be attacked by dimethyl-formamide solutions; but it is rapidly decomposed by aqueous solutions of Ca halides. This decomposition is slow in the case of aqueous solutions of calcium formate and still slower for Ca(OH) 2 ; however, except in particular conditions, the observed rate is often much higher, owing to interfering reactions between amalgam and water vapor contained in H 2 bubbles. (authors) [fr

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

    Science.gov (United States)

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

    2012-10-01

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

  1. Dual temperature isotope exchange system

    International Nuclear Information System (INIS)

    Spevack, J.S.

    1976-01-01

    Improvements in the method for isotope concentration by dual temperature exchange between feed and auxiliary fluids in a multistage system are described. In a preferred embodiment the first is a vaporizable liquid and the auxiliary fluid a gas, comprising steps for improving the heating and/or cooling and/or humidifying and/or dehumidifying operations

  2. 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

  3. Isotope Exchange in Oxide Catalyst

    Science.gov (United States)

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

    1987-01-01

    Replacement technique maintains level of CO2/18 in closed-cycle CO2 lasers. High-energy, pulsed CO2 lasers using rare chemical isotopes must be operated in closed cycles to conserve gas. Rare isotopes operated in closed cycles to conserve gas. Rare isotopes as CO2/18 used for improved transmission of laser beam in atmosphere. To maintain laser power, CO2 must be regenerated, and O2 concentration kept below few tenths of percent. Conditions achieved by recombining CO and O2.

  4. New NMR method for measuring the difference between corresponding proton and deuterium chemical shifts: isotope effects on exchange equilibria

    International Nuclear Information System (INIS)

    Saunders, M.; Saunders, S.; Johnson, C.A.

    1984-01-01

    A convenient and accurate method is described for measuring the difference between a proton frequency and the corresponding deuterium frequency in its deuterated analogue relative to a reference system by using the deuterium lock in a Fourier-transform NMR spectrometer. This measurement is a sensitive way of measuring equilibrium isotope effects for hydrogen-deuterium exchange. A value of 1.60 per H-D pair is obtained for the equilibrium 2H 3 O + + 3D 2 O in equilibrium 2D 3 O + + 3H 2 O at 30 0 C in aqueous perchloric acid (HClO 4 ). 7 references, 2 tables

  5. Catalysed hydrogen isotope exchange

    International Nuclear Information System (INIS)

    1973-01-01

    A method is described for enhancing the rate of exchange of hydrogen atoms in organic compounds or moieties with deuterium or tritium atoms. It comprises reacting the organic compound or moiety and a compound which is the source of deuterium or tritium in the presence of a catalyst consisting of a non-metallic, metallic or organometallic halide of Lewis acid character and which is reactive towards water, hydrogen halides or similar protonic acids. The catalyst is a halide or organometallic halide of: (i) zinc or another element of Group IIb; (ii) boron, aluminium or another element of Group III; (iii) tin, lead, antimony or another element of Groups IV to VI; or (iv) a transition metal, lanthanide or stable actinide; or a halohalide. (author)

  6. Isotope exchange reactions in hydrogen mixtures

    International Nuclear Information System (INIS)

    Czaplinski, W.; Gula, A.; Kravtsov, A.; Mikhailov, A.; Popov, N.

    1990-12-01

    The rates of isotopic exchange for the excited states of muonic hydrogen are calculated as functions of collision energy. Ground state population q 1s for different collision energies, target densities and isotope concentrations is obtained. It is shown that for principal quantum numbers n > 5 the isotopic exchange still considerably influences the value of q 1s . (author)

  7. 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

  8. Isotope exchange process and device

    International Nuclear Information System (INIS)

    Delvalle, Pierre.

    1974-01-01

    A process for enriching uranium in one of its isotopes is described. To do so, cascade isotopic exchanges are made by contact between U(III) and U(IV) in conditions avoiding the oxidation of U(III) in U(IV). A liquid phase containing an uranium compound and free of other group III to VIII metals of the periodic classification, in which uranium is present at a first valence is placed in contact with a second valence uranium compound, protected from any contact with a conducting solid and with an agent bringing free or release oxygen. The second phase is organic. The process includes a counter current isotopic exchange between an aqueous phase containing a U +4 salting-out agent and the uranium as U +3 ions and an organic phase containing the uranium at valence IV. This is followed by the extraction of U(IV) from the organic phase into the previously spent aqueous phase and the reduction of uranium from valence IV to valence III; finally by oxidation of U(III) of the aqueous phase into U(IV) and the transfer of U(IV) into the previously exhausted organic phase [fr

  9. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

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

    International Nuclear Information System (INIS)

    Gupta, A.R.

    1979-01-01

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

  11. Isotope effects on chemical equilibria

    International Nuclear Information System (INIS)

    Golding, P.D.

    1974-01-01

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

  12. 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

  13. Calcium isotope fractionation in ion-exchange chromatography

    International Nuclear Information System (INIS)

    Russell, W.A.; Papanastassiou, D.A.

    1978-01-01

    Significant fractionation of the isotopes of calcium has been observed during elution through short ion-exchange columns packed with Dowex 50W-X8 resin. A double isotopic tracer was used to provide correction for instrumental fractionation effects. The absolute 40 Ca/ 44 Ca ratio is determined by this method to 0.05% and provides a measure of the fractionation of all Ca isotopes. It is found that the lighter isotopes are preferentially retained by the resin, with variations in 40 Ca/ 44 Ca between the first and last fractions of up to 1.1%. An estimate of the separation factor between batch solute and resin gives epsilon = 2.1 x 10 -4 . Details of the chemical or physical mechanisms causing isotope fractionation of Li, Na, Ca, and other elements during ion-exchange chromatography are not yet clear

  14. Isotope exchange reaction on solid breeder materials

    International Nuclear Information System (INIS)

    Baba, A.; Nishikawa, M.; Eguchi, T.; Kawagoe, T.

    2000-01-01

    Lithium ceramic materials such as Li 2 O, LiAlO 2 , Li 2 ZrO 3 , Li 2 TiO 3 and Li 4 SiO 4 are considered to be as candidate for the tritium breeding material in a deuterium-tritium (D-T) fusion reactor. In the recent blanket designs, helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas to reduce tritium inventory and promote tritium release from the breeding material. In addition, the rate of isotope exchange reaction between hydrogen isotopes in the purge gas and tritium on the surface of the breeding material is necessary to analyze the tritium release behavior from the breeding materials. However, the rate of isotope exchange reactions between hydrogen isotopes in the purge gas and tritium on the surface of those materials has not been quantified until recently. Recently, the present authors quantified the rate of isotope exchange reaction on Li 2 O and Li 2 ZrO 3 . The overall mass transfer coefficients representing the isotope exchange reaction between H 2 and D 2 O on breeding materials or the same between D 2 and H 2 O are experimentally obtained in this study. Comparison to isotope exchange reaction rates on various breeding materials is also performed in this study. Discussions about the effects of temperature, concentration of hydrogen in the purge gas or flow rate of the purge gas on the conversion of tritiated water to tritium gas are also performed

  15. Studies on Some Physical, Chemical and Sorption Properties of Some Inorganic ion Exchangers and Their Application to Radioactive Isotopes Removal

    International Nuclear Information System (INIS)

    El-Sweify, F.H.; Shehata, M.K.K.; El-Shazly, E.A.A.

    1999-01-01

    In the present work, amorphous zirconium phosphate, zirconium titanium phosphate and ceric tungstate have been synthesised. Solubility of the prepared ion exchangers in different media has been examined. These media were mineral acids, aqueous solutions of organic acids: oxalic, citric and tartaric as well as ammonium and potassium carbonate solutions of different molarities. I.R. analysis is applied on some samples of the prepared ion exchangers. Sorption behaviour of different metal ion species, of elements of nuclear significance on the prepared ion exchangers has been studied from aqueous media of different compositions and concentration under different experimental conditions. The studied metal ions are, Ce(III) and Eu(III), as representative for the trivalent lanthanides, Co(II), Zr(IV), Nb(V), Hf(IV), Te(IV), Ce(IV), Th(IV) and U(V I). Optimization of the conditions for the isolation and separation of the desired element species highlighted

  16. Determination of kinetic parameters of heterogeneous isotopic exchange reaction

    International Nuclear Information System (INIS)

    Huang, Ting-Chia; Tsai, Fuan-Nan

    1977-01-01

    A mathematical model has been proposed for a heterogeneous isotopic exchange reaction which involves film diffusion, surface chemical reaction and intraparticle diffusion. The exchange equation to predict the exchange fraction as a function of time for the spherical particles immersed in a solution of finite volume has been derived. The relations between the exchange fraction and dimensionless time are plotted with xi(=ak sub(f)/KD sub(e)), xi 1 (=K 1 a 2 /D sub(e)) and final fractional uptake as parameters. From the values of the kinetic parameters xi and xi 1 , the relative importance of each limiting step is discussed. Experimental results of the isotopic exchange reaction of calcium ion in both system CaCO 3 (s)/Ca 2+ (aq) and system calcium type resin Dowex 50W-X8/Ca 2+ (aq) are coincident with the theoretical equation proposed in this study. (auth.)

  17. 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

  18. Isotope exchange in oxide-containing catalyst

    Science.gov (United States)

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

    1989-01-01

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

  19. 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

  20. Factors determining the activity of catalysts of various chemical types in the oxidation of hydrogen. I. Oxidation and isotope exchange of hydrogen on cobalt monoxide-oxide

    International Nuclear Information System (INIS)

    Polgikh, L.Y.; Golodets, G.I.; Il'chenko, N.I.

    1985-01-01

    On the basis of data on the kinetics of the reaction 2H 2 + O 2 = 2H 2 O isotope exchange H 2 + D 2 = 2HD under the conditions of oxidative catalysis, and the kinetic isotope effect, a mechanism is proposed for the oxidation of hydrogen on cobalt monoxide-oxide. At low temperatures the reaction proceeds according to a mechanism of alternating reduction-reoxidation of the surface with the participation of hydrogen adsorbed in molecular form; at increased temperature and low P 02 /P /SUB H2/ ratios, a significant contribution to the observed rate is made by a mechanism including dissociative chemisorption of hydrogen

  1. Gas-phase ion/molecule isotope-exchange reactions: methodology for counting hydrogen atoms in specific organic structural environments by chemical ionization mass spectrometry

    International Nuclear Information System (INIS)

    Hunt, D.F.; Sethi, S.K.

    1980-01-01

    Ion/molecule reactions are described which facilitate exchange of hydrogens for deuteriums in a variety of different chemical environments. Aromatic hydrogens in alkylbenzenes, oxygenated benzenes, m-toluidine, m-phenylenediamine, thiophene, and several polycyclic aromatic hydrocarbons and metallocenes are exchanged under positive ion CI conditions by using either D 2 O, EtOD, or ND 3 as the reagent gas. Aromatic hydrogens, benzylic hydrogens, and hydrogens on carbon adjacent to carbonyl groups suffer exchange under negative ion CI conditions in ND 3 , D 2 O, and EtOD, respectively. A possible mechanism for the exchange process is discussed. 1 figure, 2 tables

  2. Physico-Chemical Study of the Separation of Calcium Isotopes by Chemical Exchange Between Amalgam and Salt Solutions; Etude physico-chimique de la separation des isotopes du calcium par echange chimique entre amalgame et solution saline

    Energy Technology Data Exchange (ETDEWEB)

    Duie, P; Dirian, G [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)

    1962-07-01

    In a preliminary study of the isotopic exchange between Ca amalgam and aqueous or organic solutions of Ca salts, the main parameters governing the feasibility of a separation process based on these systems such as separation factor, exchange kinetics, rate of decomposition of the amalgam were investigated. The separation factor between {sup 40}Ca and {sup 46}Ca was found to be of the order of 1.02. The rate of the exchange reaction is rather low for aqueous solutions, extremely low for organic solutions. The amalgam seems not to be attacked by dimethyl-formamide solutions; but it is rapidly decomposed by aqueous solutions of Ca halides. This decomposition is slow in the case of aqueous solutions of calcium formate and still slower for Ca(OH){sub 2}; however, except in particular conditions, the observed rate is often much higher, owing to interfering reactions between amalgam and water vapor contained in H{sub 2} bubbles. (authors) [French] On a fait une etude preliminaire, pour des systemes amalgame de calcium - solution aqueuse ou organique de sels de calcium, des principaux parametres pouvant intervenir dans l'application d'un procede d'echange a l'enrichissement isotopique du calcium: facteur de separation, cinetique de l'echange, cinetique de la decomposition de l'amalgame. Les facteurs de separation {sup 40}Ca-{sup 46}Ca sont de l'ordre de 1,02. L'echange est assez lent pour les solutions aqueuses, extremement lent pour les solutions organiques. La decomposition de l'amalgame est pratiquement inexistante avec les solutions dans le dimethyl- formamide, appreciable pour les solutions alcooliques, rapide pour les solutions aqueuses d'halogenures; elle est normalement lente pour les solutions aqueuses de formiate et surtout de chaux, mais la decomposition est en general acceleree par une reaction parasite entre l'amalgame et l'eau a l'etat vapeur, reaction que l'on n'evite dans des conditions tres particulieres. (auteurs)

  3. Oxygen isotope exchange on palladium catalysts

    International Nuclear Information System (INIS)

    Kravchuk, L.S.; Beschetvertnaya, T.I.; Novorodskij, V.G.; Novikova, M.G.; Zaretskij, M.V.; Valieva, S.V.

    1983-01-01

    Oxygen heteromolecular isotope exchange on unreduced palladium catalysts, distingushing by metal content is studied. Content of 18 O in gaseous phase is eoual to 46%. Calculations of heteroexchange rates are conducted with decrease of the 18 O in the gaseous phase over solid sample. Method of oxygen thermodesorption has been used to establish that palladium, deposited on γ-Al 2 O 3 during exchange process is in oxidized state; in this case strength of Pd-O bond is determined by content dispersity) of the metal. It is shown that significant increase of exchange rate on the samples with Pd >> 0.5 mass.% content can be induced as by side decomposition reaction of its oxide and corresponding dilution of gaseous mixture by ''light'' oxygen so by possibility of exchange with oxygen of PdO phase

  4. Radiation-related retrograde hydrogen isotope and K-Ar exchange in clay minerals

    International Nuclear Information System (INIS)

    Halter, C.; Pagel, M.; Sheppard, S.M.F.; Weber, F.; Clauer, N.

    1987-01-01

    Hydrogen and oxygen isotope studies have been widely applied to characterize the origin of fluids during ore-foaming processes. The primary isotope record, however, may be disturbed by retrograde exchange reactions, thus complicating the interpretation of the data. The susceptibility of minerals to retrograde isotope and chemical exchange is variable, reflecting differences in the mechanism and rate of isotope exchange. Results are presented on deuterium depletion, K/Ar ages and H 2 O + content of illites associated with uranium mineralization from the Athabasca basin (Canada). (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-08-01

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

  6. Radioiodination via isotope exchange in pivalic acid

    International Nuclear Information System (INIS)

    Weichert, J.P.; Van Dort, M.E.; Groziak, M.P.; Counsell, R.E.

    1986-01-01

    A variety of benzoic and aryl aliphatic mono and polyiodinated acids and esters (sterol, triglyceride) were radioiodinated in 55-99% radiochemical yield by isotope exchange with Na 125 i in a melt of pivalic acid. In general, the reaction was complete in 1 h at 155 0 C with little or no substrate decomposition. High specific activity studies afforded 125 I-labeled iopanoic acid with a specific activity of over 700 Ci/mmol. (author)

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

    Science.gov (United States)

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

    2009-12-30

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

  8. Procedure and apparatus for isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Delvalle, Pierre

    1977-09-30

    A process for enriching uranium in one of its isotopes is described. To do so, cascade isotopic exchanges are made by contact between U(III) and U(IV) in conditions avoiding the oxidation of U(III) in U(IV). A liquid phase containing a uranium compound and free of other Group III to VIII metals of the periodic classification, in which uranium is present at a first valence is placed in contact with a second valence uranium compound, protected from any contact with a conducting solid and with an agent bringing free or release oxygen. The second phase is organic. The process includes a counter current isotopic exchange between an aqueous phase containing a U/sup +4/salting-out agent and the uranium as U/sup +3/ ions and an organic phase containing the uranium at Valence IV. This is followed by the extraction of U(IV) from the organic phase into the previously spent aqueous phase and the reduction of uranium from Valence IV to Valence III finally by oxidation of U(III) of the aqueous phase into U(IV) and the transfer of U(IV) into the previously exhausted organic phase.

  9. Hydrogen-water isotopic exchange process

    International Nuclear Information System (INIS)

    Cheung, H.

    1984-01-01

    The objects of this invention are achieved by a dual temperature isotopic exchange process employing hydrogen-water exchange with water passing in a closed recirculation loop between a catalyst-containing cold tower and the upper portion of a catalyst-containing hot tower, with feed water being introduced to the lower portion of the hot tower and being maintained out of contact with the water recirculating in the closed loop. Undue retarding of catalyst activity during deuterium concentration can thus be avoided. The cold tower and the upper portion of the hot tower can be operated with relatively expensive catalyst material of higher catalyst activity, while the lower portion of the hot tower can be operated with a relatively less expensive, more rugged catalyst material of lesser catalyst activity. The feed water stream, being restricted solely to the lower portion of the hot tower, requires minimal pretreatment for the removal of potential catalyst contaminants. The catalyst materials are desirably coated with a hydrophobic treating material so as to be substantially inaccessible to liquid water, thereby retarding catalyst fouling while being accessible to the gas for enhancing isotopic exchange between hydrogen gas and water vapor. A portion of the water of the closed loop can be passed to a humidification zone to heat and humidify the circulating hydrogen gas and then returned to the closed loop

  10. Water-hydrogen isotope exchange process analysis

    International Nuclear Information System (INIS)

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

    2008-01-01

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

  11. Isotopic anomalies - chemical memory of Galactic evolution

    International Nuclear Information System (INIS)

    Clayton, D.D.

    1988-01-01

    New mechanisms for the chemical memory of isotopic anomalies are proposed which are based on the temporal change during the chemical evolution of the Galaxy of the isotopic composition of the mean ejecta from stars. Because of the differing temporal evolution of primary and secondary products of nucleosynthesis, the isotopic composition of the bulk interstellar medium changes approximately linearly with time, and thus any dust component having an age different from that of average dust will be isotopically anomalous. Special attention is given to C, O, Mg, Si, and isotopically heavy average-stellar condensates of SiC. 20 references

  12. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

    Under the influence of tritium β-radiation, 1,4-dioxan undergoes hydrogen exchange with the solvent water. The inhibition of the reaction by known electron scavengers (Ag + , Cu 2+ , Ni 2+ , Co 2+ , Zn 2+ , H 3 + O) and also by species with high reactivity towards hydroxyl radicals but negligible reactivity towards solvated electrons (N 3 - , Br - , SCN - ) has been examined in detail. γ-irradiation similarly induces hydrogen exchange. The action of scavengers is interpreted as requiring the involvement of two separately scavengeable primary radiolysis products in the sequence of reactions leading to exchange. The presence of electron scavengers, even at high concentration, does not totally inhibit the exchange, and a secondary exchange route, involving a low vacancy state of inhibitor cations, is considered responsible for the 'unscavengeable' portion of the reaction, by providing an alternative exchange route. Analogies are drawn between the exchange reaction and other radiation-induced reactions that are thought to involve spur processes. Some implication of radiation-chemical studies in water-alcohol mixtures are indicated. (author)

  13. Bicarbonate adsorption band of the chromatography for carbon isotope separation using anion exchangers

    International Nuclear Information System (INIS)

    Takeda, Kunihiko; Obanawa, Heiichiro; Hata, Masahisa; Sato, Katsuya

    1985-01-01

    The equilibria of bicarbonate ion between two phases were studied for the carbon isotope separation using anion exchangers. The condition of the formation of a bicarbonate adsorption band was quantitatively discussed. The formation of the adsorption band depends on the difference of S-potential which is the sum of the standard redection chemical potentials and L-potential which is the sum of the reduction chemical potential. The isotopic separation factor observed was about 1.012, independent of the concentrations of acid and alkali in the solutions. The isotopic separation factor was considered to be determined by the reaction of bicarbonate ion on anion exchangers and carbon dioxide dissolved in solutions. The enriched carbon isotope whose isotopic abundance ratio ( 13 C/ 12 C) was 1.258 was obtained with the column packed with anion exchangers. (author)

  14. Safety aspects in a chemical exchange process plant

    International Nuclear Information System (INIS)

    Sharma, B.K.

    2016-01-01

    Based on a chemical exchange process involving solid liquid exchange, studies have been undertaken to enrich 10 B isotope of boron using ion exchange chromatography in which a strong base anion exchange resin in hydroxyl form is equilibrated with boric acid solution in presence of mannitol (a complexing reagent to boric acid) to enhance the acidity and hence the isotopic exchange separation factor for 10 B = 11 B exchange reaction. Using the electrochemical techniques such as pH-metry and conductimetry, the choice of a suitable complexing reagent was made amongst ethylene glycol, propylene glycol, dextrose and mannitol for cost-effective separation of isotopes of boron and monitoring of band movements using these electrochemical techniques. The optimum conditions for the regeneration of strong base anion exchange resins of type-I and type-II were determined for cost-effective separation of isotopes of boron by ion exchange chromatography. The possibility of using unspent alkali content of the effluent was also exploited. Removal of carbonate impurity from Rayon grade caustic lye (used as regenerant after dilution) and recycling of Ba(OH) 2 was studied to avoid waste disposal problems. This process is an industrially viable process. The various safety aspects followed during operation of this plant are described in this paper. (author)

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

    International Nuclear Information System (INIS)

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

    1975-01-01

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

  16. Methods of uranium isotpic separation by chemical exchange chromatography

    International Nuclear Information System (INIS)

    Pena V, L.A.; Valle M, L.

    1985-01-01

    Chemical exchange chromatography as applied to isotope separation has undergone a constant development during the last few years. The results so far indicate that this method could eventually become commercially useful. This work presents a critical review of the experimental methods presently under study by principal research groups, and which have not get been compared. (Author)

  17. Application of ion exchange to isotope separation. 2. Isotope separation of uranium

    Energy Technology Data Exchange (ETDEWEB)

    Okamoto, Makoto; Fujii, Yasuhiko; Aida, Masao; Nomura, Masao; Aoyama, Taku

    1985-10-01

    Research work on the uranium isotope separation by ion exchange chromatography done by the ahthors was reviewed and summarized in the present paper. Specifically described are the determination of separation coefficients of uranium isotopes in various chemical systems involving uranium ions and complexes. The chemical systems are classifield into three main categories; (1) uranyl, U (VI), complex formation system, (2) uranous, U (IV), complex formation system and (3) U (IV) - U (VI) redox system. The redox system showed the largest separation coefficient of approx. 7 x 10/sup -4/, while the uranyl and uranous complex systems showed the separation coefficients of -- 2 x 10/sup -4/ and approx. 6 x 10/sup -5/, respectively.

  18. Study of isotopic exchange reactions of azidothymidine with tritium

    International Nuclear Information System (INIS)

    Sidorov, G.V.; Zverkov, Yu.B.; Myasoedov, N.F.

    2003-01-01

    Different reactions of isotopic exchange of azidothymidine (3 - azido-3 - desoxythymidine) with tritium, such as solid- and liquid-phase catalytic isotopic exchange with gaseous tritium and isotopic exchange in solution with tritium water, are investigated. It is determined that catalytic reactions of azidothymidine with gaseous tritium in solution lead to practically full reduction of azido group up to amino group. In reactions of solid-phase catalytic hydrogenation this process takes place too and 3 - azido-3 - desoxythymidine yield is from 20 to 70 %. Molar radioactivity of labelled with tritium azidothymidine prepared in reactions of solid-phase catalytic isotopic exchange with gaseous tritium and so by isotopic exchange in solution with tritium water does not exceed 0.5 Cu/mmol [ru

  19. Fractionation of lithium isotopes in cation-exchange chromatography

    International Nuclear Information System (INIS)

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

    1991-01-01

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

  20. Hydrogen-water isotopic exchange process

    International Nuclear Information System (INIS)

    Cheung, H.

    1983-01-01

    Deuterium is concentrated in a hydrogen-water isotopic exchange process enhanced by the use of catalyst materials in cold and hot tower contacting zones. Water is employed in a closed liquid recirculation loop that includes the cold tower, in which deuterium is concentrated in the water, and the upper portion of the hot tower in which said deuterium is concentrated in the hydrogen stream. Feed water is fed to the lower portion of said hot tower for contact with the circulating hydrogen stream. The feed water does not contact the water in the closed loop. Catalyst employed in the cold tower and the upper portion of the hot tower, preferably higher quality material, is isolated from impurities in the feed water that contacts only the catalyst, preferably of lower quality, in the lower portion of the hot zone. The closed loop water passes from the cold zone to the dehumidification zone, and a portion of said water leaving the upper portion of the hot tower can be passed to the humidification zone and thereafter recycled to said closed loop. Deuterium concentration is enhanced in said catalytic hydrogen-water system while undue retarding of catalyst activity is avoided

  1. 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

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

    Science.gov (United States)

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

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

  3. Isotope exchange reaction in uranous-uranyl-sulphuric acid system

    International Nuclear Information System (INIS)

    Ling Daren; Yue Tingsheng; Mu Dehai; Wang Yani

    1990-01-01

    The kinetics of the isotope exchange reaction between U(IV) and U(VI) has been studied in low concentrations of sulphuric acid. A minimum exchange rate appears at 0.25 M H 2 SO 4 . From the rates at different temperatures ranging from 20deg to 35deg C, an apparent activation energy of 86 kcal/mole was calculated. The exchange rate was found to be accelerated by the addition of ferrous ions, and a half-life of less than 1 s, was obtained. Probable mechanisms for the acceleration of the uranium isotope exchange reactions by acidity and ferrous ions are proposed. (orig.)

  4. Separation of boron isotopes using NMG type anion exchange resin

    International Nuclear Information System (INIS)

    Itagaki, Takaharu; Kosuge, Masao; Fukuda, Junji; Fujii, Yasuhiko.

    1992-01-01

    Ion exchange separation of boron isotopes (B-10 and B-11) has been studied by using a special boron selective ion exchange resin; NMG (n-methyl glucamine)-type anion exchange resin. The resin has shown a large isotope separation coefficient of 1.02 at the experimental conditions of temperature, 80degC, and boric acid concentration, 0.2 M (mole/dm 3 ). Enriched B-10 (92%) was obtained after the migration of 1149 m by a recyclic operation of ion exchange columns in a merry-go-round method. (author)

  5. Novel catalysts for isotopic exchange between hydrogen and liquid water

    International Nuclear Information System (INIS)

    Butler, J.P.; Rolston, J.H.; Stevens, W.H.

    1978-01-01

    Catalytic isotopic exchange between hydrogen and liquid water offers many inherent potential advantages for the separation of hydrogen isotopes which is of great importance in the Canadian nuclear program. Active catalysts for isotopic exchange between hydrogen and water vapor have long been available, but these catalysts are essentially inactive in the presence of liquid water. New, water-repellent platinum catalysts have been prepared by: (1) treating supported catalysts with silicone, (2) depositing platinum on inherently hydrophobic polymeric supports, and (3) treating platinized carbon with Teflon and bonding to a carrier. The activity of these catalysts for isotopic exchange between countercurrent streams of liquid water and hydrogen saturated with water vapor has been measured in a packed trickle bed integral reactor. The performance of these hydrophobic catalysts is compared with nonwetproofed catalysts. The mechanism of the overall exchange reaction is briefly discussed. 6 figures

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

    International Nuclear Information System (INIS)

    Hindin, S. G.; Roberts, G. W.

    1980-01-01

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

  7. Method for enriching and separating heavy hydrogen isotopes from substance streams containing such isotopes by means of isotope exchange

    International Nuclear Information System (INIS)

    Knochel, A.; Eggers, I.; Klatte, B.; Wilken, R. D.

    1985-01-01

    A process for enriching and separating heavy hydrogen isotopes having a heavy hydrogen cation (deuterium and/or tritium) from substance streams containing them, wherein the respectively present hydrogen isotopes are exchanged in chemical equilibria. A protic, acid solution containing deuterium and/or tritium is brought into contact with a value material from the group of open-chained polyethers or aminopolyethers, macro-monocyclic or macro-polycyclic polyethers, macro-monocyclic or macro-polycyclic amino polyethers, and mixtures of these values, in their free or proton salt form to form a reaction product of the heavy hydrogen cation with the value or value salt and bring about enrichment of deuterium and/or tritium in the reaction product. The reaction product containing the value or value salt is separated from the solution. The separated reaction product is treated to release the hydrogen isotope(s) to be enriched in the form of deuterium oxide (HDO) and/or tritium oxide (HTO) by regenerating the value or its salt, respectively. The regenerated value is returned for reuse

  8. Heat Exchanger Lab for Chemical Engineering Undergraduates

    Science.gov (United States)

    Rajala, Jonathan W.; Evans, Edward A.; Chase, George G.

    2015-01-01

    Third year chemical engineering undergraduate students at The University of Akron designed and fabricated a heat exchanger for a stirred tank as part of a Chemical Engineering Laboratory course. The heat exchanger portion of this course was three weeks of the fifteen week long semester. Students applied concepts of scale-up and dimensional…

  9. Chemical kinetics: on the heterogeneous catalysis processes leading to an exchange between two phases. Example: isotopic exchange reactions; Cinetique chimique: sur les processus de catalyse 'heterogene' conduisant a un echange entre deux phases. Exemple: reactions d'echange isotopique

    Energy Technology Data Exchange (ETDEWEB)

    Dirian, G; Grandcollot, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    For an exchange reaction between a gaseous and a liquid phase proceeding by 'heterogeneous' catalysis in the liquid phase, diffusion in the liquid and the chemical reaction are two simultaneous and indivisible processes. We have nevertheless been able to establish criteria making it possible to distinguish between a really homogeneous kinetic process and a pseudo-homogeneous one. (author) [French] Pour une reaction d'echange entre une phase gazeuse et une phase liquide procedant par catalyse 'heterogene' en phase liquide, la diffusion dans le liquide et la reaction chimique sont deux etapes simultanees et indissociables. Nous avons pu neanmoins etablir des criteres permettant de distinguer entre une cinetique homogene vraie et une cinetique pseudo-homogene. (auteur)

  10. Isotope Exchange: a Potential Mechanism Regulating the Natural and Anthropogenic Pb Isotope Budget in Coastal Waters

    Science.gov (United States)

    Chen, M.; Boyle, E. A.; Zurbrick, C.; Carrasco, G. G.; Switzer, A.; Zhao, N.

    2016-02-01

    Two independent studies on anthropogenic Pb and Pb isotopes in coastal corals from the northern Arabian Gulf and the Singapore Straits have shown an isotopic excursion where the main Pb sources discharging to the water move to more crustal-like values, indicating that the Pb in coastal waters might exchange isotopically with crustal particulates without propotional change in concentration. To investigate this issue, Pb isotope exchange is assessed through a closed-system exchange experiment using estuarine waters collected at the Johor River mouth (discharging to the Singapore Straits). During the experiment, a known amount of NBS-981 (206Pb/207Pb=1.093) was spiked into the unfiltered Johor water (dissolved 206Pb/207Pb = 1.199) and the changing isotopic composition of the dissolved Pb was monitored. Shortly after the spike addition, dissolved Pb exhibited 206Pb/207Pb=1.178, reflecting the influence of the spike. Within the following few days, the 206Pb/207Pb in the water increased to >1.190 with limited changes of the dissolved Pb concentration. The observations in closed-system experiment agree with the isotope difference between Singapore aerosol and seawater in our 2-year-long field observations. The kinetics of isotope exchange were assessed using a simple model, which reproduced >70% of the observed Pb isotope variance. Both the close-system experiment and field measurements imply that isotope exchange can be an important mechanism for regulating the Pb and Pb isotopes in coastal waters. Investigations on the distribution of Pb and Pb isotope in estuaries and coastal waters should further assess the role of isotope exchange in ocean Pb chemistry.

  11. The isotope separation by ion exchange chromatography. Application to the lithium isotopes separation

    International Nuclear Information System (INIS)

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

    1993-01-01

    In this work is described the used study step to demonstrate the industrial feasibility of a lithium isotopes separation process by ion exchange chromatography. After having recalled how is carried out the exchange reaction between the lithium isotopes bound on the cations exchanger resin and those which are in solution and gave the ion exchange chromatography principle, the authors establish a model which takes into account the cascade theory already used for enriched uranium production. The size parameters of this model are: the isotopic separation factor (which depends for lithium of the ligands nature and of the coordination factor), the isotopic exchange kinetics and the mass flow (which depends of the temperature, the lithium concentration, the resins diameter and the front advance). The way they have to be optimized and the implementation of the industrial process are given. (O.M.)

  12. Magnesium isotope fractionation in cation-exchange chromatography

    International Nuclear Information System (INIS)

    Oi, T.; Yanase, S.; Kakihana, H.

    1987-01-01

    Band displacement chromatography of magnesium has been carried out successfully for the purpose of magnesium isotope separation by using a strongly acidic cation-exchange resin and the strontium ion as the replacement ion. A small but definite accumulation of the heavier isotopes ( 25 Mg, 26 Mg) has been observed at the front parts of the magnesium chromatograms. The heavier isotopes have been fractionated preferentially into the solution phase. The single-stage separation factors have been calculated for the 25 Mg/ 24 Mg and 26 Mg/ 24 isotopic pairs at 25 0 C. The reduced partition function ratios of magnesium species involved in the present study have been estimated

  13. Combined electrolysis catalytic exchange (CECE) process for hydrogen isotope separation

    International Nuclear Information System (INIS)

    Hammerli, M.; Stevens, W.H.; Butler, J.P.

    1978-01-01

    Hydrogen isotopes can be separated efficiently by a process which combines an electrolysis cell with a trickle bed column packed with a hydrophobic platinum catalyst. The column effects isotopic exchange between countercurrent streams of electrolytic hydrogen and liquid water while the electrolysis cell contributes to isotope separation by virtue of the kinetic isotope effect inherent in the hydrogen evolution reaction. The main features of the CECE process for heavy water production are presented as well as a discussion of the inherent positive synergistic effects, and other advantages and disadvantages of the process. Several potential applications of the process in the nuclear power industry are discussed. 3 figures, 2 tables

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

    International Nuclear Information System (INIS)

    Hindin, S.G.; Roberts, G.W.

    1977-01-01

    A process is described for exchanging isotopes (particularly tritium) between water and gaseous hydrogen. Isotope depleted gaseous hydrogen and water containing a hydrogen isotope are introduced into the vapour phase in a first reaction area. The steam and gaseous hydrogen are brought into contact with a supported metal catalyst in this area in a parallel flow at a temperature range of around 225 and 300 0 C. An effluent flow comprising a mixture of isotope enriched gaseous hydrogen and depleted steam is evacuated from this area and the steam condensed into liquid water [fr

  15. Isotope exchange reaction of tritium on precious metal catalyst based on cation-exchanged mordenite for blanket tritium recovery

    Energy Technology Data Exchange (ETDEWEB)

    Kawamura, Yoshinori, E-mail: kawamura.yoshinori@jaea.go.jp [Japan Atomic Energy Agency, 801-1 Mukoyama, Naka, Ibaraki 311-0193 (Japan); Hayashi, Takumi [Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai, Ibaraki 319-1195 (Japan); Yamanishi, Toshihiko [Japan Atomic Energy Agency, 2-166 Omotedate Obuchi, Rokkasho, Aomori 039-3212 (Japan)

    2016-11-01

    Highlights: • Precious metal catalyst based on cation-exchanged mordenite was prepared. • Isotope exchange reaction between H{sub 2} and HTO on the catalyst was investigated. • The order of entire reaction is not clear, but it is the first-order reaction as for HTO. • Effect of exchanged cation may appear as the difference of the surface area of catalyst. - Abstract: It is known that the chemical forms of tritium released from a ceramic breeder blanket are hydrogen form and water form. To recover tritiated water vapor, adoption of dryer that is packed column of synthetic zeolite has been proposed. On the other hand, synthetic zeolite is often used as a support of precious metal catalyst. Such catalysts usually have a capability of hydrogen isotope exchange between gas and water vapor. If this catalyst is used to dryer, the dryer may obtain a preferable function for tritium recovery by isotopic exchange reaction. To assess such functions, reaction rate should be estimated. The results of water adsorption experiment on cation-exchanged mordenite-type zeolite suggested the possibility that state of adsorbed water varied by exchanged cation. So, in this work, precious metal catalyst based on cation-exchanged mordenite was prepared, and the reaction rate of chemical exchange between hydrogen and tritiated water was investigated under temperature range between 30 °C and 80 °C by the steady-state approximation. In the case of platinum on Na-mordenite, the reaction between gaseous hydrogen and tritiated water vapor was almost expressed as first-order reaction concerning tritiated water vapor concentration.

  16. Chemical stability of levoglucosan: An isotopic perspective

    Science.gov (United States)

    Sang, X. F.; Gensch, I.; Kammer, B.; Khan, A.; Kleist, E.; Laumer, W.; Schlag, P.; Schmitt, S. H.; Wildt, J.; Zhao, R.; Mungall, E. L.; Abbatt, J. P. D.; Kiendler-Scharr, A.

    2016-05-01

    The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4-levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas-phase OH, a reaction rate constant of (2.67±0.03)·10-12 cm3 molecule-1S-1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.

  17. Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

    International Nuclear Information System (INIS)

    Janecky, D.R.

    1988-01-01

    A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs

  18. Technological procedure for chemical cleaning prior to re-pyritization of H2O-H2S isotopic exchange installations

    International Nuclear Information System (INIS)

    Stefanescu, I.; Smaranda, D.; Titescu, Gh.

    1996-01-01

    In normal operation the anti-corrosive shielding of the GS installations undergo a slow, irreversible degradation in time so that after 6 - 8 years their protection characteristics break down. In order to put them back in operation the regeneration of anti-corrosive is required. The procedure achieved at ICIS - Rm.Valcea consists in chemical cleaning of the impaired layers and re-pyritization of the interior surface of installations. Chemical cleaning include the following operations: - mechanical cleaning; - water washing; - alkaline washing with sodium hydroxide, tri-sodium phosphate and sodium tri-polyphosphate; - final mechanical cleaning; - neutralizing washing; - chemical cleaning with phosphoric acid solution; - neutralizing washing. After applying this procedure, the surface is prepared for the pyritization regeneration of the anti-corrosive shielding which ensures the prolongation of the equipment service lifetime with another six year period

  19. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

    Shugard, Andrew D.; Buffleben, George M.; Johnson, Terry A.; Robinson, David B.

    2014-01-01

    Highlights: • Isotope exchange between hydrogen gas and uranium hydride powder can be rapid and reversible. • Gas–solid exchange rate is controlled by transport within ∼0.7 μm hydride particles. • Gas chromatographic separation of hydrogen isotopes using uranium hydride is feasible. - Abstract: Isotope exchange between gaseous hydrogen and solid uranium hydride has been studied by flowing hydrogen (deuterium) gas through packed powder beds of uranium deuteride (hydride). We used a residual gas analyzer system to perform real-time analysis of the effluent gas composition. We also developed an exchange and transport model and, by fitting it to the experimental data, extracted kinetic parameters for the isotope exchange reaction. Our results suggest that, from approximately 70 to 700 kPa and 25 to 400 °C, the gas-to-solid exchange rate is controlled by hydrogen and deuterium transport within the ∼0.7 μm diameter uranium hydride particles. We use our kinetic parameters to show that gas chromatographic separation of hydrogen and deuterium using uranium hydride could be feasible

  20. Isotopic enrichment of 15N by ionic exchange cromatography

    International Nuclear Information System (INIS)

    Trivelin, P.C.O.; Matsui, E.; Salati, E.

    1979-01-01

    The ionic exchange chromatographic method in columns of resin which is employed in the study of isotopic enrichment of 15 N is presented. Determinations are made of the isotopic separation constant for the exchange of isotopes 15 N and 14 N in the equilibrium involving ammonium hidroxide in the solution phase and ions NH 4 + adsorbed in cationic resins: Dowex 50W-X8 and X12, 100-200 mesh. Experiments are also conducted for determination of height of theoretical plates for situations of equilibrium of the NH 4 + band in two systems of resin's columns aimed at estimating the experimental conditions used. The isotopic analyses of nitrogen are carried out by mass spectrometry [pt

  1. Isotopically exchangeable Al in coastal lowland acid sulfate soils

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  2. Isotope effects of sulfur in chemical reactions

    International Nuclear Information System (INIS)

    Mikolajczuk, A.

    1999-01-01

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

  3. Contact isotopic- and contact ion-exchange between two adsorbents

    International Nuclear Information System (INIS)

    Bunzl, K.; Mohan, R.; Haimerl, M.

    1975-01-01

    The kinetics of contact ion exchange processes between an ion exchange membrane and resin ion exchange beads, stirred in pure water, was investigated. A general criterion was derived, which indicates whether diffusion of the ions between the intermingling electric double layers or the collision frequency between the two adsorbents is the rate dermining step. Since the latter process proved to be rate controlling under our experimental conditions, the corresponding rate equations were derived under various initial and boundary conditions. Experimentally, the kinetics of contact isotopic exchange of Cs + - and Na + -ions as well as of the reverse contact ion exchange process of Cs + -versus Na + -ions were investigated by using Na 22 and Cs 137 radioisotopes. The experiments reveal in quantitative accord with the theory that the rate of collision controlled contact ion exchange processes depends mainly on the 'exchange coefficient', the separation factor and the collision frequency. While the latter two quantities were determined independently by separate experiments, the 'exchange coefficient' was evaluated from a contact isotopic exchange experiment. (orig.) [de

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

    Science.gov (United States)

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

    1987-01-01

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

  5. Chemical exchange between UF6 and UF6- ion in anhydrous hydrofluoric acid

    International Nuclear Information System (INIS)

    Chatelet, J.; Luce, M.; Plurien, P.; Rigny, P.

    1975-01-01

    The chemical exchange between UF 6 and the UF 6 - ion is of potential interest for the separation of U isotopes. In this paper, results concerning the value of the separation factor and the kinetics of the homogeneous exchange are given [fr

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

    Science.gov (United States)

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

    2004-04-01

    The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate that the number of D atoms incorporated during

  7. Isotopic Exchange in Porous and Dense Magnesium Borohydride.

    Science.gov (United States)

    Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

    2015-09-01

    Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Comparative study on bromide and iodide ion-isotopic exchange reactions using strongly basic anion exchange resin Duolite A-113

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Dole, M.H.; Singare, P.U.

    2006-01-01

    Kinetics of ion-isotopic exchange reaction was studied using industrial grade ion exchange resin Duolite A-113. The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reaction. The experiments were performed in the temperature range of 26.0degC to 43.0degC and the concentration of external ionic solution varying from 0.005 M to 0.100 M. For bromide ion-isotopic exchange reaction, the calculated values of specific reaction rate, initial rate of bromide ion exchange, and amount of bromide ions exchanged were obtained higher than that for iodide ion-isotopic exchange reaction under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (author)

  9. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-11-01

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

  10. Rate of radiocarbon retention onto calcite by isotope exchange

    International Nuclear Information System (INIS)

    Lempinen, Janne; Lehto, Jukka

    2016-01-01

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

  11. Nitrogen isotope exchange between nitric oxide and nitric acid

    International Nuclear Information System (INIS)

    Axente, D.; Abrudean, M.; Baldea, A.

    1996-01-01

    The rate of nitrogen isotope exchange between NO and HNO 3 has been measured as a function of nitric acid concentration of 1.5-4M x 1 -1 . The exchange rate law is shown to be R=k[HNO 3 ] 2 [N 2 O 3 ] and the measured activation energy is E=67.78 kJ x M -1 (16.2 kcal x M -1 ). It is concluded that N 2 O 3 participates in 15 N/ 14 N exchange between NO and HNO 3 at nitric acid concentrations higher than 1.5M x 1 -1 . (author). 7 refs., 3 figs., 4 tabs

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

    International Nuclear Information System (INIS)

    Ravoire, Jean

    1979-11-01

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

  13. Hydrogen isotope exchange in metal hydride columns

    International Nuclear Information System (INIS)

    Wiswall, R.; Reilly, J.; Bloch, F.; Wirsing, E.

    1977-01-01

    Several metal hydrides were shown to act as chromatographic media for hydrogen isotopes. The procedure was to equilibrate a column of hydride with flowing hydrogen, inject a small quantity of tritium tracer, and observe its elution behavior. Characteristic retention times were found. From these and the extent of widening of the tritium band, the heights equivalent to a theoretical plate could be calculated. Values of around 1 cm were obtained. The following are the metals whose hydrides were studied, together with the temperature ranges in which chromatographic behavior was observed: vanadium, 0 to 70 0 C; zirconium, 500 to 600 0 C; LaNi 5 , -78 to +30 0 C; Mg 2 Ni, 300 to 375 0 C; palladium, 0 to 70 0 C. A dual-temperature isotope separation process based on hydride chromatography was demonstrated. In this, a column was caused to cycle between two temperatures while being supplied with a constant stream of tritium-traced hydrogen. Each half-cycle was continued until ''breakthrough,'' i.e., until the tritium concentration in the effluent was the same as that in the feed. Up to that point, the effluent was enriched or depleted in tritium, by up to 20%

  14. Critical overview on water - hydrogen isotopic exchange; a case study

    International Nuclear Information System (INIS)

    Peculea, Marius

    2002-01-01

    Water - hydrogen isotopic exchange process is attractive due to its high separation factor; it is neither corrosive or pollutant and, when used as a technological process of heavy water production, it requires water as raw material. Its efficiency depends strongly on the catalyst performance and geometry of the isotopic water - hydrogen exchange zone in which the isotopic transfer proceeds in two steps: liquid vapor distillation in the presence of an inert gas and a catalytic reaction in vapor - gas gaseous phase. An overview of the water hydrogen isotopic exchange is presented and technological details of the Trail - Canada facility as well as characteristics of the two pilots operated in Romania with Ni, Cr and hydrophobic catalysts are described. The mathematical approach of the successive water-water vapor-hydrogen isotopic exchange process given is based on a mathematical model worked out earlier by Palibroda. Discrepancies between computation and experimental results, lower than 11% for extreme cases and around 6% for the average range are explained as due to the ratio of the exchange potentials. Assumption is made in the theoretical approach that this ratio is positive and constant all long the column while the measurements showed that it varies within 0.7 and 1.1 at the upper end and within - 2.5 and - 4.4 at the lower end, what indicates a strong end effect. In conclusion it is stressed that a competing technological solution is emerging based on a monothermal electrolytic process or a bithermal - bibaric process both for heavy water and tritium separation process

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

    International Nuclear Information System (INIS)

    Popov, L.

    2016-01-01

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

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

    International Nuclear Information System (INIS)

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

    1992-01-01

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

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

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Kitamoto, Asashi

    1985-01-01

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

  18. Chlorine isotopes potential as geo-chemical tracers

    Digital Repository Service at National Institute of Oceanography (India)

    Shirodkar, P.V.; Pradhan, U.K.; Banerjee, R.

    The potential of chlorine isotopes as tracers of geo-chemical processes of earth and the oceans is highlighted based on systematic studies carried out in understanding the chlorine isotope fractionation mechanism, its constancy in seawater and its...

  19. Determination of the energetics of the UDP-glucose pyrophosphorylase reaction by positional isotope exchange inhibition

    International Nuclear Information System (INIS)

    Hester, L.S.; Raushel, F.M.

    1987-01-01

    A method has been developed for obtaining qualitative information about enzyme-catalyzed reactions by measuring the inhibitory effects of added substrates on positional isotope exchange rates. It has been demonstrated for ordered kinetic mechanisms that an increase in the concentration of the second substrate to add to the enzyme will result in a linear increase in the ratio of the chemical and positional isotope exchange rates. The slopes and intercepts from these plots can be used to determine the partitioning ratios of binary and ternary enzyme complexes. The method has been applied to the reaction catalyzed by UDP-glucose pyrophosphorylase. A positional isotope exchange reaction was measured within oxygen-18-labeled UTP as a function of variable glucose 1-phosphate concentration in the forward reaction. In the reverse reaction, a positional isotope exchange reaction was measured within oxygen-18-labeled UDP-glucose as a function of increasing pyrophosphate concentration. The results have been interpreted to indicate that the interconversion of the ternary central complexes is fast relative to product dissociation in either direction. In the forward direction, the release of UDP-glucose is slower than the release of pyrophosphate. The release of glucose 1-phosphate is slower than the release of UTP in the reverse reaction

  20. Hydrogen, deuterium, and tritium isotope exchange experiments in JET

    Energy Technology Data Exchange (ETDEWEB)

    Horton, L.D.; Andrew, P.; Bracco, G.; Conroy, S.; Corti, S.; Ehrenberg, J.; Goodall, D.H.J.; Jarvis, O.N.; Lomas, P.; Loughlin, M.; Peacock, A.T.; Saibene, G.; Sadler, G.; Sartori, R.; Stamp, M.F.; Thomas, P.R.; Belle, P. van (JET Joint Untertaking, Abingdon, Oxfordshire (United Kingdom))

    1992-12-01

    Isotope exchange experiments have been performed in JET using hydrogen, deuterium, and, in the recent preliminary tritium experiment (PTE), tritium. The rate of change-over from one isotope to another involves two quite different time constants. We have modelled this behaviour using a multireservoir model which splits the accessible hydrogenic particles into two groups, each having a different rate of exchange of particles with the plasma. By applying this model to the sequence of discharges during and after the PTE, we can determine the parameters in the model. The resulting fit also gives a good representation of hydrogen/deuterium change-over experiments, indicating that the tritium behaves in the same manner as other hydrogen isotopes, at least as far as recycling is concerned. Discrepancies between the model and the actual measurements of tritium recovery after the PTE lead us to conclude that isotope exchange processes resulting from collisions of molecules with the vessel walls play a significant role in spreading tritrium around the machine. (orig.).

  1. Chemical exchange effects in spectral line shapes

    International Nuclear Information System (INIS)

    Diaz, M.A.; Veguillas, J.

    1990-01-01

    A theory of spectral-line shapes has been extended to the case in which relaxation broadening may be influenced by reactive interactions. This extension is valid for gaseous systems in the same way it is valid for condensed media, and particularly, for such chemical mechanisms as isomerizations. The dependence of the spectral rate on the chemical exchange rate is clarified. Finally, a discussion concerning the above aspects and their applications has been included. (author)

  2. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  3. Study of kinetics, equilibrium and isotope exchange in ion exchange systems Pt. 6

    International Nuclear Information System (INIS)

    Plicka, J.; Stamberg, K.; Cabicar, J.; Gosman, A.

    1986-01-01

    The description of kinetics of ion exchange in ternary system was based upon three Nernst-Planck equations, each of them describing the particle diffusion flux of a given counterion as an independent process. For experimental verification, the strongly acidic cation exchanger OSTION KS 08 the shallow-bed technique, and 0.2 mol x dm -3 aqueous nitrate solutions were chosen. The kinetics of ion exchange in the system of cations Na + - Mg 2+ - UO 2 2+ was studied. The values of diffusion coefficients obtained by evaluating of kinetics of isotope exchange and binary ion exchange were used for calculation. The comparison of calculated exchange rate curves with the experimental ones was made. It was found that the exchanging counterions were affected by each other. (author)

  4. Isotope exchange of strontium and molybdate ions in strontium polymolybdates

    International Nuclear Information System (INIS)

    Atun, G.

    2002-01-01

    The heterogeneous isotopic exchange reactions in strontium polymolybdates of Sr 2+ and MoO 4 2- ions in the strontium nitrate and sodium molybdate solutions have been studied using 90 Sr and 99 Mo as tracers. Electrometric methods have been used to study the compositions of strontium molybdates obtained by adding strontium chloride to a progressively acidified solution of sodium molybdate. It has been found that the exchange fraction increases with increasing chain length of strontium polymolybdate. The exchange equilibrium constant (K ex ) has been calculated between 298 and 348 K as well as ΔG deg, ΔH deg and ΔS deg. The results indicate that Sr 2+ cations have a much higher affinity for exchangers than MoO 4 2- anions. By fitting the data to the Dubinin-Radushkevich (D-R) isotherm it has been shown that the exchange capacity (X m ) for both ions is affected by the ion adsorption process at low temperatures and by the ion exchange process at high temperatures. At high concentrations, the recrystallization process contributes to on the cation exchange but is ineffective on the anion exchange mechanism. (author)

  5. Isotope dependence of chemical erosion of carbon

    International Nuclear Information System (INIS)

    Reinhold, C.O.; Krstic, P.S.; Stuart, S.J.; Zhang, H.; Harris, P.R.; Meyer, F.W.

    2010-01-01

    We study the chemical erosion of hydrogen-supersaturated carbon due to bombardment by hydrogen isotopes H, D, and T at energies of 1-30 eV using classical molecular dynamics simulations. The chemical structure at the hydrogen-saturated interface (the distribution of terminal hydrocarbon moieties, in particular) shows a weak dependence on the mass of the impinging atoms. However, the sputtering yields increase considerably with increasing projectile mass. We analyze the threshold energies of chemical sputtering reaction channels and show that they are nearly mass independent, as expected from elementary bond-breaking chemical reactions involving hydrocarbons. Chemical sputtering yields for D impact are compared with new experimental data. Good agreement is found for small hydrocarbons but the simulations overestimate the production of large hydrocarbons for energies larger than 15 eV. We present a thorough analysis of the dependence of our simulations on the parameters of the bombardment schemes and discuss open questions and possible avenues for development.

  6. Isotopic exchange in mixed valence compounds in the solid state

    International Nuclear Information System (INIS)

    Fernandez Valverde, S.M.

    1986-01-01

    This work aims at the determination of isotopic exchange kinetics and mechanism in two mixed valence compounds: Cs 10 (Sbsup(V)Cl 6 ) (Sbsup(III)Cl 6 ) 3 and Tl 3 sup(I)(Tlsup(III)Cl 6 ). The synthesis of the first compound is very difficult because in most of the cases mixtures of chloroantimoniates are obtained. Exchange in Tl 4 Cl 6 labelled on Tlsup(III) is studied in detail by radiochemical analysis and physical techniques: ionic conductivity and positon annihilation. Cation vacancies are easily created in the lattice with formation enthalpy of 0.35 eV and migration enthalpy of 0.52 eV. Isochronic and isothermal exchange curves are described by a kinetic based on species diffusion. Models are given. Exchange is increased by grinding probably because extrinseque defects are introduced [fr

  7. 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

  8. Determination of traces of phosphorus using isotope exchange

    International Nuclear Information System (INIS)

    Zeman, A.; Kratzer, K.

    1976-01-01

    A simple and selective radioanalytical method for the determination of phosphorus (0.015 - 5 μg in a 5 ml sample), based on the heterogeneous isotope exchange, has been developed. The sample containing phosphorus is shaken in the presence of molybdate with a standard solution of tetraphenylarsonium molybdophosphate labelled with phosphorus-32 in 1-2 dicloroethan. From the distribution of the activity between the aqueous and organic phases the amount of phosphorus in the sample can be determined. (Authors)

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

    International Nuclear Information System (INIS)

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

    1984-01-01

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

  10. Hydrogen isotopic exchange reaction in a trickle-bed

    International Nuclear Information System (INIS)

    Paek, Seung Woo; Ahn, Do Hee; Kim, Kwang Rag; Lee, Min Soo; Yim, Sung Paal; Chung, Hong Suk

    2005-01-01

    The CECE (Combined Electrolysis Catalytic Exchange) with a hydrophobic catalyst is ideally suited for extracting tritium from water because of its high separation factor and mild operating conditions. This process for different hydrogen isotope applications has been developed by AECL. A laboratory scale CECE was built and operated at Mound Laboratory. Belgium and Japan have also developed independently similar processes which are based on a hydrophobic catalyst. The CECE column is composed of an electrolysis cell and a liquid phase catalytic exchange column. The liquid phase catalytic exchange columns having various structures were developed; and it has been recognized that a multistage type and a trickle-bed type are promising. The multistage type gave more successful results than the trickle-bed type. However, the structure of the column is complicated. The trickle-bed type has a significant advantage in that the structure of the column is quite simple: the hydrophobic catalysts or the catalysts and packings are packed within the column. This structure would lead us to a smaller column height than the multistage type. This paper deals with the experiment for the hydrogen isotope exchange in a trickle-bed reactor packed with a hydrophobic catalyst and the design of the catalytic column for the CECE to tritium recovery from light water

  11. Hydrogen isotopic exchange reaction in a trickle-bed

    Energy Technology Data Exchange (ETDEWEB)

    Paek, Seung Woo; Ahn, Do Hee; Kim, Kwang Rag; Lee, Min Soo; Yim, Sung Paal; Chung, Hong Suk [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    The CECE (Combined Electrolysis Catalytic Exchange) with a hydrophobic catalyst is ideally suited for extracting tritium from water because of its high separation factor and mild operating conditions. This process for different hydrogen isotope applications has been developed by AECL. A laboratory scale CECE was built and operated at Mound Laboratory. Belgium and Japan have also developed independently similar processes which are based on a hydrophobic catalyst. The CECE column is composed of an electrolysis cell and a liquid phase catalytic exchange column. The liquid phase catalytic exchange columns having various structures were developed; and it has been recognized that a multistage type and a trickle-bed type are promising. The multistage type gave more successful results than the trickle-bed type. However, the structure of the column is complicated. The trickle-bed type has a significant advantage in that the structure of the column is quite simple: the hydrophobic catalysts or the catalysts and packings are packed within the column. This structure would lead us to a smaller column height than the multistage type. This paper deals with the experiment for the hydrogen isotope exchange in a trickle-bed reactor packed with a hydrophobic catalyst and the design of the catalytic column for the CECE to tritium recovery from light water.

  12. Positional isotope exchange studies on enzyme using NMR spectroscopy

    International Nuclear Information System (INIS)

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, 18 O-β,γ-ATP and 18 O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field 31 P NMR, we were able to differentiate between 18 O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with 18 O-β,γ-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the 18 O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN 1 /sub P/) type of mechanism

  13. Boron isotope separation by ion exchange chromatography using weakly basic anion exchange resin

    International Nuclear Information System (INIS)

    Sakuma, Yoichi; Aida, Masao; Okamoto, Makoto; Kakihana, Hidetake

    1980-01-01

    Isotopic plateau displacement chromatography, a useful method for isotope separation is presented. The boric acid band formed in a column of weakly basic anion exchange resin Diaion WA21 can be eluted with pure water. In order to obtain good accumulation of the isotope effect, a series of experiments with different migration length were carried out. The boron-10 enriched part of the boric acid absorbed band was always preceded by the isotopic plateau part, in which the atomic fraction of boron-10 was maintained at its original value. The atomic fraction of boron-10 at the end of the chromatogram increased with migration length, and in the case of 256-m migration, boron-10 was enriched from its original atomic fraction of 19.84 to 91.00%, the separation factor S being constant irrespective of migration length: S = 1.0100 +- 0.0005. (author)

  14. Comparative study on ion-isotopic exchange reaction kinetics by application of tracer technique

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Singare, P.U.

    2007-01-01

    The radioactive isotopes 131 I and 82 Br were used to trace the ion-isotopic exchange reactions using industrial grade ion exchange resins Amberlite IRA-400. The experiments were performed to understand the effect of temperature and concentration of ionic solution on kinetics of exchange reactions. Both the exchange reactions were greatly influenced by rise in temperature, which result in higher percentage of ions exchanged. For bromide ion-isotopic exchange reactions, the calculated values of specific reaction rate/min -1 , and amount of ions exchanged/mmol were obtained higher than that for iodide ion-isotopic exchange reactions under identical experimental conditions. The observed variation in the results for two ion-isotopic exchange reactions was due to the difference in the ionic size of bromide and iodide ions. (orig.)

  15. Speciation and isotopic exchangeability of nickel in soil solution.

    Science.gov (United States)

    Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

    2009-01-01

    Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. In this study, free Ni(2+) activities were determined in pore waters of long-term Ni-contaminated soils using a Donnan dialysis membrane technique. The pore water free Ni(2+) concentration as a percentage of total soluble Ni ranged from 21 to 80% (average 53%), and the average amount of Ni bound to dissolved organic matter estimated by Windermere Humic Aqueous Model VI was < or = 17%. These data indicate that complexed forms of Ni can constitute a significant fraction of total Ni in solution. Windermere Humic Aqueous Model VI provided reasonable estimates of free Ni(2+) fractions in comparison to the measured fractions (R(2) = 0.83 with a slope of 1.0). Also, the isotopically exchangeable pools (E value) of soil Ni were measured by an isotope dilution technique using water extraction, with and without resin purification, and 0.1 mol L(-1) CaCl(2) extraction, and the isotopic exchangeability of Ni species in soil water extracts was investigated. The concentrations of isotopically non-exchangeable Ni in water extracts were <9% of total water soluble Ni concentrations for all soils. The resin E values expressed as a percentage of the total Ni concentrations in soil showed that the labile Ni pool ranged from 0.9 to 32.4% (average 12.4%) of total soil Ni. Therefore the labile Ni pool in these well-equilibrated contaminated soils appears to be relatively small in relation to total Ni concentrations.

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

    DEFF Research Database (Denmark)

    FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

    1992-01-01

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

  17. Electron exchange reaction in anion exchangers as observed in uranium isotope separation

    International Nuclear Information System (INIS)

    Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

    1991-01-01

    The mechanism of electron exchange in an ion exchanger, as occurring between U 4+ and UO 2 2+ in uranium isotope separation, was investigated. The height of the separation unit (H q ) in the presence of metal ion catalysts, as obtained from the separation experiments, was found to be almost coincident with the theoretical value of H q as calculated on the basis of the intrasolution acceleration mechanism of the metal ion, suggesting that the electron exchange mechanism in the ion-exchanger is essentially the same as that in the solution when metal ion catalysts are present. Separation experiments with no metal ion catalyst, on the other hand, showed the electron exchange reaction in the ion exchanger to be substantially higher than that in the solution, suggesting an acceleration of the electron exchange reaction by the ion-exchanger which is due to the close existence of higher order Cl - complexes of UO 2 2+ and U 4+ in the vicinity of the ion-exchange group. (author)

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  19. Isotopic enrichment of 15N by ionic exchange chromatography

    International Nuclear Information System (INIS)

    Trivelin, P.C.O.

    1979-01-01

    The present paper presents some studies on production of 15 N-enriched ammonium sulphate with 5% atoms by ionic exchange chromatography method. Two systems are described of columns of resin, where experiments were conducted by eluition of NH 4 + bands with sodium hydroxide solution. Analyses were made of the cost of production of 15 N-enriched ammonium sulphate 5% atoms and, based on the experiments developed, a cost was obtained which was compatible with the international price of the product. The isotopic analyses of nitrogen were made by mass spectrometry. (Author) [pt

  20. Progress in 15N and 13C separation by isotopic exchange

    International Nuclear Information System (INIS)

    Axente, D.

    2004-01-01

    An experimental study of 15 N separation by isotopic exchange in NO, NO 2 - HNO 3 system under pressure is presented. The pressure increase in 15 N separation plant improved the isotopic transport between the two phases circulated in counter-current in the packed column according to a better kinetics of isotopic exchange at higher pressures. The operation of 15 N separation plant at a pressure of 1.8 atm (absolute) will permit doubling of 10 M nitric acid flow rate and of 15 N production of a given column. The improved performance at a higher pressure is significant for large scale 15 N production, which would be utilized for uranium nitride fuels for FBRs. Enrichment of 13 C by chemical exchange between CO 2 and amine carbamate in nonaqueous solvent has been modelled. For process optimization the steady state separation and the height equivalent to a theoretical plate (HETP) have been determined for different experimental conditions and simulated for higher pressures than atmospheric one. At lower temperature (5 deg C) as the pressure increases the quantity of CO 2 dissolved in amine solution increases. For process analysis at higher pressures and lower temperatures, the two steps model has been considered. At 0.9 MPa pressure and 5 deg C the reaction rate is higher than at 25 deg C and atmospheric pressure, the value of HETP being lower with more than 100% than at 25 deg C. (author)

  1. 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

  2. Chemical reaction on solid surface observed through isotope tracer technique

    International Nuclear Information System (INIS)

    Tanaka, Ken-ichi

    1983-01-01

    In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

  3. Study on influencing factors for hydrogen isotopic exchange

    International Nuclear Information System (INIS)

    Gu Mei; Liu Jun; Luo Yangming

    2013-01-01

    Background: Hydrogen-water catalytic exchange reaction offers an approach to hydrogen isotope separation, which can be applied in heavy water detritiation. Purpose: To optimize the operating condition for hydrogen-water catalytic exchange reaction, we analysed the influence of different factors on the transfer coefficient. Methods: In detail, the isotope exchange experiments of H-D system were carried out in a self-designed catalytic bed loaded with hydrophobic catalyst and hydrophilic packing with certain volume ratio. The experiments showed the changes of both the transfer coefficient and the pressure drop of column with the changing of the operational temperatures (29℃, 45℃, 60℃ and 75℃), the ratios of gas to liquid (0.58, 1.17, 2.65, 3.54) and the deuterium concentrations (5.05×10 -3 , 1.0144×10 -2 , 2.01×10 -2 ). Results: Results showed that 45℃ is the optimal temperature for operating. The transfer coefficient increases with the increasing of the ratio of gas to liquid in the ranges of 0.58 to 1.17 and 2.65 to 3.56, while decreases with the deuterium concentration increases from 5.05×10 -3 to 2.01×10 -2 . The pressure drop of column increases with increasing of gas flow rate. Conclusions: The experiment proves that the ratio of gas to liquid, the reaction temperature and the deuterium concentration are all important factors, which influence the transfer coefficient of deuterium obviously. The optimal operating condition for hydrogen-water catalytic exchange reaction are as follows: the temperature is 45℃, the ratio of gas to liquid is 3.56, and the deuterium concentration is 2.01×10 -2 . (authors)

  4. Regeneration of the iodine isotope-exchange efficiency for nuclear-grade activated carbons

    International Nuclear Information System (INIS)

    Deitz, V.R.

    1985-01-01

    The removal of radioactive iodine from air flows passing through impregnated activated carbons depends on a minimum of three distinguishable reactions: (1) adsorption on the carbon networks of the activated carbons, (2) iodine isotope exchange with impregnated iodine-127, and (3) chemical combination with impregnated tertiary amines when present. When a carbon is new, all three mechanisms are at peak performance and it is not possible to distinguish among the three reactions by a single measurement; the retention of methyl iodide-127 is usually equal to the retention of methyl iodide-131. After the carbon is placed in service, the three mechanisms of iodine removal are degraded by the contaminants of the air at different rates; the adsorption process degrades faster than the other two. This behavior will be shown by comparisons of methyl iodide-127 and methyl iodide-131 penetration tests. It was found possible to regenerate the iodine isotope-exchange efficiency by reaction with airborne chemical reducing agents with little or no improvement in methyl iodine-127 retention. Examples will be given of the chemical regeneration of carbons after exhaustion with known contaminants as well as for many carbons removed from nuclear power operations. The depth profile of methyl iodide-131 penetration was determined in 2-inch deep layers before and after chemical treatments

  5. Tritium separation factors in distillation and chemical exchange processes

    International Nuclear Information System (INIS)

    Dave, S.M.; Ghosh, S.K.; Sadhukhan, H.K.

    1982-01-01

    The vapour pressures of different isotopic hydrogen, water and ammonia molecules have been calculated. These vapour pressures can be used to evaluate relative volatilities of different species for separation of tritium isotopes by distillation. The equilibrium constants for various exchange reactions involving different deuterated and tritiated species of hydrogen, water and ammonia molecules have also been calculated for different temperatures. (author)

  6. The isotope separation by ion exchange chromatography. Application to the lithium isotopes separation; La separation isotopique par chromatographie ionique

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-12-31

    In this work is described the used study step to demonstrate the industrial feasibility of a lithium isotopes separation process by ion exchange chromatography. After having recalled how is carried out the exchange reaction between the lithium isotopes bound on the cations exchanger resin and those which are in solution and gave the ion exchange chromatography principle, the authors establish a model which takes into account the cascade theory already used for enriched uranium production. The size parameters of this model are: the isotopic separation factor (which depends for lithium of the ligands nature and of the coordination factor), the isotopic exchange kinetics and the mass flow (which depends of the temperature, the lithium concentration, the resins diameter and the front advance). The way they have to be optimized and the implementation of the industrial process are given. (O.M.). 5 refs.

  7. The advanced CECE process for enriching tritium by the chemical exchange method with a hydrophobic catalyst

    International Nuclear Information System (INIS)

    Kitamoto, Asashi; Shimizu, Masami; Masui, Takashi.

    1992-01-01

    The monothermal chemical exchange process with electrolysis, i.e., CECE process, was an effective method for enriching and removing tritium from tritiated water with low to middle level activity. The purpose of this study is to propose the theoretical background of the two-parameter evaluation method, which is based on a two-step isotope exchange reaction between hydrogen gas and liquid water, for improvement of the performance of a hydrophobic catalyst by a trickle bed-type column. Finally, a two-parameter method could attain the highest performance of isotope separation and the lowest liquid holdup for a trickle bed-type column. Therefore, this method will present some effective and practical procedures in scaling up a tritium enrichment process. The main aspect of the CECE process in engineering design and system evaluation was to develop the isotope exchange column with a high performance catalyst. (author)

  8. Study of the isotopic exchange associated with ionic exchange for the radiochemical separation of 233-Th

    International Nuclear Information System (INIS)

    Sepulveda Munita, C.J.A.

    1983-01-01

    The isotopic ion exchange procedure is applied in order to establish an analytical method for the determination of thorium by means of the 233 Th activity, when the presence of interfering elements does not allow a direct non-destructive activation analysis. The separation is based on the retention of 233 Th by a thorium saturated resin, due to the isotopic exchange effect, and subsequent elution of the interfering radioisotopes with a solution of thorium in diluted hydrochloric acid. The interfering elements were those which either present a great affinity for the resin or emit gamma rays with energies close to that of 233 Th (86.6 KeV), when a NaI(Tl) detector is used to obtain the gama-ray spectra of the irradiated samples. The equilibrium time for the thorium isotopic ion exchange and the distribution coefficients for the interfering elements were determined by using Bio-Rad AG 50W resins (100-200 mesh), with 4% to 8% of divinylbenzene. The best separation conditions were established in terms of the thorium and hydrochloric acid concentrations in the solution, the resin cross-linking degree, and the solution flow through the resin. The analytical method was applied to the determination of thorium in samples of ammonium diuranate as well in standard rock samples from the United States Geological Survey. The sensitivity, precision and accuracy of the method are also discussed. (Author) [pt

  9. Isotope and chemical tracers in groundwater hydrology

    International Nuclear Information System (INIS)

    Kendall, C.; Stewart, M.K.; Morgenstern, U.; Trompetter, V.

    1999-01-01

    The course sessions cover: session 1, Fundamentals of stable and radioactive isotopes; session 2, Stable oxygen and hydrogen isotopes in hydrology: background, examples, sampling strategy; session 3, Catchment studies using oxygen and hydrogen isotopes: background - the hydrologic water balance, evapotranspiration - the lion's share, runoff generation - new water/old water fractions, groundwater recharge - the crumbs; session 4, Isotopes in catchment hydrology: survey of applications, future developments; session 5, Applications of tritium in hydrology: background and measurement, interpretation, examples; session 6, Case studies using mixing models: Hutt Valley groundwater system, an extended mixing model for simulating tracer transport in the unsaturated zone; session 7, Groundwater dating using CFC concentrations: background, sampling and measurement, use and applications; session 8, Groundwater dating with carbon-14: background, sampling and measurement, use and applications; session 9, NZ case studies: Tauranga warm springs, North Canterbury Plains groundwater; session 10, Stable carbon and nitrogen isotopes: background and examples, biological applications of C-N-S isotopes; session 11, New developments in isotope hydrology: gas isotopes, compound specific applications, age dating of sediments etc; session 12, NZ case studies: North Canterbury Plains groundwater (continued), Waimea Plains groundwater. (author). refs., figs

  10. Proton NMR investigation of heme pocket mobility in hemoglobin via hydrogen isotope exchange kinetics

    International Nuclear Information System (INIS)

    Han, K.

    1985-01-01

    Dynamic mobility of heme cavity, the active site of Hb, was investigated by analyzing the hydrogen isotope exchange kinetics of the proximal histidyl ring NH of various kinds of Hbs with the aid of the high field Fourier Transform 1 H NMR spectroscopy. The exchange reaction occurs faster in oxy or R-state Hb than in deoxy or T-state Hb and there exists a good correlation between the oxygen affinity of Hb and the heme pocket mobility reflected in the hydrogen exchange rate. The effect of pH on the exchange is dramatically different for the two subunits of Hb A. Studying the exchange characteristics of mutant Hbs and chemically modified Hbs not only showed the existence of three well-defined localized paths for transmission of conformational changes between different heme pockets through a 1 b 2 subunit interface, but also indicated that the heme pocket mobility is regulated by the quaternary state of Hb as well as by the ligation state of Hb. Finally, the effect of the quaternary state on the heme pocket mobility is separated from that of the ligation by following the exchange reactions in Hbs where only their quaternary structure transition can be achieved without changing their ligation states by adjusting experimental conditions such as adding inositol hexaphosphate

  11. Antibodies and isotopes, a chemical approach to tumour targeting

    International Nuclear Information System (INIS)

    Vaughan, A.T.M.; Yankuba, S.C.S.; Anderson, P.

    1986-01-01

    In this study, scandium-47 and yttrium-90 have been used as representatives of potential cytotoxic labels. Both isotopes have a high yield of energetic beta particles and half-lives of the same order as indium-111. In addition they are both members of Group III and so may be used as a base for chemical comparisons in the future with radiotoxic isotopes from other chemical groups

  12. Preparation of inorganic ion exchangers with high selectivity for lithium isotopes

    International Nuclear Information System (INIS)

    Oi, Takao

    2004-01-01

    Development of ion exchangers that show large lithium isotope effects is hoped for to establish highly efficient chromatographic processes of lithium isotope separation. In this paper, preparation, characterization, ion exchange properties, and lithium isotope selectivity of inorganic materials that have been and still are being studied by my research group at Sophia University are reviewed. They include manganese oxides-based ion exchangers, antimonic acids and titanium/zirconium phosphates-based ion exchangers. As a result, the lithium isotope separation effects that were one order of magnitude larger than those of organic ion exchangers were obtained. Some inorganic ion exchangers were found to show ion exchange rates more than comparable to those of organic ones. (author)

  13. Thermoneutral isotope exchange reactions of cations in the gas phase

    International Nuclear Information System (INIS)

    Ausloos, P.; Lias, S.G.

    1981-01-01

    Rate constants have been measured for reactions of the type AD 2 + + MH → MD + ADH + , where AD 2 + is CD 3 CND + , CD 3 CDOD + , (CD 3 COCD 3 )D + , or (C 2 D 5 ) 2 OD + and the MH molecules are alcohols, acids, mercaptans, H 2 S, AsH 3 , PH 3 , or aromatic molecules. Rate constants are also presented for the reactions Ar/sub H/D + + D 2 O → Ar/sub d/D + + HDO, where Ar/sub H/D + is a deuteronated aromatic molecule and Ar/sub D/D + is the same species with a D atom incorporated on the ring. In all but two cases, the competing deuteron transfer is sufficiently endothermic that it cannot be observed under the conditions of the ICR experiments at 320 to 420 K. The efficiencies of the isotope exchange reactions are interpreted in terms of estimated potential surface cross sections for the reactions AD 2 + + MH → [AD 2 + MH] → [ADMHD + ] → [ADH + MD] → ADH + + MD. When the formation of the [ADMHD + ] complex is estimated to be thermoneutral or slightly endothermic, the isotope exchange process is inefficient (probability of a reactive collision 2 + MH] → [ADMHD + ] is exothermic. For most of the systems, trends in reaction efficiency appear to be related to factors such as dipole moments of reactant species (or for aromatic compounds, the electron-donating or -withdrawing properties of ring substituents) which influence the relative orientation of the two reactant species in the complex

  14. Separation of boron isotopes by ion exchange chromatography: studies with Duolite-162, a type-II resin

    International Nuclear Information System (INIS)

    Sharma, B.K.; Subramanian, R.; Balasubramanian, R.; Mathur, P.K.

    1994-01-01

    The selection of resin plays an important role in the process of separation of boron isotopes by ion exchange chromatography. The determination of (i) ion exchange capacity of Duolite-162 resin for hydroxyl - chloride exchange, (ii) hydroxyl - borate exchange, (iii) isotopic exchange separation factor by batch method and (iv) effect of concentration of boric acid on isotopic exchange separation factor to test the suitability of the above resin for this process are discussed in this report. (author)

  15. A determination of elementary separation factors of isotopes 235U and 238U in the ionic exchange process and of eluents in the water-glycerine system

    International Nuclear Information System (INIS)

    Murgulescu, S.E.

    1977-01-01

    In the experiments focused on uranium isotope separation by ion and chemical exchange, the water-glycerine system was employed. The principle of the method consists in shifting a uranium band along an ion-exchange resin column by means of an eluent. The isotope effect of reactions determining the band heading into the column where complex bands between the metal ion and the ligand form and break up under the resin influence, is determined by the difference in affinity between the two isotopes as against the eluent. The isotope effect in question determines a unit deviation of the equilibrium constant for the classical isotope exchange reaction. Starting from the experimental results obtained, it was concluded that the ion and chemical exchange between the IV and VI valence forms of uranium can be applied to isotope separation in terms of the separation unit. As against the methods that have been applied at present (gaseous scattering, hydro-extracting and the nozzle method), for which every new stage corresponds to a separation elementary factor, several separation elementary factors can be cumulated into a single stage in a chemical and ion exchange unit, by the optimization of the shifting band and length. (author)

  16. Chemical methods for Sm-Nd separation and its application in isotopic geological dating

    International Nuclear Information System (INIS)

    Guo Qifeng.

    1990-01-01

    Three chemical methods for Sm-Nd separation are mainly desribed: low chromatography of butamone-ammonium thiocyanate for hight concentration Sm and Nd separation, P 240 column chromatography for medium concentration Sm-Nd separation, and pressure ion exchange for low concentration Sm-Nd. The first Sm-Nd synchrone obtained in China with Sm-Nd methods is introduced and Sm-Nd isotopic geological dating in Early Archaean rocks in eastern Hebei has been determined

  17. 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%

  18. Sulfur isotope separation by anion exchange chromatography: 34 S isotope enrichment

    International Nuclear Information System (INIS)

    Bendassolli, Jose Albertino; Trivelin, Paulo Cesar O.; Carneiro Junior, Francisco

    1995-01-01

    The 34 S isotope separation was carried out by isotopic exchange reactions between sulphurous acid in solution and bisulphite anions adsorbed on an ammonium quaternary (Dowex 1 x 8 and Dowex 2 x 8, 100-200 mesh) anion exchange resin packed in columns. Each resin column had 130 cm length and 2.2 cm diameter. The columns were connected in series during displacement of bisulphite bands. For the experiments, a band of bisulphite was fixed to the anion resin, initially in the hydroxyl ion form, and subsequently eluted with 0.2 0.3, 0.4 and 0.6 mol L -1 HCL solution. The hydrochloric acid solution was kept under a nitrogen atmosphere at 245 KPa of pressure, in order to prevent the evolution of gases and also the oxidation of the bisulphite. The experiments showed that the best results were obtained with the elution of bisulphite with 0.2 mol.L -1 HCL, with the Dowex 1 x 8 resin. Enrichments in 34 S of 17.33 atoms% were obtained using Dowex 1 x 8 resin, 0.2 mol.L -1 HCL solution and band displacement of 50 m. Replacing the depleted portion of the band with natural bisulphite, for each 10 m of band displacement, produced 6.79 mmol of sulphurous acid enriched with approximately 17% of 34 S, after 14 m of band dislocation. (author). 7 refs., 1 fig., 2 tabs

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

    International Nuclear Information System (INIS)

    Chiba, H.; Sakai, H.

    1985-01-01

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

  20. Hydrogen and oxygen isotope exchange reactions over illuminated and nonilluminated TiO2

    International Nuclear Information System (INIS)

    Sato, S.

    1987-01-01

    Hydrogen isotope exchange between H 2 , gaseous H 2 O, and the surface hydroxyls of TiO 2 , and oxygen isotope exchange between O 2 , CO 2 , CO, H 2 O vapor, and the hydroxyls over TiO 3 were studied at room temperature in the dark and under illumination. Hydrogen isotope exchange between H 2 O and the hydroxyls occurred rapidly in the dark, but the exchange involving H 2 did not occur at all even under illumination. Oxygen isotope exchange among H 2 O vapor, CO 2 , and the hydroxyls easily took place in the dark, but the exchange involving O 2 required band-gap illumination. Dioxygen isotope equilibration was much faster than the other photoexchange reactions. Although the oxygen exchange between O 2 and illuminated TiO 2 has been considered to involve lattice-oxygen exchange, the present experiments revealed that the hydroxyls of TiO 2 mainly participate in the exchange reaction. The oxygen exchange between O 2 and H 2 O vapor was strongly inhibited by H 2 O vapor itself probably because oxygen adsorption was retarded by adsorbed water. Oxygen in CO was not exchanged with the other substrates under any conditions tested

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

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

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  3. 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.

  4. Laser isotope separation - a new class of chemical process

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  5. Efficiency of Al2O3 supported palladium sorbents in the process of hydrogen isotope exchange

    International Nuclear Information System (INIS)

    Andreev, B.M.; Perevezentsev, A.N.; Yasenkov, V.I.

    1981-01-01

    It is found that in the hydrogen-palladium system while applying the metal to aluminium oxide a considerable increase of the heterogeneous hydrogen isotopic exchange rate is observed due to the increase of its specific surface at 167-298 K temperatures and 350-500 Torr hydrogen pressures. It is shown that in the process of thermal treatment of the supported palladium sorbent resulting in reconstruction of the carrier porous structure, as well as in increasing the metal crystal size, the change of the stage, limiting the isotopic exchange process, occurs. The values of the rate and energy of activation of the hydrogen isotopic exchange are presented [ru

  6. Isotopic Abundance and Chemical Purity Analysis of Stable Isotope Deuterium Labeled Sudan I

    Directory of Open Access Journals (Sweden)

    CAI Yin-ping;LEI Wen;ZHENG Bo;DU Xiao-ning

    2014-02-01

    Full Text Available It is important that to analysis of the isotopic abundance and chemical purity of Sudan I-D5, which is the internal standard of isotope dilution mass spectrometry. The isotopic abundance of Sudan I-D5 is detected by “mass cluster” classification method and LC-MS. The repeatability and reproducibility experiments were carried out by using different mass spectrometers and different operators. The RSD was less than 0.1%, so the repeatability and reproducibility were satisfactory. The accuracy and precision of the isotopic abundance analysis method was good with the results of F test and t test. The high performance liquid chromatography (HPLC had been used for detecting the chemical purity of Sudan I-D5 as external standard method.

  7. Nucleophilic radioiodination of 6-bromocholesterol via non-isotopic exchange reaction in molten state

    International Nuclear Information System (INIS)

    El-Shaboury, G.; Farah, K.; El-Tawoosy, M.

    2001-01-01

    A synthetic method for preparing radioiodinated 6-[ 125 I]iodocholesterol [CL-6- 125 I] for adrenal evaluation is described. The radioiodine atom was incorporated onto the cholesterol molecule via non-isotopic exchange between 6-bromocholesterol [CL-6-Br] and radioiodine as iodide ion [ 125 I - ] in a molten state. The different parameters affecting the yield of exchange were investigated using 125 I (T 1/2 ≅ 60 d) to centralize the different physical and chemical reaction conditions and purification of the final product as pure as 6-[ 125 I]iodocholesterol. The method was suitable to either 131 I (T 1/2 ≅ 8 d) nucleophilic radioiodination which facilitates the scanning of the adrenal for a few days after administration or the use of 124 I (T 1/2 ≅ 4.16 d) nucleophilic radioiodination for PET evaluation of the adrenal. TLC as well as HPLC chromatographic analysis is used to determine the efficiency of the exchange reactions under different chemical reaction conditions and to monitor the stability of the final product as pure as CL-6- 125 I with radiochemical purity of ≅99%. This no-carrier-added method improved the speed of the reaction and affords high radiochemical yield of 90% and suitable specific activity due to the use of CL-6-Br rather than CL-6-I as substrate. Kinetic studies revealed second order iodine-bromine exchange reaction. The activation energy for the exchange reaction in ammonium acetate (m.p. 114 deg C) was calculated to be 4.576 kcal/mole. (author)

  8. Isotopic composition of chemical elements in natural cycles

    International Nuclear Information System (INIS)

    Wetzel, K.

    1977-12-01

    Mathematical models developed for planning and evaluating tracer experiments have been applied in investigations of the isotopic composition of carbon in its natural cycle through various periods of the last billion years. The influence on the natural isotope ratio due to industrial combustion of fossil fuels is shown. In order to describe regional differences from the global behaviour of carbon a parameter has been introduced, which represents the time needed for one total exchange of the atmosphere in a certain region with the global atmosphere

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

    Directory of Open Access Journals (Sweden)

    P.U. Singare

    2014-06-01

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

  10. Differential multiple quantum relaxation caused by chemical exchange outside the fast exchange limit

    International Nuclear Information System (INIS)

    Wang Chunyu; Palmer, Arthur G.

    2002-01-01

    Differential relaxation of multiple quantum coherences is a signature for chemical exchange processes in proteins. Previous analyses of experimental data have used theoretical descriptions applicable only in the limit of fast exchange. Theoretical expressions for differential relaxation rate constants that are accurate outside fast exchange are presented for two-spin-system subject to two-site chemical exchange. The theoretical expressions are validated using experimental results for 15 N- 1 H relaxation in basic pancreatic trypsin inhibitor. The new theoretical expression is valuable for identification and characterization of exchange processes in proteins using differential relaxation of multiple quantum coherences

  11. Preparation of [125I]triiodothyronine by isotopic exchange

    International Nuclear Information System (INIS)

    Kopicka, K.; Kronrad, L.; Hradilek, P.

    1981-01-01

    The effect was studied of various factors on isotopic exchange. The reaction proceeded in an ethanol-water (1:1) medium under the catalytic effect of elemental iodine added in form of an ethanol solution at a temperature of 25 degC. The yield is significantly affected by the sequence of adding components in the reaction mixture. The highest yield of labelled triiodothyronine was obtained using the following procedure: a solution of radioactive sodium iodide and elemental iodine was mixed and after 5 seconds, a triiodothyronine solution was added. The yield also depended on the concentrations of I 2 , of triiodothyronine and of the nonactive carrier in the radioactive sodium iodide solution. The specific activity of 2.6 GBq/mg was achieved for a triiodothyronine concentration in the reaction mixture of 2.4x10 -4 M and an I 2 concentration of 10 -4 N. For analytical chromatographic separation of reaction products, the n-hexane/amyl alcohol/2M ammonia system was used reliably separating triiodothyronine and thyroxine. (Ha)

  12. Chemical uranium enrichment with ion exchanger

    International Nuclear Information System (INIS)

    Takeda, Kunihiko; Onitsuka, Hatsuki; Obanawa, Heiichiro

    1991-01-01

    The uranium enrichment by using ion-exchange has been studied and developed since 1972. The ion-exchange rate has been improved approx. 3000 times and the electron exchange reaction, which occurs with ion-exchange reaction, was also accelerated with catalyst. Flow disturbance in a ion-exchange column has been fully studied and the value of turbulence has been reduced to 150μm. These results allowed us to design a very fine separation column, in which about 10000 stages can be obtained even when the column is more than 1 m in diameter. In the course of the development, a self-regenerating reaction between the redox agents was discovered and incorporated into the process, and has resulted in a reduction of 70 % in the separation energy requirement. (author)

  13. Influence of chemical structure on carbon isotope composition of lignite

    Science.gov (United States)

    Erdenetsogt, Bat-Orshikh; Lee, Insung; Ko, Yoon-Joo; Mungunchimeg, Batsaikhan

    2017-04-01

    During the last two decades, a number of studies on carbon isotopes in terrestrial organic matter (OM) have been carried out and used to determine changes in paleoatmospheric δ13C value as well as assisting in paleoclimate analysis. Coal is abundant terrestrial OM. However, application of its δ13C value is very limited, because the understanding of changes in isotopic composition during coalification is relatively insufficient. The purpose of this study was to examine the influence of the chemical structure on the carbon isotope composition of lignite. Generally, lignite has more complex chemical structures than other higher rank coal because of the existence of various types of oxygen-containing functional groups that are eliminated at higher rank level. A total of sixteen Lower Cretaceous lignite samples from Baganuur mine (Mongolia) were studied by ultimate, stable carbon isotope and solid-state 13C CP/MAS NMR analyses. The carbon contents of the samples increase with increase in depth, whereas oxygen content decreases continuously. This is undoubtedly due to normal coalification process and also consistent with solid state NMR results. The δ13C values of the samples range from -23.54‰ to -21.34‰ and are enriched in 13C towards the lowermost samples. Based on the deconvolution of the NMR spectra, the ratios between carbons bonded to oxygen (60-90 ppm and 135-220 ppm) over carbons bonded to carbon and hydrogen (0-50 ppm and 90-135 ppm) were calculated for the samples. These correlate well with δ13C values (R2 0.88). The results indicate that the δ13C values of lignite are controlled by two mechanisms: (i) depletion in 13C as a result of loss of isotopically heavy oxygen-bounded carbons and (ii) enrichment in 13C caused by a loss of isotopically light methane from aliphatic and aromatic carbons. At the rank of lignite, coal is enriched in 13C because the amount of isotopically heavy CO2 and CO, released from coal as a result of changes in the chemical

  14. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

    Science.gov (United States)

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

    2015-04-28

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

  15. Study of reactions of isotopic exchange of trans-zeatin with tritium

    International Nuclear Information System (INIS)

    Sidorov, G.V.; Myasoedov, N.F.

    2006-01-01

    Reactions of isotopic exchange of trans-zeatin with high-radioactive tritium water, with gaseous tritium in solution and solid-phase catalytic hydrogenation are studied to prepare trans-zeatin and dihydrozeatin labelled with tritium. It is shown that reaction of isotopic exchange of trans-zeatin with gaseous tritium both in solutions and without solvents at 160 Deg C and above leads to practically total hydrogenation of initial compound with formation of dihydrozeatin labelled with tritium. Isotopic exchange with tritium water permits to prepare zeatin labelled with tritium with 67 % yield and specific radioactivity 0.68 PBq/mol. It is determined that in the case of solid-phase isotopic exchange within 150-155 Deg C temperature interval both dihydrozeatin and trans-zeatin labelled with tritium are formed [ru

  16. Spin-locking vs. chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2010-01-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of non-equivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolites with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: i) On-resonance SL is most sensitive to chemical exchanges in the intermediate exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. ii) Offset frequency-dependent SL and CEST spectra are very similar, and can be explained well with an SL model recently developed by Trott and Palmer. iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. iv) The asymmetry of the magnetization transfer ratio (MTRasym) is highly dependent on the choice of saturation pulse power. In the intermediate exchange regime, MTRasym becomes complicated and should be interpreted with care. PMID:21500270

  17. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2011-05-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care. Copyright © 2010 Wiley-Liss, Inc.

  18. Enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvent

    International Nuclear Information System (INIS)

    Raica, Paula; Axente, D.

    2009-01-01

    Full text: Enrichment of 13 C by chemical exchange between CO 2 and amine carbamate in nonaqueous solvent has been mathematically modelled in two ways. The height equivalent to a theoretical plate and steady-state separation, based on the two models, have been obtained. If only the isotopic exchange between CO 2 gas and amine carbamate is considered, the model can estimate the process performance for pressures close to the atmospheric one and room temperature. For process analysis at pressures higher than atmospheric one and lower temperatures, a two-step model has been developed. Using the two models the effects of pressure increasing have been studied. At atmospheric pressure and 2M DNBA - methanol solution the isotope transfer rate is lower at 5 deg. C than at 25 deg. C. The isotope transfer is supported by pressure increasing according the increase of the CO 2 concentration in the amine solution. A lower temperature determines also an increase in the concentration of dissolved CO 2 and, for this reason, at 5 deg.C and higher pressures the isotope exchange reaction rate is higher than at 25 deg. C, HETP being lower with more than 100% at 5 deg. C than at 25 deg. C. (authors)

  19. The exchange of acetaldehyde between plants and the atmosphere: Stable carbon isotope and flux measurements

    Science.gov (United States)

    Jardine, Kolby Jeremiah

    The exchange of acetaldehyde between plant canopies and the atmosphere may significantly influence regional atmospheric chemistry and plant metabolism. While plants are known to both produce and consume acetaldehyde, the exchange of this compound with forested ecosystems is complicated by physical, biological, and chemical processes that range from being poorly understood to completely unknown. This precludes a quantitative understanding of acetaldehyde exchange rates between the atmosphere and the biosphere. In this study, the processes controlling the exchange of acetaldehyde with plant canopies was investigated using concentration, flux, and natural abundance 13C measurements of gas phase acetaldehyde from individual plants, soils, and entire ecosystems. Although previously only considered important in anoxic tissues, it was discovered that acetaldehyde is produced and consumed in leaves through ethanolic fermentation coupled to the pyruvate dehydrogenase bypass system under normal aerobic conditions. These coupled pathways determine the acetaldehyde compensation point, a major factor controlling its exchange with the atmosphere. Carbon isotope analysis suggests a new pathway for acetaldehyde production from plants under stress involving the peroxidation of membrane fatty acids. This pathway may be a major source of acetaldehyde to the atmosphere from plants under biotic and abiotic stresses. Plant stomata were found to be the dominant pathway for the exchange of acetaldehyde with the atmosphere with stomatal conductance influencing both emission and uptake fluxes. In addition, increasing temperature and solar radiation was found to increase the compensation point by increasing the rates of acetaldehyde production relative to consumption. Under ambient conditions, bare soil was neutral to the exchange of acetaldehyde while senescing and decaying leaves were found to be strong source of acetaldehyde to the atmosphere due to increased decomposition processes and

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

    Energy Technology Data Exchange (ETDEWEB)

    Frierdich, Andrew J. [Univ. of Wisconsin, Madison, WI (United States); Univ. of Iowa, Iowa City, IA (United States); Beard, Brian L. [Univ. of Wisconsin, Madison, WI (United States); Rosso, Kevin M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Scherer, Michelle M. [Univ. of Iowa, Iowa City, IA (United States); Spicuzza, Michael J. [Univ. of Wisconsin, Madison, WI (United States); Valley, John W. [Univ. of Wisconsin, Madison, WI (United States); Johnson, Clark M. [Univ. of Wisconsin, Madison, WI (United States)

    2015-07-01

    The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Fe isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II)aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II)aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II)aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous

  1. Process for improving the separation efficiency in the isolation of radioactive isotopes in elementary or chemically bonded form from liquids and gases

    International Nuclear Information System (INIS)

    Schmidberger, R.; Kirch, R.; Kock, W.

    1986-01-01

    In the process for the improvement of the separation efficiency in the isolation of radioactive isotopes in elementary or chemically bonded form from liquids or gases by ion exchange and adsorption, non-radioactive isotopes of the element to be isolated are added to the fluid before the isolation, whereas at the same time a large surplus of the non-radioactive isotopes to the radioactive isotopes is achieved by addition of only small quantities of compounds of the non-radioactive isotopes. (orig./RB) [de

  2. Chemical and isotopic composition of precipitations in Syria

    International Nuclear Information System (INIS)

    Abou Zakhem, B.; Hafez, R.

    2008-01-01

    13 meteoric stations were selected in syria for cumulative monthly rainfall sampling during two hydrological cycles; 1991-1992 and 1992-1993. The chemical and isotopic compositions of monthly precipitation were studied. The winter and spring rainfall isotopic characteristics were determined, in addition to the syrian or local meteoric line (SMWL) was estimated with a slope of 6.63 and that of both syria and Jordan of 6.73. The effect of climatic factors as temperature and relative air humidity on oxygen-18, deuterium and d-excess were studied and it was found that the relationship between temperature and oxygen-18 and deuterium is a positive linear correlation; however, it is a negative correlation with d-excess. The mean seasonal variation amplitude was determined by 6%, and the amount effect on isotopic content of precipitation was studied. The geographic factors and its affect on isotopic contents of precipitation such as altitude were considered, furthermore, the isotopic gradient with altitude was determined for both oxygen-18 and deuterium (-0.14% and - 0.84%/100 m elevation respectively). The spatial variability of oxygen-18, deuterium, tritium and d-excess indicted the effect of mountain chains and gaps between mountains on the isotopic content of precipitation, the continental effect on tritium build-up by about 33% per 100 Km from the coast. The increase of d-excess values towards the south west proves the eastern mediterranean climate type over this region. (author)

  3. Chemical and isotopic composition of precipitations in Syria

    International Nuclear Information System (INIS)

    Abou Zakhem, B.; Hafez, R.

    2007-05-01

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

  4. Method for separating the isotopes of a chemical element

    International Nuclear Information System (INIS)

    Devienne, F.M.

    1977-01-01

    A beam of positive or negative primary ions of at least one compound of a chemical element is accelerated in order to pass through collision boxes placed in series. As a result of inelastic collisions of the ions with the molecules of a neutral target gas within each collision box, a given percentage of primary ions is dissociated into at least two fragments, one of which is a secondary ion in the form of at least two isotopic species. The collision boxes are brought to a potential V 2 so as to trap preferentially one isotopic species which is condensed within each box. 15 claims, 4 figures

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1975-12-01

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

  6. Some considerations on the treatment of the kinetic data of heterogeneous isotope exchange

    International Nuclear Information System (INIS)

    Koernyei, J.; Szirtes, L.; Lakatos, M.

    1985-01-01

    A direct curve simulation treatment was worked out for the evaluation of the kinetic curves of heterogeneous isotope exchange. Based on the data obtained by a personal computer, some considerations were made on the transport processes in the fully and half exchanged sodium forms of crystalline zirconium phosphate. (author)

  7. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    Science.gov (United States)

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  8. Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

    Science.gov (United States)

    Yurimoto; Ito; Nagasawa

    1998-12-04

    A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

  9. Relative mobility of 1-H atoms of carbohydrates in heterogeneous isotope exchange reactions

    International Nuclear Information System (INIS)

    Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskii, Yu.L.

    1988-01-01

    The method of competitive reactions was used to determine the relative mobilities of the 1-H atoms of carbohydrates in reactions of heterogeneous isotope exchange, using various reference standards, catalysts, and buffer systems. On the basis of the results obtained, the investigated carbohydrates are ranged in a series of decreasing mobility of the hydrogen atoms exchanged in heterogeneous isotope exchange reactions. It was demonstrated that the mobility of the 1-H atoms is related to the concentration of the acyclic forms of the carbohydrates

  10. Calcium isotope effects in ion exchange electromigration and calcium isotope analysis by thermo-ionization mass spectrometry

    International Nuclear Information System (INIS)

    Fujii, Y.; Hoshi, J.; Iwamoto, H.; Okamoto, M.; Kakihana, H.

    1985-01-01

    Calcium ions were made to electromigrate along a cation exchange membrane. The abundance ratios of the calcium isotopes (Ca-40, 42, 43, 44, 48) in the migrated bands were measured by thermo-ionization mass spectrometry. The lighter isotopes were enriched in the front part of the migrated band. The increments in the isotope abundance ratios were found to be proportional to the mass difference of the isotopes. The observed epsilon-values per unit mass difference (epsilon/ΔM) were 1.26 x 10 -4 (at 20 0 C), 1.85 x 10 -4 (at 25 0 C) and 2.4 x 10 -4 (at 40 0 C). The mass spectrometry was improved by using a low temperature for the evaporation of CaI 2 . (orig.)

  11. Mechanistic study of the isotopic-exchange reaction between gaseous hydrogen and palladium hydride powder

    International Nuclear Information System (INIS)

    Outka, D.A.; Foltz, G.W.

    1991-01-01

    A detailed mechanism for the isotopic-exchange reaction between gaseous hydrogen and solid palladium hydride is developed which extends previous model for this reaction by specifically including surface reactions. The modeling indicates that there are two surface-related processes that contribute to the overall rate of exchange: the desorption of hydrogen from the surface and the exchange between surface hydrogen and bulk hydrogen. This conclusion is based upon measurements examining the effect of small concentrations of carbon monoxide were helpful in elucidating the mechanism. Carbon monoxide reversibly inhibits certain steps in the exchange; this slows the overall rate of exchange and changes the distribution of products from the reactor

  12. Kinetics of isotopic exchange between strontium polymolybdate and strontium ions in aqueous solution

    International Nuclear Information System (INIS)

    Atun, Gulten; Bilgin, Binay; Kilislioglu, Ayben

    2002-01-01

    A heterogeneous isotopic exchange reaction of strontium polymolybdate in strontium chloride solution was studied using 90 Sr as a tracer. The effects of low and high strontium chloride concentration on the rate and mechanism of the isotopic exchange reaction were investigated. It was found that, at high concentrations, the rate is independent of strontium concentration, but, at low concentrations, the rate is proportional to the strontium concentration. These results support a hypothesis that, at low concentrations, the rate is controlled by film diffusion, whereas at high concentrations it is controlled by particle diffusion. Experiments were performed at 293, 303 and 313 K. Activation energy of isotopic exchange reaction and thermodynamic parameters ΔH*, ΔS*, and ΔG* were calculated using the Arrhenius and Eyring equations. The results also indicated that recrystallization is a predominant factor in the present exchange reaction

  13. Kinetics of isotopic exchange between strontium polymolybdate and strontium ions in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Atun, Gulten E-mail: gultena@istanbul.edu.tr; Bilgin, Binay; Kilislioglu, Ayben

    2002-06-01

    A heterogeneous isotopic exchange reaction of strontium polymolybdate in strontium chloride solution was studied using {sup 90}Sr as a tracer. The effects of low and high strontium chloride concentration on the rate and mechanism of the isotopic exchange reaction were investigated. It was found that, at high concentrations, the rate is independent of strontium concentration, but, at low concentrations, the rate is proportional to the strontium concentration. These results support a hypothesis that, at low concentrations, the rate is controlled by film diffusion, whereas at high concentrations it is controlled by particle diffusion. Experiments were performed at 293, 303 and 313 K. Activation energy of isotopic exchange reaction and thermodynamic parameters {delta}H*, {delta}S*, and {delta}G* were calculated using the Arrhenius and Eyring equations. The results also indicated that recrystallization is a predominant factor in the present exchange reaction.

  14. Isotope exchange kinetic of phosphorus in soils from Pernambuco State -Brazil

    International Nuclear Information System (INIS)

    Figueiredo, F.J.B. de.

    1989-12-01

    The applicability of isotopic exchange kinetics of 32 p to characterize phosphorus available to plants and to diagnose the reactivity of soil-fertilizer-P in six soils from Pernambuco is described. This methodology was compared with anion exchange resin, isotopic exchange equilibrium methods (E-value and L-value) and P absorption by plants. The first greenhouse experiment had the following treatments: 1) with P and, 2) with addition of 43.7 mg P/Kg of soil, incubated for O, 42 and 84 days before seeding. The kinetic of isotopic exchange (KIE), resin-P and E-value were determined before seeding and after harvesting pearl millet grown for 42 days. Results indicated that the KIE parameters rated the soils more efficiently, in terms of available P and soil-fertilizer-P reactivity, than resin-P, E-value and L-value. (author). 38 refs, 2 figs, 18 tabs

  15. Separation of boron isotopes by ion exchange chromatography: studies on regeneration of strong base anion exchange resins

    International Nuclear Information System (INIS)

    Sharma, B.K.; Subramanian, R.; Mathur, P.K.

    1994-01-01

    The optimum conditions for the regeneration of strong base anion exchange resins of type-I and type-II were determined for cost-effective separation of isotopes of boron by ion exchange chromatography where the hydroxyl form of an anion exchange resin is equilibrated with boric acid solution containing mannitol as a complexing reagent. The possibility of using unspent alkali content of the effluent was also exploited. Removal of carbonate impurity from Rayon grade caustic lye (used as regenerant after dilution) and recycling of Ba(OH) 2 was studied to avoid waste disposal problems. (author)

  16. On-line stable isotope measurements during plant and soil gas exchange

    International Nuclear Information System (INIS)

    Yakir, D.

    2001-01-01

    Recent techniques for on-line stable isotope measurements during plant and soil exchange of CO 2 and/or water vapor are briefly reviewed. For CO 2 , these techniques provide means for on-line measurements of isotopic discrimination during CO 2 exchange by leaves in the laboratory and in the field, of isotopic discrimination during soil respiration and during soil-atmosphere CO 2 exchange, and of isotopic discrimination in O 2 during plant respiration. For water vapor, these techniques provide means to measure oxygen isotopic composition of water vapor during leaf transpiration and for the analysis of sub microliter condensed water vapor samples. Most of these techniques involve on-line sampling of CO 2 and water vapor from a dynamic, intact soil or plant system. In the laboratory, these systems also allow on-line isotopic analysis by continuous-flow isotope ratio mass spectrometry. The information obtained with these on-line techniques is becoming increasingly valuable, and often critical, for ecophysiologial research and in the study of biosphere-atmosphere interactions. (author)

  17. Kinetics of isotopic exchange of [1-3H]saccharides with hydrogen using palladium catalysts

    International Nuclear Information System (INIS)

    Akulov, G.P.; Kayumov, V.G.; Snetkova, E.V.; Kaminskij, Yu.L.

    1988-01-01

    The kinetics was studied of the isotopic exchange of [1- 3 H]saccharides with hydrogen on palladium catalysts. The effect was studied of different factors on the rate of isotopic exchange, e.g., of the composition and structure of saccharides, their concentration in the solution (C), the type of catalyst and of the buffer solution. It was found that by reduced rate of isotopic exchange with hydrogen, all studied saccharides may be arranged into a series independent of the type of catalyst in accordance with the sequence of declining coefficient of relative mobility of l-H atoms during the reaction. Linear dependence was found to exist between the rate constant of the isotopic exchange reaction (r) and the coefficient of relative lability. It was also found that in the range of low concentrations the observed rate constants of isotopic exchange were not dependent on concentration and in the range of higher concentrations, r decreased with increasing C. This character of dependence is justified by the side effect of the processes of sorption on the catalyst. (author). 3 figs., 1 tab., 4 refs

  18. Isotopic exchange reaction between barium ion and tri barium phosphate

    International Nuclear Information System (INIS)

    Bilgin, G.B.; Cetin, I.

    1982-01-01

    Heterogeneous exchange reaction of tri barium phosphate in barium chloride solution has been studied using 133 Ba as a tracer. The results show that the exchange fraction increases as barium chloride concentration increases for different mole ratio of the exchange ion on the solid surface and in the solution. The phenomenon was studied with respect to the previous treatment of the precipitate leading to different crystal sizes and the effect of reaction time. (author)

  19. Empirical Correction for Differences in Chemical Exchange Rates in Hydrogen Exchange-Mass Spectrometry Measurements.

    Science.gov (United States)

    Toth, Ronald T; Mills, Brittney J; Joshi, Sangeeta B; Esfandiary, Reza; Bishop, Steven M; Middaugh, C Russell; Volkin, David B; Weis, David D

    2017-09-05

    A barrier to the use of hydrogen exchange-mass spectrometry (HX-MS) in many contexts, especially analytical characterization of various protein therapeutic candidates, is that differences in temperature, pH, ionic strength, buffering agent, or other additives can alter chemical exchange rates, making HX data gathered under differing solution conditions difficult to compare. Here, we present data demonstrating that HX chemical exchange rates can be substantially altered not only by the well-established variables of temperature and pH but also by additives including arginine, guanidine, methionine, and thiocyanate. To compensate for these additive effects, we have developed an empirical method to correct the hydrogen-exchange data for these differences. First, differences in chemical exchange rates are measured by use of an unstructured reporter peptide, YPI. An empirical chemical exchange correction factor, determined by use of the HX data from the reporter peptide, is then applied to the HX measurements obtained from a protein of interest under different solution conditions. We demonstrate that the correction is experimentally sound through simulation and in a proof-of-concept experiment using unstructured peptides under slow-exchange conditions (pD 4.5 at ambient temperature). To illustrate its utility, we applied the correction to HX-MS excipient screening data collected for a pharmaceutically relevant IgG4 mAb being characterized to determine the effects of different formulations on backbone dynamics.

  20. Study of stratosphere-troposphere exchange via 10Be/7Be isotope ratios

    International Nuclear Information System (INIS)

    Priller, A.; Berger, M.; Golser, R.; Kutschera, W.; Steier, P.; Vockenhuber, C.; Wild, E.M.

    2001-01-01

    Full text: The present study is part of the European project STACCATO (influence of stratosphere-troposphere exchange in a changing climate on atmospheric transport and oxidation capacity). Stratosphere-troposphere exchange (STE) is one of the key factors controlling the budgets of ozone, water vapor and other substances in both the troposphere and the lower stratosphere. However, its contribution to their ozone budget relative to photo-chemical ozone formation from natural and anthropogenic precursor emissions is still uncertain. An international effort is made to estimate the strength of STE and its impact on tropospheric chemistry. The two cosmogenic radioisotopes of beryllium, 10 Be and 7 Be have very different half-lives of 1.51 Ma and 53.4 d, respectively. The combination of production rates, half-lives and different residence times in the stratosphere and troposphere, respectively, results in 10 Be/ 7 Be isotope ratios which can be used as fingerprints for STE. This ratio helps to give a much improved estimate of STE. However, only few 10 Be measurements exist, because its detection requires the rather elaborate method of accelerator mass spectrometry (AMS). At the AMS facility VERA we are now measuring the 10 Be content of air filters from the high-alpine stations 'Hoher Sonnblick', Austria, and 'Zugspitze', Germany. The TBe content is measured separately by decay counting. In this presentation, we want to describe the method of measuring 10 Be with AMS, and to discuss the results of first 10 Be/ 7 Be ratios. (author)

  1. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  2. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  3. Kinetics of isotopic exchange between calcium molybdate and molybdate ions in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Atun, G.; Ayar, N.; Bilgin, B. [Istanbul Univ. (Turkey). Dept. of Chemistry, Fac. of Engineering; Bodur, N.; Ayyildiz, H. [Cekmece Nuclear Research and Training Center, Istanbul (Turkey)

    2007-07-01

    The heterogeneous isotopic anion exchange kinetics and equilibria between calcium molybdate and sodium molybdate solutions have been studied by using {sup 99}Mo as tracer in batch experiments. The values of exchange ratio lower than unity suggest that rate-limiting step is particle diffusion process and the effect of re-crystallization can be neglected. The self-diffusion coefficients calculated using both Paterson's and Nernst-Plank approximations are increased by the temperature. The observed values for isotope exchange characteristics such as exchange fractions, exchanging amounts and fractional attainment of equilibrium are consistent with those of their calculated values. Activation energy and thermodynamic parameters calculated based on transition state theory indicate the existence of both energy and entropy barrier in the system. (orig.)

  4. Kinetics of isotopic exchange between calcium molybdate and molybdate ions in aqueous solution

    International Nuclear Information System (INIS)

    Atun, G.; Ayar, N.; Bilgin, B.

    2007-01-01

    The heterogeneous isotopic anion exchange kinetics and equilibria between calcium molybdate and sodium molybdate solutions have been studied by using 99 Mo as tracer in batch experiments. The values of exchange ratio lower than unity suggest that rate-limiting step is particle diffusion process and the effect of re-crystallization can be neglected. The self-diffusion coefficients calculated using both Paterson's and Nernst-Plank approximations are increased by the temperature. The observed values for isotope exchange characteristics such as exchange fractions, exchanging amounts and fractional attainment of equilibrium are consistent with those of their calculated values. Activation energy and thermodynamic parameters calculated based on transition state theory indicate the existence of both energy and entropy barrier in the system. (orig.)

  5. Chemical exchange rotation transfer imaging of intermediate-exchanging amines at 2 ppm.

    Science.gov (United States)

    Zu, Zhongliang; Louie, Elizabeth A; Lin, Eugene C; Jiang, Xiaoyu; Does, Mark D; Gore, John C; Gochberg, Daniel F

    2017-10-01

    Chemical exchange saturation transfer (CEST) imaging of amine protons exchanging at intermediate rates and whose chemical shift is around 2 ppm may provide a means of mapping creatine. However, the quantification of this effect may be compromised by the influence of overlapping CEST signals from fast-exchanging amines and hydroxyls. We aimed to investigate the exchange rate filtering effect of a variation of CEST, named chemical exchange rotation transfer (CERT), as a means of isolating creatine contributions at around 2 ppm from other overlapping signals. Simulations were performed to study the filtering effects of CERT for the selection of transfer effects from protons of specific exchange rates. Control samples containing the main metabolites in brain, bovine serum albumin (BSA) and egg white albumen (EWA) at their physiological concentrations and pH were used to study the ability of CERT to isolate molecules with amines at 2 ppm that exchange at intermediate rates, and corresponding methods were used for in vivo rat brain imaging. Simulations showed that exchange rate filtering can be combined with conventional filtering based on chemical shift. Studies on samples showed that signal contributions from creatine can be separated from those of other metabolites using this combined filter, but contributions from protein amines may still be significant. This exchange filtering can also be used for in vivo imaging. CERT provides more specific quantification of amines at 2 ppm that exchange at intermediate rates compared with conventional CEST imaging. Copyright © 2017 John Wiley & Sons, Ltd.

  6. Chromatographic separation process with pellicular ion exchange resins that can be used for ion or isotope separation and resins used in this process

    International Nuclear Information System (INIS)

    Carles, M.; Neige, R.; Niemann, C.; Michel, A.; Bert, M.; Bodrero, S.; Guyot, A.

    1989-01-01

    For separation of uranium, boron or nitrogen isotopes, an isotopic exchange is carried out betwen an isotope fixed on an ion exchange resin and another isotope of the same element in the liquid phase contacting the resin. Pellicular resins are used comprising composite particulates with an inert polymeric core and a surface layer with ion exchange groups [fr

  7. 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.)

  8. Relation between separation factor of carbon isotope and chemical reaction of CO2 with amine in nonaqueous solvent

    International Nuclear Information System (INIS)

    Takeshita, Kenji; Kitamoto, Asashi

    1989-01-01

    The separation factor for carbon isotope exchange reaction between CO 2 and amine in nonaqueous solvent was related to absorption reaction of CO 2 in a solution. The test solutions were mixtures of primary amine (such as butylamine and tert-butylamine) or secondary amine (such as diethylamine, dipropylamine and dibutylamine) diluted with nonpolar solvent (octane or triethyalmine) or polar solvent (methanol), respectively. The isotope exchange reaction consists of three steps related to chemical reaction of CO 2 in amine and nonaqueous solvent mixture, namely the reaction between CO 2 and carbamic acid, that between CO 2 and amine carbamate, and that between CO 2 and carbamic ion. Above all, the isotope separation factor between CO 2 and carbamic acid had the highest value. The overall separation factor can be higher in amine-nonaqueous solvent mixture where the concentration of carbamic acid becomes higher. (author)

  9. 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)

  10. Isotope exchange study of nickel xanthate in presence of aniline and isomeric toluidines

    International Nuclear Information System (INIS)

    Naidu, G.R.K.; Naidu, P.R.

    1982-01-01

    Isotopic exchange behaviour of nickel xanthate is studied in the presence of aniline and three isomeric toluidines at 18degC. The effect of base concentration is also studied on the exchange rate. The results show that the complex is labile in the kinetic sense in the presence of aniline meta and para toluidines. The rate of exchange increases with and para toluidines. The rate of exchange increases with increase in concentration of the base. The complex displays inert behaviour in the presence of o-toluidine and it is ascribed to dominant steric effect. (author)

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

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi

    1991-01-01

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

  12. Hydrogen isotope exchange in a metal hydride tube

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, David B. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2014-09-01

    This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

  13. Isotope exchange investigation of nitrogen redistribution in expanded austenite

    International Nuclear Information System (INIS)

    Christiansen, T.L.; Drouet, M.; Martinavičius, A.; Somers, M.A.J.

    2013-01-01

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

  14. The outline of the processes for lithium isotope separation by ion exchange method

    International Nuclear Information System (INIS)

    Fujine, Sachio; Saito, Keiichiro; Naruse, Yuji; Shiba, Koreyuki; Kosuge, Masao; Itoi, Toshiaki; Kitsukawa, Tomohiko.

    1981-10-01

    A plant of lithium isotope separation by displacement chromatography is preliminary designed. The construction expenses of a 100 kg 7 Li/year plant and the unit cost of separation are estimated on the basis of the data taken from the literature, and the feasibility is studied. Experimental equipment of continuous displacement chromatography is set up and is tested with the stable automatic operation. These results indicate that the ion exchange method is promising for industrial lithium isotope separation. (author)

  15. Charge exchange of excited mesic atoms of hydrogen isotopes in triple collisions with molecules

    International Nuclear Information System (INIS)

    Men'shikov, L.I.; Ponomarev, L.I.

    1985-01-01

    At high densities of deuterium-tritium mixture the probability for the occurrence of the isotope-exchange reaction (dμ)/sub n/+t → d+(tμ)/sub n/ from the excited states of n mesic atoms of deuterium is high in the triple collisions of mesic atoms with the molecules of hydrogen isotopes. This reaction should be taken into account in describing the kinetics of muon catalysis

  16. Chemical and isotopic fingerprinting of ancient Chinese porcelains

    International Nuclear Information System (INIS)

    Zhao, J.-X.; Li, B.-P.; Greig, A.; Collerson, K.D.; Feng, Y.-X.

    2005-01-01

    We have obtained unequivocal fingerprinting for many Chinese porcelains of utmost significance, based on high-precision multi-element and isotopic analysis by inductively-coupled mass spectrometry (ICP-MS) and thermal ionization mass spectrometry (TIMS) in our laboratory. As most ancient Chinese kilns used raw materials mined from local areas, differences in the geochemistry and mineralogy of these raw materials are expected to be preserved as distinctive geochemical and isotopic signatures in finished products and this may be useful for identifying their sources. Production techniques, such as purifying and mixing of different raw materials, may also vary from kiln to kiln, or may even change over time. All of that could also potentially leave a characteristic chemical and isotopic signature in a kiln's finished products. Using a tiny amount (often a few tens milligrams) of porcelain material, more than 40 element concentrations and Sr-Nd isotopic compositions can be rapidly and precisely determined on the ICP-MS and TIMS, respectively. The analytical results show that visibly similar Chinese porcelains made in different places and/or dynasties are strikingly distinctive. The data also allow modern fakes to be readily distinguished from antique porcelains. (author). 4 refs., 7 figs

  17. Investigation of Chemical Exchange at Intermediate Exchange Rates using a Combination of Chemical Exchange Saturation Transfer (CEST) and Spin-Locking methods (CESTrho)

    Science.gov (United States)

    Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

    2011-01-01

    Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer (CEST) and T1ρ magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. PMID:22009759

  18. Investigation of chemical exchange at intermediate exchange rates using a combination of chemical exchange saturation transfer (CEST) and spin-locking methods (CESTrho).

    Science.gov (United States)

    Kogan, Feliks; Singh, Anup; Cai, Keija; Haris, Mohammad; Hariharan, Hari; Reddy, Ravinder

    2012-07-01

    Proton exchange imaging is important as it allows for visualization and quantification of the distribution of specific metabolites with conventional MRI. Current exchange mediated MRI methods suffer from poor contrast as well as confounding factors that influence exchange rates. In this study we developed a new method to measure proton exchange which combines chemical exchange saturation transfer and T(1)(ρ) magnetization preparation methods (CESTrho). We demonstrated that this new CESTrho sequence can detect proton exchange in the slow to intermediate exchange regimes. It has a linear dependence on proton concentration which allows it to be used to quantitatively measure changes in metabolite concentration. Additionally, the magnetization scheme of this new method can be customized to make it insensitive to changes in exchange rate while retaining its dependency on solute concentration. Finally, we showed the feasibility of using CESTrho in vivo. This sequence is able to detect proton exchange at intermediate exchange rates and is unaffected by the confounding factors that influence proton exchange rates thus making it ideal for the measurement of metabolites with exchangeable protons in this exchange regime. Copyright © 2011 Wiley Periodicals, Inc.

  19. Ion exchange nonwoven fabric chemical filter. 2

    International Nuclear Information System (INIS)

    Sekiguchi, Hideaki

    2000-01-01

    This report outlined the characteristics of EPIX filter and its complex with activated carbon to eliminate organic compounds from solvent. Elimination performance of this filter was determined using an ion chromatographic analyzer. EPIX filter showed high performance to eliminate trace amount of ionic compounds. The rate of elimination was both 99% or more for NH 3 and SO 2 in an early phase of filtration. Release of dust as well as impurities was significantly reduced by the use of EPIX filter. Gases once adsorbed on the filter were not released even at an elevated temperature of atmosphere. Combined use of non-woven fabrics was possible. For EPIX filter, there are three kinds; strong acid cation exchange filter and strong/weak basic anion filters. The weak basic anion filter has been applied to the conventional apparatus in wafer makers because the filter was very effective for selective boron trapping. When polyethyleneterephthalate was used as the base polymer, radical groups produced on the polymer were co-polymerized with monomer substances. The lifetime of filter was estimated on a base of gas concentration and wind velocity to determine the time to replace with a new one. Furthermore, the loss of pressure became less than a half when EPIX filter was used. (M.N.)

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

    International Nuclear Information System (INIS)

    Uda, Tatsuhiko

    1992-01-01

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

  1. Experimental studies of the transfer phenomena of tritium in an isotope exchange column for tritium recovery

    International Nuclear Information System (INIS)

    Bornea, Anisia; Cristescu, Ion; Zamfirache, Marius; Varlam, Carmen

    2003-01-01

    To extract the tritium generated in the heavy water moderated power reactor, we have chosen the catalytic isotope exchange process in liquid phase combined with cryogenic distillation LPCE-CD. This paper presents the experimental studies of the catalytic isotope transfer of tritium. The catalytic isotope exchange process is performed in a column filled with successive layers of catalyst PT/C/PTFE and B7 type ordered package of phosphorous bronze. The catalyst and the package are manufactured in our institute and corresponding patents were issues. The catalyst consists of 95.5 wt.% PTFE, 4.1 wt. % carbon and 0.40 wt. % platinum and was made with 10'10'2 mm Raschig rings. The ordered package was consists of wire mesh phosphor bronze of 4'1 wire with a mesh size of 0.18 x 0.48 mm. The paper also presents the mathematical model which is used to evaluate the performance of the process. The mathematical model and the experimental data allowed determining two speed constants for isotope exchange process and for distillation process, respectively. By considering the values of these speed constants it is possible to improve the hydrophobic Pt catalyst and to design the H 2 /H 2 O isotopic exchange column package with this catalyst. (authors)

  2. Chemical composition of HAL, an isotopically-unusual Allende inclusion

    International Nuclear Information System (INIS)

    Davis, A.M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G.J.

    1982-01-01

    Thirty-seven major, minor and trace elements were determined by INAA and RNAA in samples of hibonite, black rim and portions of friable rim from an unusual Allende inclusion, HAL. The peculiar isotopic, mineralogical and textural properties of HAL are accompanied by very unusual trace element abundances. The most striking feature of the chemistry is the virtual absence of Ce from an inclusion otherwise highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os and Ir, relative to other refractory elements. Of the lithophile elements determined which are normally considered to be refractory in a gas of solar composition, Sr, Ba, Ce, U and V are the most volatile in oxidizing gases. The distribution of REE between hibonite and rims seems to have been established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. On the basis of HAL's chemical and isotopic composition, possible locations for the chemical and mass dependent isotopic fractionation are discussed. (author)

  3. Isotope exchange investigation of nitrogen redistribution in expanded austenite

    DEFF Research Database (Denmark)

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

    2013-01-01

    Sequential plasma and gaseous nitriding of Fe–18Cr–10Ni–3Mo stainless steel at 390°C with 14N and 15N isotopes followed by denitriding in flowing hydrogen was investigated. Redistribution of plasma-inserted nitrogen atoms (15N) by subsequent gaseous nitriding (14N) was observed. Denitriding after...

  4. New method for the hydrogen isotope exchange reaction in a hydrophobic catalyst bed

    International Nuclear Information System (INIS)

    Asakura, Y.; Kikuchi, M.; Yusa, H.

    1982-01-01

    To improve the isotope exchange reaction efficiency between water and hydrogen, a new reactor in which water mists and hydrogen gas react cocurrently was studied. To apply this to the enrichment of tritium in heavy water, a dual temperature isotope exchange reactor which is composed of cocurrent low temperature reactors and the usual countercurrent high temperature reactor was proposed and analyzed using a McCabe-Thiele diagram. By utilizing cocurrent reactors, in combination, the necessary catalyst volume can be reduced to one-tenth as compared with the usual countercurrent low temperature reactor. 17 refs

  5. A new type separation column for the water-hydrogen isotope catalytic exchange process

    International Nuclear Information System (INIS)

    Fedorchenko, O.A.; Alekseev, I.A.; Trenin, V.D.

    2001-01-01

    The catalytic water/hydrogen isotope exchange process is by right considered the most attractive for the solution a number of urgent problems of hydrogen isotope separation. A new type exchange reaction column is described and studied in details by computer simulation and with the help of McCabe-Thiele diagrams. It is shown that the new column in comparison with a traditional one needs less catalyst quantity and a smaller diameter for the solving of the same separation tasks. Generalized calculation data are presented in graphical form

  6. Performance characterization of hydrogen isotope exchange and recombination catalysts for tritium processing

    International Nuclear Information System (INIS)

    Suppiah, S.; Ryland, D.; Marcinkowska, K.; Boniface, H.; Everatt, A.

    2010-01-01

    AECL's hydrogen isotope exchange catalyst and recombination catalysts have been successfully applied to a wide range of industrial tritium-removal applications. The catalysts are used for Liquid Phase Catalytic Exchange (LPCE) and for gas-phase and trickle-bed recombination of hydrogen isotopes and have led to process simplification, improved safety and operational advantages. Catalyst performance design equations derived from laboratory testing of these catalysts have been validated against performance under industrial conditions. In a Combined Electrolysis and Catalytic Exchange (CECE) demonstration plant analyses of LPCE and recombiner efficiency were carried out as a function of catalyst activity over a wide range of operation. A steady-state process simulation used to model and design the hydrogen-water isotopic exchange processes, such as the CECE detritiation plant, was validated using the results of this demonstration. Catalyst development for isotope-exchange and recombination applications has continued over the last decade. As a result, significant improvements in catalyst performance have been achieved for these applications. This paper outlines the uniqueness of AECL's specialized catalysts and process designs for these applications with examples from laboratory and industrial case studies.

  7. Application of personal computers to study the kinetics of heterogeneous isotopic exchange

    International Nuclear Information System (INIS)

    Koernyei, Jozsef; Lakatos, Mihaly

    1985-01-01

    The kinetics of some heterogeneous isotopic exchange reactions of alkaline metal ions between solid (crystalline zirconium phosphate) and liquid phases were investigated. Ion diffusion in solid phase was considered as rate controlling step. The Laplace transformation solution of Fick's II law was used with a Sinclair ZX Spectrum personal computer. In some cases the exchange reaction should be regarded as a superposition of diffusion and a first order process. (author)

  8. Increased recovery in dual temperature isotope exchange process

    International Nuclear Information System (INIS)

    Babcock, D.F.; Neill, J.S.

    1978-01-01

    The improvement comprises increasing the flow ratio of liquid with respect to gas within the upper portion of the first tower, wherein the liquid is enriched in the isotope, and within the lower portion of the second tower, wherein the liquid is depleted in the isotope each to a value of at least 5% above the corresponding flow ratio within the remaining lower portion of the first tower and the remaining upper portion of the second tower respectively. The increased flow ratios are provided by increasing the rate of liquid substance being fed to the first tower and withdrawing up to about 50% of the increased liquid substance flow from a location within the upper one-half of the first tower and reintroducing the withdrawn liquid at a location within the lower one-half portion of the second tower. (author)

  9. Theoretical study of the Cs isotope exchange reaction of CsI + Cs' → Cs + ICs' (Contract research)

    International Nuclear Information System (INIS)

    Kobayashi, Takanori; Hashimoto, Masashi; Yokoyama, Keiichi

    2015-12-01

    To discuss the exchange reaction of Cs isotope by CsI + Cs' → Cs + ICs', the structure and chemical properties of Cs 2 I intermediate and potential energy surface of the entrance reaction are calculated using M06/def2-TZVPPD density functional calculation. The calculation shows that the reaction to the intermediate has no barrier and the two Cs-I bonds of Cs 2 I are chemically equivalent. These results suggest that the rate of the Cs exchange reaction of CsI + Cs' → Cs + ICs' is as high as the collision rate. (author)

  10. Separation of hydrogen isotope by hydrogen-water exchange

    International Nuclear Information System (INIS)

    Isomura, Shohei; Kaetsu, Hayato; Nakane, Ryohei

    1979-01-01

    The deuterium exchange reaction between gaseous hydrogen and liquid water is studied by use of three kinds of trickle bed exchange columns packed with hydrophobic catalysts supporting platinum. All columns have the effective lengths of 30 cm. They are 17 mm, 30 mm, and 95 mm in diameters, respectively. The separation experiments are carried out by the once-through methods. The separation efficiencies of the columns are evaluated by the parameters such as the height equivalent to a theoretical plate (H. E. T. P.) and the mass transfer co-efficient. It is found that the operating condition of the exchange column is optimum when the superficial hydrogen flow velocity is 0.3 m/sec. (author)

  11. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    Science.gov (United States)

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

    2012-09-30

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

  12. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

    Science.gov (United States)

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

    2016-12-01

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

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

    International Nuclear Information System (INIS)

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

    1985-01-01

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

  14. Assessing the identifiability in isotope exchange depth profiling measurements

    DEFF Research Database (Denmark)

    Ciucci, Francesco; Panagakos, Grigorios; Chen, Chi

    2014-01-01

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

  15. Tritium enrichment in aqueous phase by catalytic isotopic exchange

    International Nuclear Information System (INIS)

    Schindewolf, U.

    1983-01-01

    At normal pressure, the most promising enrichment method appears to be an inverse current exchanger system using electrolysis at the bottom of the inverse current column apparatus and recombination in an oxyhydrogen gas flame at the top of the column apparatus. A hydrophobic catalyst is used which is made of a pulverized mix of platinized activated carbon and PTFE. (DG) [de

  16. Preparation of radioactive labelled compounds. Pt. 2. 82Br labelled organic bromine compounds by isotopic exchange

    International Nuclear Information System (INIS)

    Otto, R.

    1988-05-01

    Studies on isotopic exchange between organic bromine compounds and 82 Br labelled dioxane dibromide in the presence of AlCl 3 are described. The results obtained enable to develop a simple and quick preparation method for the labelling with 82 Br [fr

  17. Isotope exchange study of the dissociation of metal - humic substance complexes

    Czech Academy of Sciences Publication Activity Database

    Mizera, J.; Jansová, A.; Hvoždová, I.; Beneš, P.; Novák, František

    2003-01-01

    Roč. 53, A (2003), s. A97-A101 ISSN 0011-4626 Institutional research plan: CEZ:AV0Z6066911; CEZ:MSM 210000019 Keywords : isotope exchange * dissociation of metal * humic substance complexes Subject RIV: EH - Ecology, Behaviour Impact factor: 0.263, year: 2003

  18. Process for the production of heavy water by H2-methylamine isotopic exchange

    International Nuclear Information System (INIS)

    Briec, M.; Ravoire, J.; Rostaing, M.

    1977-01-01

    An isotopic exchange process for separating D 2 from H 2 is presented. The H 2 -monomethylamine system is studied on the laboratory scale (kinetics, H 2 solubility, thermal stability and solubility of the catalyst) and on the pilot plant scale (operating conditions and economics) [fr

  19. The introduction of tritium in lactose and saccharose by isotope exchange with gaseous tritium

    International Nuclear Information System (INIS)

    Akulov, G.P.; Snetkova, E.V.; Kaminskij, Yu.L.; Kudelin, B.K.; Efimova, V.L.

    1991-01-01

    Methods for conducting reactions of catalytic protium-tritium isotopic exchange with gaseous tritium were developed in order to synthesize tritium labelled lactose and saccharose. These methods enabled to prepare these labelled disaccharides with high molar activity. The yield was equal to 50-60%, radiochemical purity ∼ 95%

  20. Surface area of antimony oxide by isotope exchange and other methods

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Y.K.; Acharya, B.V.; Rangamannar, B.

    1985-06-17

    Specific surface areas of antimony oxide samples, one commercial, the other prepared from antimony trichloride were measured by heterogeneous isotope exchange, gas adsorption, air permeability and microscopic methods. Specific surface areas obtained by these four methods for the two samples were compared and the observed differences are explained.

  1. Speciative determination of phosphorus in environmental water by the isotope exchange method

    International Nuclear Information System (INIS)

    Ikeda, N.; Yoshikawa, M.; Murakami, S.; Kunika, J.

    1988-01-01

    An isotope exchage method for the speciative determination of phosphorus (PO 4 3- ,PO 3 3- and total P) in natural water samples is proposed by using the exchange system of molybdophosphate in the aqueous phase and tetraphenylarsonium molybdophosphate in the organic phase. In this exchange system, only PO 4 3- exchanges and is determined. When the sample water is treated with Br 2 water in advance, the amount of PO 4 3- +PO 3 3- can be obtained. When the sample is treated with H 2 SO 4 and HNO 3 , the amount of total P can be determined. (author) 4 refs.; 5 tabs

  2. Kinetics of tritium isotope exchange between liquid pyrrole and gaseous hydrogen

    International Nuclear Information System (INIS)

    Stolarz, A.

    1994-01-01

    The kinetics of tritium isotope exchange between liquid pyrrole and gaseous hydrogen has been studied over the temperature range of 290-303 K. The reaction was carried out in the presence of platinum black but in spite of that, it appeared to be relatively slow. The kinetics of the exchange reaction studied could be described by the simple McKay equation. The results obtained suggest that diffusion is the rate-determining step. A mechanism of exchange is proposed. (author) 10 refs.; 2 figs.; 1 tab

  3. Solvent extraction as a method of promoting uranium enrichment by chemical exchange

    International Nuclear Information System (INIS)

    Fathurrachman.

    1995-01-01

    This thesis examines a chemical exchange process for uranium enrichment using solvent extraction. The system selected is the isotope exchange for uranium species in the form of uranous and uranyl chloride complexes. Solvent extraction has been studied before by French workers for this application but little was published on this. Much of this present work is therefore novel. The equilibrium data for the extraction of U(IV) as U 4+ and U(VI) as UO 2 2+ from hydrochloric media into an organic phase containing tri-n-octylamine (TOA) in benzene is given. Benzene is used to prevent third phase formation. In 4 M HCl U(VI) was found to be very soluble in the organic phase but U(IV) was virtually insoluble. Most of the equilibrium data has been correlated by the Langmuir isotherm. This thesis also outlines the methodology that has to be used to design a plant based on this process. (author)

  4. Chemical composition of HAL, an isotopically-unusual Allende inclusion

    Science.gov (United States)

    Davis, A. M.; Tanaka, T.; Grossman, L.; Lee, T.; Wasserburg, G. J.

    1982-01-01

    Samples of hibonite, black rim, and portions of friable rim from an unusual Allende inclusion, named HAL, were analyzed by INAA and RNAA for 37 major, minor, and trace elements. An unusually low amount of Ce was found in HAL, although it otherwise was highly enriched in REE compared to C1 chondrites. HAL is also depleted in Sr, Ba, U, V, Ru, Os, and Ir relative to other refractory elements. It is concluded that the distribution of REE between hibonite and rims was established when hibonite and other refractory minerals were removed at slightly different temperatures from a hot, oxidizing gas in which they previously coexisted as separate grains. Possible locations for the chemical and mass dependent isotopic fractionation are considered to be in ejecta from the low temperature helium-burning zone of a supernova and in the locally oxidizing environment generated by evaporation of interstellar grains of near-chondritic chemical composition.

  5. Chemical equilibria relating the isotopic hydrogens at low temperatures

    International Nuclear Information System (INIS)

    Pyper, J.W.; Souers, P.C.

    1976-01-01

    Hydrogen fusion will require a fuel mixture of liquefied or frozen D 2 and T 2 . The composition of this fuel mixture is described by the equilibrium constant K/sub DT/. The theory of isotopic exchange reactions is discussed as applied to the hydrogen isotopes. A literature survey of the values of K/sub HD/, K/sub HT/, and K/sub DT/ found no values of K/sub DT/ for temperatures below 25 0 K and no values of K/sub HD/ and K/sub HT/ for temperatures below 50 0 K. The existing data are critically evaluated, and simplified formulas for the three equilibrium constants in the temperature range 50 to 300 0 K are derived from them. Harmonic approximation theory with rotational correction was used to calculate values of K/sub HD/, K/sub HT/, and K/sub DT/ in the temperature range 4.2 to 50 0 K. It is found that K/sub DT/ = 2.995 exp(-10.82/T) in the temperature range 16.7 to 33.3 0 K to an accuracy of 1%. Tables, graphs, and equations of K/sub HD/, K/sub HT/, and K/sub DT/ are given for the temperature range 4.2 to 50 0 K. 27 references, 14 tables, 8 figures

  6. Lithium isotope separation on an ion exchange resin having azacrown ether as an anchor group

    International Nuclear Information System (INIS)

    Kim, D.W.; Jeong, Y.K.; Lee, J.K.; Hong, Ch.P.; Kim, Ch.S.; Jeon, Y.Sh.

    1997-01-01

    As study on the separation of lithium isotopes was carried out with an ion exchange resin having 1,7,13-trioxa-4,10,16-triazacyclooctadecane (N 3 O 3 ) as an anchor group. The lighter isotope, 6 Li concentrated in the resin phase, while the heavier isotope, 7 Li is enriched in the fluid phase. Upon column chromatography [0.6 cm (I. D.) x 20 cm (height) using 1.0M ammonium chloride solution as an eluent, single separation factor, α, 1.068 ( 6 Li/ 7 Li) r esin/( 6 Li/ 7 Li) s olution was obtained by the GLUECKAUF method from the elution curve and isotope ratios. (author)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-01

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

  8. Oxygen isotope exchange in La2NiO(4±δ).

    Science.gov (United States)

    Ananyev, M V; Tropin, E S; Eremin, V A; Farlenkov, A S; Smirnov, A S; Kolchugin, A A; Porotnikova, N M; Khodimchuk, A V; Berenov, A V; Kurumchin, E Kh

    2016-04-07

    Oxygen surface exchange kinetics and diffusion have been studied by the isotope exchange method with gas phase equilibration using a static circulation experimental rig in the temperature range of 600-800 °C and oxygen pressure range of 0.13-2.5 kPa. A novel model which takes into account distributions of the dissociative adsorption and incorporation rates has been developed. The rates of the elementary stages have been calculated. The rate-determining stages for a La2NiO(4±δ) polycrystalline specimen have been discussed. The diffusion activation energies calculated using the gas phase equilibration method (1.4 eV) differ significantly from those calculated using isotope exchange depth profiling (0.5-0.8 eV), which was attributed to the influence of different oxygen diffusion pathways.

  9. Separation of lithium isotopes on ion exchangers; Separation des isotopes du lithium sur echangeurs d'ions

    Energy Technology Data Exchange (ETDEWEB)

    Menes, F; Saito, E; Roth, E [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    A survey of the literature shows that little information has been published on the separation of lithium isotopes with ion exchange resins. We have undertaken a series of elutions using the ion-exchange resins 'Dowex 50 x 12' and IRC 50, and various eluting solutions. Formulae derived from the treatment of Mayer and Tompkins permit the calculation of the separation factor per theoretical plate. For the solutions tried out in our experiments the separation factors lie in the interval 1.001 to 1.002. These values are quite low in comparison to the factor 1.022 found by Taylor and Urey for ion exchange with zeolites. (author) [French] Nous avons trouve relativement peu de donnees dans la litterature scientifique sur la separation des isotopes de lithium par les resines echangeuses d'ions. Nous avons effectue un certain nombre d'essais sur Dowex 50 X 12 et IRC 50 utilisant divers eluants. Des formules derivees de celles de Mayer et Tompkins permettent le calcul du coefficient de separation par plateau theorique. Pour les eluants etudies, ces facteurs de separation se trouvent entre 1,001 et 1,002. Ces valeurs sont faibles en comparaison du facteur 1,022 trouve par Taylor et Urey pour les zeolithes. (auteur)

  10. Study of kinetics, equilibrium and isotope exchange in ion exchange systems Pt. 4

    International Nuclear Information System (INIS)

    Stamberg, K.; Plicka, J.; Calibar, J.; Gosman, A.

    1985-01-01

    The kinetics of ion exchange in the Nasup(+)-Mgsup(2+)-strongly acidic cation exchanger system in a batch stirred reactor was studied. The samples of exchangers OSTION KS (containing DVB in the range of 1.5 - 12%) and AMBERLITE IR 120 for experimental work were used; the concentration of the aqueous nitrate solution was always 0.2M. The Nernst-Planck equation for description of diffusion of ions in a particle was used. The values of diffusion coefficients of magnesium ions in the exchangers and their dependence on the content of DVB were obtained by evaluating the experimental data and using the self-diffusion coefficients of sodium. (author)

  11. Isotopic and chemical features of hot springs in Akita Prefecture

    International Nuclear Information System (INIS)

    Matsubaya, Osamu

    1997-01-01

    All over the Akita Prefecture, many hot springs are located. Most of them are of meteoric water, fossil sea water and volcanic gas origins. In the Ohdate-Kazuno area, moderate temperature hot springs of meteoric water origin are found, which may exist as rather shallow formation water in the Green Tuff formations. On the contrary, high temperature geothermal waters of meteoric origin, which are used for power generation, are obtained in two volcanic area of Hachimantai and Oyasu. Those geothermal waters are expected to come up through vertical fissures from depth deeper than 2 km. The difference of these two manners of meteoric water circulation should be necessarily explained to understand the relationship of shallow and deep geothermal systems. About some hot springs of fossil sea water origin, the relationships of δ D and Cl - don't agree to the mixing relation of sea water and meteoric water. This may be explained by two different processes, one of which is mixing of sea water with saline meteoric water (Cl - ca. 12 g/kg). The other is modification of δD by hydrogen isotopic exchange with hydrous minerals underground, or by exchange with atmospheric vapor during a relic lake before burying. (author)

  12. Exchange of hydrogen isotopes in oxide ceramics at room temperature

    International Nuclear Information System (INIS)

    Suzuki, H.; Morita, K.; Soda, K.

    2001-01-01

    The decay curves of D and up-take curves of H on the exchange of D implanted into Li 2 TiO 3 for H in H 2 O vapor caused by exposure to normal-air at room temperature have been measured as a function of exposure time at different implantation concentrations by means of the elastic recoil detection technique. The re-emission curves of D retained and H up-taken in a specimen by isochronal annealing for 10 min have been also measured. It is found that the thermal re-emission of D and H takes place uniformly over the whole specimen due to local molecular recombination in the bulk and that the re-emission rates of H and D in the near-surface layers are slower than those in the deeper layers. It is also found that the decay of D caused by the D-H exchange takes place rapidly in the beginning and the retained amount of D attains at a constant level and the retained fraction of D are higher as the initial implantation concentrations of D are lower. The decay curves of D and the up-take curves of H have been analysed using the mass balance equations, in which the elementary processes are taken into account according to the exchange model of one way diffusion from the surface into the bulk. It is shown that the solution of the mass balance equations reproduces well the experimental data. The rate constants of the elementary processes determined are discussed. (orig.)

  13. Tritium removal by hydrogen isotopic exchange between hydrogen gas and water on hydrophobic catalyst

    International Nuclear Information System (INIS)

    Morishita, T.; Isomura, S.; Izawa, H.; Nakane, R.

    1980-01-01

    Many kinds of the hydrophobic catalysts for hydrogen isotopic exchange between hydrogen gas and water have been prepared. The carriers are the hydrophobic organic materials such as polytetrafluoroethylene(PTFE), monofluorocarbon-PTFE mixture(PTFE-FC), and styrene-divinylbenzene copolymer(SDB). 0.1 to 2 wt % Pt is deposited on the carriers. The Pt/SDB catalyst has much higher activity than the Pt/PTFE catalyst and the Pt/PTFE-FC catalyst shows the intermediate value of catalytic activity. The observation of electron microscope shows that the degrees of dispersion of Pt particles on the hydrophobic carriers result in the difference of catalytic activities. A gas-liquid separated type column containing ten stages is constructed. Each stage is composed of both the hydrophobic catalyst bed for the hydrogen gas/water vapor isotopic exchange and the packed column type bed for the water vapor/liquid water isotopic exchange. In the column hydrogen gas and water flow countercurrently and hydrogen isotopes are separated

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

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi; Itami, Akira

    1989-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-03-01

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

  16. Minutes of the 28th annual plutonium sample exchange meeting. Part I: isotopic sample exchange

    International Nuclear Information System (INIS)

    1984-01-01

    Contents of this publication include the following: list of participating laboratories; agenda; attendees; minutes of October 24 meeting; and handout materials supplied by speakers. The handout materials cover the following: interlaboratory comparisons of plutonium isotope ratios. The plutonium ratios considered are 240/239, 241/239, 242/239, 238/239, 239/240, 241/240, 242/240, and 238/240; carbon, uranium, iron, and nickel data; mass spectroscopy data; determination of plutonium 241 half-life; review of plutonium overplating sample loading technique; on-line measurement evaluation system for isotopic analysis; and description of a new thermal ionization mass spectrometer

  17. Chemical exchange in biomacromolecules: Past, present, and future

    Science.gov (United States)

    Palmer, Arthur G.

    2014-01-01

    The perspective reviews quantitative investigations of chemical exchange phenomena in proteins and other biological macromolecules using NMR spectroscopy, particularly relaxation dispersion methods. The emphasis is on techniques and applications that quantify the populations, interconversion kinetics, and structural features of sparsely populated conformational states in equilibrium with a highly populated ground state. Applications to folding, mol ecular recognition, catalysis, and allostery by proteins and nucleic acids are highlighted. PMID:24656076

  18. Determination of phosphorus in urban sewage sludge using the isotopic exchange kinetics method

    International Nuclear Information System (INIS)

    Rojas de Tramontini, Susana; Barbaro, Nestor O.; Lopez, Silvia C.

    1999-01-01

    The aim of this work was to assess the differences among soil available P, the use by the plants of sludge P, and of a water soluble fertilizer (Ca(H 2 PO 4 ) 2 ) P, using isotopic exchange kinetics methods. The sludge was provided by the Sewage Sludge Treatment Plant of Tucuman City, Argentina. The isotopic exchange kinetics experiment, in which the fate of carrier free 32 PO 4 added to the soil solution at a steady state was studied, gives information on soil P exchangeability. The experiment was carried out in the laboratory, where sewage sludge and water soluble fertilizer were added to soil samples taken at a depth of 0-25 and 25-40 cm. Changes in the soil P isotopically exchangeable within 1 minute measurements in the soil with sludge and in the soil with water soluble fertilizer showed that the 0-25 cm deep soil samples had a low P sorption capacity (r1 /R values were low). The sludge had high total and organic P, but the P in the soil solution was lower than the P provided by the water soluble fertilizer. Therefore, despite its higher total P content, this sludge contained slow available forms of P

  19. Hydrogen isotope exchange of organic compounds in dilute acid at elevated temperatures

    International Nuclear Information System (INIS)

    Werstiuk, N.H.

    1987-01-01

    Introduction of one or more deuterium (or tritium) atoms into organic molecules can be accomplished in many ways depending on the nature of the substrate and the extent and sterochemistry of deuteriation or tritiation required. Some of the common methods include acid- and base-catalyzed exchange of carbonyl compounds, metal hydride reductions, dissolving metal reductions, catalytic reduction of double bonds, chromatographic exchange, homogeneous and heterogeneous metal-catalyzed exchange, base-catalyzed exchange of carbon acids other than carbonyl compounds and acid-catalyzed exchange via electrophilic substitution. Only the latter three methods have been used for perdeuteriation of organic compounds. A very useful compendium of labeling methods with examples has been available to chemists for some time. Although metal-catalyzed exchange has been used extensively, the method suffers from some deficiencies: irreproducibility of catalyst surfaces, catalyst poisoning, side reactions such as coupling and hydrogenolysis of labile groups and low deuterium incorporation. Usually a number of cycles are required with fresh catalyst and fresh deuterium source to achieve substantial isotope incorporation. Acid-catalyzed exchange of aromatics and alkenes, strongly acidic media such as liquid DBr, concentrated DBr, acetic acid/stannic chloride, concentrated D 3 PO 4 , concentrated DC1, D 3 PO 4 /BF 3 SO 2 , 50-80% D 2 SO 4 and DFSO 4 /SbF 5 at moderate temperatures (<100 degrees) have been used to effect exchange. The methods are not particularly suitable for large scale deuteriations because of the cost and the fact that the recovery and upgrading of the diluted deuterium pool is difficult. This paper describes the hydrogen isotope exchange of a variety of organic compounds in dilute aqueous acid (0.1-0.5 M) at elevated temperatures (150-300 degrees)

  20. Chemical and environmental isotopes study of precipitation in Syria

    International Nuclear Information System (INIS)

    Al-Charideh, A.; Abou Zakhem, B.

    2009-02-01

    Chemical and isotopic compositions of monthly precipitation were monitored at 12 stations distributed over the entire region in Syria for a period of 4 years from December 1999 to April 2003. Amount of precipitation and mean air temperature of rain monthly were also recorded. The conductivity of rain waters varies between 35 μ/cm in the mountainous stations and 336 μ/cm at Deir Az-Zor station. Excepted Tartous station, the mean value of Cl in the rainfall in all station is 3.8 mg/l. The seasonal variations in δ 18 O are smaller at west stations than to the east stations due to low seasonal temperature variations. All stations are characterized by water lines with slopes significantly lower than GMWL, except Bloudan, suggesting the influence of local factors on the isotopic composition of the precipitation. d-excess values decrease from 19% in the western part to 13% in the eastern part of Syria, indicating the influence of the precipitation generated by the air masses coming from the Mediterranean Sea over Syria. A reliable altitude effect represent by depletion of heavy stable isotopes of about -0.21, and -1.47, per 100 m elevation of 18 O and δ 2 H, respectively. Monthly tritium activity and seasonal variations pattern are low in the west stations than at the east stations. The weighted mean tritium values are between 3 to 9 TU during 2000-2003, and it is increasing with distance from the Syrian coast by 1 TU /100 Km. (author)

  1. [Solid state isotope hydrogen exchange for deuterium and tritium in human gene-engineered insulin].

    Science.gov (United States)

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

    2014-01-01

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

  2. Chemical and environmental isotope study of precipitation in Syria

    International Nuclear Information System (INIS)

    Kattan, Z.

    1999-01-01

    Waters from a network of rainfall collection covering mine meteorological stations distributed mainly in the western part of Syria have been assayed using chemical and environmental isotope techniques for a period of 5 months from Dec. 1989 to Apr. 1990. The chemistry of rain waters falling over the mountainous stations shows a low solute concentration (20-105 mg 1 -1 ) compared with those falling over the coastal and anterior stations (50-210 mg 1 -1 ). The rain waters was generally characterized by a high deuterium excess (d=19%) compared with that of typical global meteoric waters (d=10%). The estimated deuterium excess is lower than that for the eastern Mediterranean meteoric waters (d=22%). The altitude effect is shown up by a depletion of heavy stable isotopes of about - 0.23% and -1.65% per 100 m elevation of δ 1 8 O and δD, respectively. The spatial distribution pattern of tritium contents shows a gradual build up with increasing distance from the Syrian coast. The weighted mean tritium content in rain waters falling over the country is estimated to amount to 9.5 tritium units (TU) during the period of observation. (author)

  3. Isotopic and chemical investigations on Angra dos Reis

    International Nuclear Information System (INIS)

    Wasserburg, G.J.; Tera, F.; Papanastassiou, D.A.; Huneke, J.C.

    1977-01-01

    Extensive isotopic studies of Pb, Sr and Xe and chemical abundance measurements of K, Rb, Sr, Ba, Nd, Sm, U and Th for total meteorite and mineral separates of the Angra dos Reis achondrite are reported on. U-Pb, Th-Pb and Pb-Pb ages are concordant at 4.54 AE for the total meteorite and for high-purity whitlockite in Angra dos Reis. This establishes Angra dos Reis as an early planetary differentiate which has not been disturbed for these systems since 4.54 AE ago. Measured 87 Sr/ 86 Sr in pyroxene and whitlockite for Angra dos Reis (ADOR) are distinctly below BABI by two parts in 10 4 and only one part in 10 4 above the lowest 87 Sr/ 86 Sr (ALL) measured in an Allende inclusion. The difference in ADOR-ALL corresponds to an interval of condensation in the solar nebula of approximately 3 m.y. If 26 Al was the heat source for the magmatism on the parent planets of Angra dos Reis and the basaltic achondrites (BABI) then the relatively large difference in 87 Sr/ 86 Sr, BABI - ALL, must be the result of planetary evolution rather than condensation over approximately 10 m.y. Xe isotopic measurements confirm the presence of large amounts of 244 Pu-produced fission Xe and show that 244 Pu was enriched in the whitlockite relative to the pyroxene by a factor of approximately 18. Chemical element enrichment factors between the whitlockite and the fassaitic pyroxene in Angra dos Reis are presented. The enrichment factors demonstrate close analogy between the rare earth elements and their actinide analogs. The enrichment factor for Pu is intermediate to the enrichment factors of Nd and Sm. (Auth.)

  4. Lead isotope exchange between dissolved and fluvial particulate matter: a laboratory study from the Johor River estuary

    Science.gov (United States)

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

    2016-11-01

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

  5. Measurements of tritium recycling and isotope exchange in TFTR

    International Nuclear Information System (INIS)

    Skinner, C.H.; Kamperschroer, J.; Mueller, D.; Nagy, A.; Stotler, D.P.

    1996-05-01

    Tritium Balmer-alpha (T α ) emission, along with H α and D α is observed in the current D-T experimental campaign in TFTR. The data are a measure of the fueling of the plasma by tritium accumulated in the TFTR limiter and the spectral profile maps neutral hydrogenic velocities. T α is relatively slow to appear in tritium neutral beam heated discharges, (T α /(H α + D α + T α ) = 11% after 8 tritium-only neutral beam discharges). In contrast, the T α fraction in a sequence of six discharges fueled with tritium puff,s increased to 44%. Larger transient increases (up to 75% T α ) were observed during subsequent tritium gas puffs. Analysis of the Doppler broadened spectral profiles revealed overall agreement with the dissociation, charge exchange, sputtering and reflection velocities predicted by the neutral Monte-Carlo code DEGAS with some deficiency in the treatment of dissociation products in the 10--100 eV range

  6. Mixed filling for the successive isotopic exchange in the phase sequence water - water vapors - hydrogen

    International Nuclear Information System (INIS)

    Stefanescu, D.; Peculea, M.; Hirean, I.; Croitoru, C.

    1995-01-01

    The paper deals with the process of the isotopic exchange implied in heavy water production. Details concerning the structural arrangement of the process contact elements inside the exchange columns are presented. A hydrophilic filling, based on phosphorous bronze, and the platinum catalyst structure , resulted from this work, are to be implemented in the column equipment of the heavy water distillation pilot operating in connection with the CANDU type reactors. The performances of the mixed catalyst components were derived from experimental data by means of the three fluids model equations

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

    DEFF Research Database (Denmark)

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

    2013-01-01

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

  8. Preparation of Pt-PTFE hydrophobic catalyst for hydrogen-water isotope exchange

    International Nuclear Information System (INIS)

    Li Junhua; Kang Yi; Han Yande; Ruan Hao; Dou Qincheng; Hu Shilin

    2001-01-01

    The hydrophobic catalyst used in the hydrogen-water isotope exchange is prepared with Pt as the active metal, PTFE as the hydrophobic material, active carbon or silicon dioxide as the support. The isotope catalytic exchange reaction between hydrogen and water is carried out in the trickle bed and the effects of different carriers, mass fraction of Pt and PTFE on the catalytic activity are discussed. The experimental results show that the activity of Pt-C-PTFE hydrophobic catalyst with the ratio between PTFE and Pt-C from 1 to 2 is higher than other kinds of catalysts and the overall volume transfer coefficient is increased with the increasing of the hydrogen flow rate and reaction temperature

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

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  10. Determination of phosphorus traces in platinum alloys by two-phase isotope exchange

    International Nuclear Information System (INIS)

    Vlacil, F.

    1980-01-01

    The method of ZEMAN and KRATZER for the determination of phosphorus traces by means of two-phase isotope exchange was modified for the determination of phosphorus in pure platinum or pure platinum alloys. It was found that Pt, Rh, Ag and As do not interfere with the determination. Among the elements usually present in platinum metal or platinum alloys, only gold interferes. It was removed by extraction from 7M HCl by MIBK and AmOAc. Hydrochloric acid also interferes but it can be removed by evaporation. The analytical procedure is given for the solution obtained by pressure decomposition of the sample (0.5 g) in a steel bomb with PTFE inlay. It is possible to determine > 2 ppm P (approximate error -10%). If using calibration dependence instead of the well known equation for isotope exchange it is not necessary to know the content of P in the standard solution labelled with 32 P. (author)

  11. Assessment of phosphorus fertility by means of isotopically exchangeable phosphorus and the fixing capacity of soils

    International Nuclear Information System (INIS)

    Gachon, L.

    1979-01-01

    Using over 400 soils representative of French pedological types, the absorption kinetics of phosphorus were studied on Italian rye-grass grown in pots until assimilable reserves had been exhausted. At the same time, Russell's E value (isotopically exchangeable P in vitro), Larsen's L value (isotopically exchangeable P in vivo) and the fixing capacity of the soils were measured. The study shows a very close correlation between the phosphorus removed by the first four cuttings and fertility indices combining E or L with the fixing capacity. The agricultural value of the two indices proposed, Isub(E) and Isub(L), is confirmed by the results of about forty one-year and multi-year field experiments. Norms for the interpretation of these indices are deduced; these are independent of the pedological type but need to be modified as a function of the type of crop and the cultural practice. (author)

  12. Process for the exchange of hydrogen isotopes using a catalyst packed bed assembly

    International Nuclear Information System (INIS)

    Butler, J.P.; den Hartog, J.; Molson, F.W.R.

    1978-01-01

    A process for the exchange of hydrogen isotopes between streams of gaseous hydrogen and liquid water is described, wherein the streams of liquid water and gaseous hydrogen are simultaneously brought into contact with one another and a catalyst packed bed assembly while at a temperature in the range 273 0 to 573 0 K. The catalyst packed bed assembly may be composed of discrete carrier bodies of e.g. ceramics, metals, fibrous materials or synthetic plastics with catalytically active metal crystallites selected from Group VIII of the Periodic Table, partially enclosed in and bonded to the carrier bodies by a water repellent, water vapor and hydrogen gas permeable, porous, polymeric material, and discrete packing bodies having an exterior surface which is substantially hydrophilic and relatively noncatalytically active with regard to hydrogen isotope exchange between hydrogen gas and water vapor to that of the catalyst bodies

  13. Ligand isotopic exchange of tris(acetylacetonato)germanium(IV) perchlorate in organic solvents

    International Nuclear Information System (INIS)

    Nagasawa, Akira; Saito, Kazuo

    1978-01-01

    The ligand isotopic exchange between tris(acetylacetonato)germanium(IV) perchlorate and acetylacetone[ 14 C] has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane (NM), and acetonitrile (AN), at 100 - 120 0 C. In these solvents, the rate formula was R = k[H 2 O][complex]; the concentrations of the complex, free ligand, and water in solution were in the ranges from 0.01 to 0.1 mol dm -3 . The activation enthalpies and entropies for the k's are 105, 98, and 90 kJ mol -1 ; and -25, -53, and -69 JK -1 mol -1 , in TCE, NM, and AN, respectively. Influence of acid and base concentrations, and deuterium isotope effect on the rate in AN suggest that the rate controlling step of the exchange is governed by the ease of the proton transfer between the leaving and the incoming acac - in an intermediate. (auth.)

  14. Calculation of isotopic profile during band displacement on ion exchange resins

    International Nuclear Information System (INIS)

    Sonwalkar, A.S.; Puranik, V.D.; D'Souza, A.B.

    1981-01-01

    A method has been developed to calculate the isotopic profile during band displacement on ion exchange resins using computer simulation. Persoz had utilized this technique earlier for calculating the isotopic profile during band displacement as well as frontal analysis. The present report deals with a simplification of the method used by Persoz by reducing the number of variables and making certain approximations where the separation factor is not far from unity. Calculations were made for the typical case of boron isotope separation. The results obtained by the modified method were found to be in very good agreement with those obtained by using an exact equation, at the same time requiring conside--rably less computer time. (author)

  15. Separation of 15N by isotopic exchange in NO, NO2-HNO3 system under pressure

    International Nuclear Information System (INIS)

    Axente, D.; Baldea, A.; Teaca, C.; Horga, R.; Abrudean, M.

    1998-01-01

    One of the most used method for production of 15 N with 99% at. concentration is the isotopic exchange between gaseous nitrogen oxides and HNO 3 solution 10M: ( 15 NO, 15 NO 2 ) g + H 14 NO 3,l = ( 14 NO, 14 NO 2 ) g + H 15 NO 3,l . The isotopic exchange is characterized by an elemental separation factor α=1.055 at 25 deg. C and atmospheric pressure. Recently, kinetics data pointed to the linear dependence of the exchange rate 15 N/ 14 N(R) on the nitrogen oxide pressure with a rate law R = k[HNO 3 ] 2 · [N 2 O 3 ]. In this work, the influence of the nitrogen oxide pressure on the 15 N separation efficiency was determined by the use of a laboratory equipment with a separation column pack of Helipack type, with dimensions 1.8 mm x 1.8 mm x 0.2 mm. The increase of nitrogen oxide pressure led to a better isotopic transfer between the two counter-flow phases in the column pack. The HETP (Height Equivalent to a Theoretical Plate) determined for a 3.14 ml ·cm -2 · min -1 load is equal to that obtained at atmospheric pressure for a two times lower load. The operation of the equipment for isotopic separation of 15 N at 1.8 atm instead of atmospheric pressure allows doubling the HNO 3 10 M load of the column and consequently, doubling the production rate. A better performance of the separation process at higher pressure is essential for the industrial production of 15 N isotope which is used for the production of uranium nitride in FBR type reactors. (authors)

  16. Studies of the hydrous titanium oxide ion exchanger. 4. Rate of the isotopic exchange of sodium ions between the exchanger in the Na+ form and aqueous solution

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi; Kasuga, Fuminori

    1995-01-01

    The isotopic exchange rate of Na + between hydrous titanium(IV) oxides, precipitated at pH 6 and 13, in the Na + form and aqueous solution of sodium salt was determined radiochemically. The rate in the exchanger precipitated at pH 6 is controlled by the diffusion of Na + in the exchanger particles (particle diffusion). The diffusion coefficient and its activation energy are 1.9 x 10 -11 m 2 s -1 (pH 12, 5.0degC) and 29 kJ mol -1 (pH 12), respectively. The rate in the exchanger precipitated at pH 13 is also controlled by the particle diffusion. The rate is much slower than that in the other; this can be explained by assuming the existence of two kinds of independently diffusing ions (fast and slow species) in the exchanger. The diffusion coefficients are of the order of 10 -12 and 10 -13 m 2 s -1 for the fast and the slow species, respectively. Their activation energies are 48-60 kJ mol -1 at pH 12. The marked difference in kinetics between two exchanges was interpreted in terms of the difference in the acid-base property and in the microstructure of the matrix. (author)

  17. Factors affecting the determination of the isotopically exchangeable phosphorus in soils

    International Nuclear Information System (INIS)

    Morales, L.E.M.

    1981-06-01

    In order to evaluate the factors that affect the determination of the isotopically exchangeable phosphorus in soils (L value), various greenhouse experiments were carried out. The following factors were considered: carrier level; plant species; harvest time; nitrogen doses; nitrogen sources; culture conditions and soil type. A radioactive solution with an activity level of approximately 10 μCi 32 p/3 kg soil with different carrier levels was located in layers or mixed completely with the soil depending upon the experiment. (author)

  18. Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

    Energy Technology Data Exchange (ETDEWEB)

    Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H. [KAERI, Taejon (Korea, Republic of)

    2005-11-15

    Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities.

  19. Hydrophobic catalyst mixture for the isotopic exchange reaction between hydrogen and water

    International Nuclear Information System (INIS)

    Paek, S.; Ahn, D. H.; Choi, H. J.; Kim, K. R.; Lee, M.; Yim, S. P.; Chung, H.

    2005-01-01

    Pt/SDBC catalyst, which is used for the hydrogen-water isotopic exchange reaction, was prepared. The various properties of the catalyst, such as the thermal stability, pore structure and the platinum dispersion, were investigated. A hydrophobic Pt/SDBC catalyst which has been developed for the LPCE column of the WTRF (Wolsong Tritium Removal Facility) was tested in a trickle bed reactor. An experimental apparatus was built for the test of the catalyst at various temperatures and gas velocities

  20. Use of water as displacing agent in ion exchange chromatographic separation of isotope of boron using weak base ion exchange resin

    International Nuclear Information System (INIS)

    Sharma, B.K.; Mohanakrishnan, G.; Anand Babu, C.; Krishna Prabhu, R.

    2008-01-01

    Experiments were undertaken to study the feasibility of using weakly basic anion exchange resin for enrichment of isotopes of boron by ion exchange chromatography and water as eluent. The results of experiments carried out to determine total chloride capacity (TCC), strong base capacity (SBC) of the resin at different concentrations of boric acid and enrichment profiles are reported in this paper. (author)

  1. Isotope exchange study of the dissociation of metal-humic complexes

    International Nuclear Information System (INIS)

    Mizera, J.; Jansova, A.; Hvozdova, I.; Benes, P.

    2002-01-01

    Prediction of the migration of toxic metals and radionuclides in the environment requires knowledge of equilibrium and kinetic parameters characterising their interaction with humic substance (HS). In this work, isotope exchange of Eu and Co in the systems containing HS has been used to study dissociation of the cations from their complexes with HS under quasi-stationary conditions. In the experimental arrangement of the so-called diaphragm method, a dialysis membrane divides two compartments containing solutions of metal and HS, identical in both half-cells but for radiolabeling ( 152 Eu and 60 Co) applied only in one cell. The membrane is permeable for free metal cation but not for the metal-HS complex. The slow dissociation of metal cation from HS is reflected by retardation (compared to a reference system in the absence of HS) of the rate of the isotope exchange between the two compartments. However, only an apparent dissociation rate can be observed, as detection of fast dissociation is limited by the rate of diffusion of dissociated cations through membrane and by their recombination with available binding sites of HS. The rate of isotope exchange of Eu and Co in the systems with HS (Aldrich sodium humate, soil humic and fulvic acid) was monitored as function of pH (4 and 6), ionic strength (0.01 and 0.1 M), and the degree of HS loading with metal ([M] 0 = 10 -7 - 2x10 -5 M at 10 mg/L HS). For Co, the rate of 60 Co 2+ diffusion through the membrane showed up to control the rate of the isotope exchange indicating that the Co-HS dissociation is too fast to be followed by the diaphragm method, and that the abundance of non-complexed Co is not negligible. The apparent rate of Eu-HS dissociation was found to be enhanced by decreasing pH value, increasing ionic strength, and increasing metal loading (i.e., metal/HS ratio). For interpretation of the experimental kinetic data, a discrete 2-component model (bi-exponential decay function) was applied. Based on

  2. Exchange rates of creatine kinase metabolites: feasibility of imaging creatine by chemical exchange saturation transfer MRI.

    Science.gov (United States)

    Haris, Mohammad; Nanga, Ravi Prakash Reddy; Singh, Anup; Cai, Kejia; Kogan, Feliks; Hariharan, Hari; Reddy, Ravinder

    2012-11-01

    Creatine (Cr), phosphocreatine (PCr) and adenosine-5-triphosphate (ATP) are major metabolites of the enzyme creatine kinase (CK). The exchange rate of amine protons of CK metabolites at physiological conditions has been limited. In the current study, the exchange rate and logarithmic dissociation constant (pKa) of amine protons of CK metabolites were calculated. Further, the chemical exchange saturation transfer effect (CEST) of amine protons of CK metabolites with bulk water was explored. At physiological temperature and pH, the exchange rate of amine protons in Cr was found to be 7-8 times higher than PCr and ATP. A higher exchange rate in Cr was associated with lower pKa value, suggesting faster dissociation of its amine protons compared to PCr and ATP. CEST MR imaging of these metabolites in vitro in phantoms displayed predominant CEST contrast from Cr and negligible contribution from PCr and ATP with the saturation pulse parameters used in the current study. These results provide a new method to perform high-resolution proton imaging of Cr without contamination from PCr. Potential applications of these finding are discussed. Copyright © 2012 John Wiley & Sons, Ltd.

  3. Investigation into reaction of heterogenous isotopic exchange with gaseoUs tritium in solution for preparation labelled lipid compounds

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Myasoedov, N.F.

    1983-01-01

    The applicability of the method of heterogeneous catalytic isotopic exchange with gaseous tritium in the solution for the production of labelled lipide preparations is studied. Labelled saturated and unsaturated aliphatic acids, prostaglandins, phospholipides and sphingolipides are prepared

  4. High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes

    Science.gov (United States)

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

    2017-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-02-21

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

  6. Effect of complexing reagents on the ionization constant of boric acid and its relation to isotopic exchange separation factor

    International Nuclear Information System (INIS)

    Sharma, B.K.; Subramanian, R.; Mathur, P.K.

    1991-01-01

    The effect of change in concentration of complexing reagents having two or more hydroxyl groups, viz., ethylene glycol, propylene glycol, dextrose and mannitol on the ionization constant of boric acid has been studied by pH-metric titration method. The effect of increase in ionization constant of boric acid on isotopic exchange separation factor for the separation of isotopes of boron by ion exchange chromatography has been studied by the batch method. (author). 9 refs

  7. Kinetics of liquid-phase catalytic heterogeneous protium-tritium isotope exchange with participation of gaseous hydrogen

    International Nuclear Information System (INIS)

    Akulov, G.P.; Snetkova, E.V.; Kayumov, V.G.; Kaminskij, Yu.L.

    1990-01-01

    Reaction rate constants of catalytic (PdO/BaSO 4 (Al 2 O 3 ) catalyst) heterogeneous protium - tritium isotopic exchange D - [1- 3 H] of carbohydrates and gaseous oxygen have been measured. It is ascertained that the rate of isotopic exchange depends on the nature of carbohydrate, catalyst, buffer and medium acidity. The value of concentration of carbohydrate acyclic forms plays the determining role in the process

  8. Isotopic study of water exchange between atmosphere and biosphere at Changa Manga site in Pakistan

    International Nuclear Information System (INIS)

    Fazil, M.; Ali, M.; Latif, Z.; Butt, S.

    2012-01-01

    Study of water exchange between atmosphere and biosphere was initiated to understand the ties between these two spheres. Samples of leaves and stems of 23 woody plants along with soil from the surface and from the depth of 7 cm were collected from Changa Manga forest. Moisture content from these samples was extracted using the vacuum distillation method and analyzed for stable isotopes (/sup 18/O and /sup 2/H). Air moisture was also collected in the field. Isotopic data plotted long with the Local Meteoric Water Line (LMWL) indicates that /sup 18/O and /sup 2/H contents of moisture in the leaves of woody plants are higher than their respective stems. This behavior is due to the evaporative enrichment trend originating from the soil moisture in active root zone and also from the leaf surface. The stem samples did not show any significant variation in gamma /sup 18/O suggesting no significant evaporation from stems of big trees. Degree of enrichment of leave samples of woody plants indicated the species-specific effects in isotopes during transpiration. Pine and Eucalyptus leaves showed more variation in the isotopic contents as compared to other species. Temporal variations of /sup 18/O and /sup 2/H in the leaves indicated enriched isotopic values during hot and dry periods as compared to those during wet period (monsoon and winter rains) mainly due to higher transpiration rates at high temperature and low humidity. (orig./A.B.)

  9. Study of iodine-iodate isotopic exchange reaction in neutral aqueous solutions by radiotracer technique

    International Nuclear Information System (INIS)

    Tripathi, R.; Ram, K.D.

    1993-01-01

    The isotopic exchange of iodine atoms in neutral aqueous solutions of iodate ions and iodine (in KI) is found to obey the rate law R = k [IO 3 - ] 0.4 [I 2 ] 1.2 at 175 o C. The addition of neutral ionic salts, e.g. KCl and KNO 3 , in the reaction mixture showed a slight catalytic effect on the exchange rate. Further, the kinetic salt effect indicated the involvement of at least one neutral species on the rate-determining step. The activation energy in neutral aqueous solutions of iodate ions and iodine is found to be 86 ± 3 kJ mol -1 , which decreases in the presence of KCl (79 ± 3 kJ mol -1 and KNO 3 (82 + 3 kJ mol -1 ). The activation parameters, viz. free energy of activation, enthalpy of activation and entropy of activation, were also calculated. Based on these results, an association-dissociation type of reaction mechanism is proposed for this exchange reaction in neutral aqueous medium, similar to that proposed earlier for iodide-iodate isotopic exchange reaction in neutral aqueous solutions, nitrate eutectic melts and iodide-iodate melts. (author)

  10. Isotopic exchange between deuterium and neohexane on supported platinum and palladium catalysts

    International Nuclear Information System (INIS)

    Eskinazi, V.

    1979-01-01

    The isotopic exchange reaction between neohexane and deuterium on supported Pt/SiO 2 and Pd/SiO 2 catalysts has been investigated in the temperature range 86.5 to 110 0 C. Rates of exchange were studied as functions of percentage of metal atoms exposed, the conditions of catalyst pretreatment, and the reaction temperature. The rates of exchange were not strongly dependent upon percentage exposed; however, the relative yields of d 1 through d 5 in the ethyl moiety or neohexane were dependent on the percentage metal atoms exposed. The Pt/SiO 2 catalysts were found to be more active for exchange than the Pd/SiO 2 catalysts by an order of magnitude. Both the turnover frequencies and the exchange pattern were observed to be influenced by the pretreatment of the catalyst. Maxima in the exchange pattern occurred at d 3 and d 5 in the case of Pt/SiO 2 and at d 5 only in the case of the Pd/SiO 2 catalysts. In order to account for the d 3 maximum observed for Pt catalysts, some extension of the Horiuti-Polanyi mechanism is required. Mechanisms by which the d 3 species might be formed are proposed and discussed. On Pd/SiO 2 catalysts exchange occurs preferentially in the ethyl substituent of the quaternary carbon atom rather than on the three methyl substituents of the quaternary carbon atom. Such preference is not observed on Pt/SiO 2 catalysts; in fact, in some cases, this preference is reversed. Whenever exchange occurs in the three methyl substituents, mostly the d 1 product is obtained. For Pt/SiO 2 catalysts, the exchange pattern appears to be influenced by steric effects, but the data suggest that factors other than steric effects are important on Pd

  11. Process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas and catalyst assembly therefor

    International Nuclear Information System (INIS)

    Stevens, W.H.

    1975-01-01

    A bithermal, catalytic, hydrogen isotope exchange process between liquid water and hydrogen gas to effect concentration of the deuterium isotope of hydrogen is described. Liquid water and hydrogen gas are contacted with one another and with at least one catalytically active metal selected from Group VIII of the Periodic Table; the catalyst body has a water repellent, gas and water vapor permeable, organic polymer or resin coating, preferably a fluorinated olefin polymer or silicone resin coating, so that the isotope exchange takes place by two simultaneously occurring, and closely coupled in space, steps and concentration is effected by operating two interconnected sections containing catalyst at different temperatures. (U.S.)

  12. Isotopic exchange between CO2 and H2O and labelling kinetics of photosynthetic oxygen

    International Nuclear Information System (INIS)

    Gerster, Richard

    1971-01-01

    The reaction of carbon dioxide with water has been studied by measuring the rate of oxygen exchange between C 18 O 2 and H 2 16 O. The mathematical treatment of the kinetics allows to determine with accuracy the diffusion flow between the gas and the liquid phase, in the same way as the CO 2 hydration rate. The velocity constant of this last process, whose value gives the in situ enzymatic activity of carbonic anhydrase, has been established in the case of chloroplast and Euglena suspensions and of aerial leaves. The study of the isotopic exchange between C 18 O 2 and a vegetable submitted to alternations of dark and light has allowed to calculate the isotopic abundance of the metabolized CO 2 whose value has been compared to that of the intracellular water and that of photosynthetic oxygen. In addition, a new method using 13 C 18 O 2 gives the means to measure with accuracy eventual isotopic effects. The labelling kinetics of the oxygen evolved by Euglena suspensions whose water has been enriched with 18 O have been established at different temperatures. (author) [fr

  13. Process and device for step by step enrichment of deuterium and/or tritium by isotope exchange

    International Nuclear Information System (INIS)

    Iniotakis, N.; Decken, C.B. von der.

    1984-01-01

    Deuterium and/or tritium are bound to steam by isotope exchange after permeation through an exchange wall. Primary and secondary flows are guided by the counterflow principle. The secondary side has a metal oxide as oxidation catalyst. The plant can consist of several enrichment stages. The various flows and parts of the plant are described. (PW) [de

  14. Isotopic exchange kinetics of zinc ions in Zn-A zeolite

    Energy Technology Data Exchange (ETDEWEB)

    Radak, V M; Gal, I J; Salai, J J [Belgrade Univ. (Yugoslavia)

    1976-01-01

    The isotopic exchange kinetics of Zn/sup 2 +/ ions in hydrated Zn-A zeolite of composition (Znsub(5.55)Nasub(0.90)(A10/sub 2/)/sub 12/(Si0/sub 2/)/sub 12/.aq) have been investigated by measuring the fractional attainment of isotopic equilibrium between a ZnCl/sub 2/ solution and a /sup 65/Zn-labelled Zn-A zeolite (30 and 45 ..mu..m particle radii) as a function of time, in the temperature range 25 to 60/sup 0/C. The exchange mechanism is a two-step process which has been resolved, using the Brown-Sherry-Krambeck model (J.Phys.Chem.;75:3846(1971)) into diffusion in the solid particles, with Zn/sup 2 +/ diffusivity of D = 10sup(-3.97 + -0.03) exp(-Esub(D)/RT)m/sup 2/ s/sup -1/, Esub(D) = 67.1 +- 0.5 kJ molee/sup -1/, and an intracrystalline first-order exchange between bound and mobile Zn/sup 2 +/ ions in the network, with a rate constant of k/sub 2/ = 10sup(3.05 +- 0.25) exp(-Esub(k)/RT)s/sup -1/, Esub(k) = 56.5 +- 1.5 kJ mol/sup -1/.

  15. Positional isotope exchange analysis of the uridine-diphosphoglucose pyrophosphorylase reaction

    International Nuclear Information System (INIS)

    Hester, L.; Hilscher, L.; Raushel, F.M.

    1986-01-01

    The enzyme uridine-diphosphoglucose pyrophosphorylase catalyzes the reversible formation of pyrophosphate and UDP-glucose from UTP and glc-1P. The positional isotope exchange reaction was measured using oxygen-18 labelled UTP. The synthesis of [β- 18 O 2 , βγ- 18 O, γ- 18 O 3 ]UTP was accomplished by the coupled activities of carbamate kinase, nucleoside diphosphate kinase, and nucleoside monophosphate kinase. The exchange of an oxygen-18 from a β-nonbridge position of the labelled UTP to the αβ-bridge position was measured with 31 P NMR. The ratio of the rate of net substrate turnover and the positional isotope exchange rate was measured as a function of the initial glc-1P concentration. This ratio was found to increase with an increasing concentration of glc-1P. The intercept at low glc-1P was found to be 1.2 and the slope was 4.5 mM -1 . These results have been interpreted to mean that this enzyme has an ordered addition of substrates. The lower limit for the release of pyrophosphate from E-UDPG-PP/sub i/ relative to V 2 is 1.2. The rate constant for the release of UTP from E-UTP relative to V 1 is 9

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-15

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

  17. Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model

    Science.gov (United States)

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

    2017-08-01

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

  18. Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

    Science.gov (United States)

    Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

    2017-10-01

    Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

  19. Boron isotope separation by ion exchange chromatography using weakly basic anion exchange resin

    International Nuclear Information System (INIS)

    Itoh, S.; Aida, M.; Okamoto, M.; Nomura, M.; Fujii, Y.

    1985-01-01

    Influences of operating temperatures and concentrations of feed boric acid solutions were examined on the above titled process over the ranges of 25 - 70 0 C and 0.1 - 1.6 mol/dm 3 (M), respectively. The ideal displacement chromatography with a very sharp-cut boundary of the boric acid adsorption band was realized at higher temperatures and lower boric acid concentrations within the experimental conditions. The isotope separation coefficient epsilon was found to decrease with increases in either temperature or the boric acid concentration. The observed values of epsilon at 25 0 C were 0.013, 0.012 and 0.011 corresponding to feed boric acid concentrations of 0.1 M, 0.4 M and 0.8 M, respectively. The epsilon's at 70 0 C were 0.0097 (0.1 M), 0.0086 (0.4 M), 0.0083 (0.8 M) and 0.0073 (1.6 M). A temperature of 40 0 C and 0.4 M of boric acid concentration was considered the optimum operating condition for the production of enriched 10 B. (author)

  20. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis.

    Science.gov (United States)

    Larsen, K K; Wielandt, D; Schiller, M; Bizzarro, M

    2016-04-22

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of these species can result in incomplete Cr recovery during chromatographic purification. Because of large mass-dependent inter-species isotope fractionation, incomplete recovery can affect the accuracy of high-precision Cr isotope analysis. Here, we demonstrate widely differing cation distribution coefficients of Cr(III)-species (Cr(3+), CrCl(2+) and CrCl2(+)) with equilibrium mass-dependent isotope fractionation spanning a range of ∼1‰/amu and consistent with theory. The heaviest isotopes partition into Cr(3+), intermediates in CrCl(2+) and the lightest in CrCl2(+)/CrCl3°. Thus, for a typical reported loss of ∼25% Cr (in the form of Cr(3+)) through chromatographic purification, this translates into 185 ppm/amu offset in the stable Cr isotope ratio of the residual sample. Depending on the validity of the mass-bias correction during isotope analysis, this further results in artificial mass-independent effects in the mass-bias corrected (53)Cr/(52)Cr (μ(53)Cr* of 5.2 ppm) and (54)Cr/(52)Cr (μ(54)Cr* of 13.5 ppm) components used to infer chronometric and nucleosynthetic information in meteorites. To mitigate these fractionation effects, we developed strategic chemical sample pre-treatment procedures that ensure high and reproducible Cr recovery. This is achieved either through 1) effective promotion of Cr(3+) by >5 days exposure to HNO3H2O2 solutions at room temperature, resulting in >∼98% Cr recovery for most types of sample matrices tested using a cationic chromatographic retention strategy, or 2) formation of Cr(III)-Cl complexes through exposure to concentrated HCl at high temperature (>120 °C) for several hours, resulting in >97.5% Cr recovery using a

  1. Isotope dilution analysis

    Energy Technology Data Exchange (ETDEWEB)

    Fudge, A.

    1978-12-15

    The following aspects of isotope dilution analysis are covered in this report: fundamental aspects of the technique; elements of interest in the nuclear field, choice and standardization of spike nuclide; pre-treatment to achieve isotopic exchange and chemical separation; sensitivity; selectivity; and accuracy.

  2. Improvements on heavy water separation technology by isotopic water-hydrogen sulfide exchange

    International Nuclear Information System (INIS)

    Peculea, M.

    1987-01-01

    A series of possible variance is presented for the heavy water separation technology by isotopic H 2 O-H 2 S exchange at dual temperatures. The critical study of these variants, which are considered as characteristic quantities for the isotopes transport (production) and the extraction level is related to a dual temperature plant fed by liquid and cold column, which is the up-to-date technology employed in all heavy water production plants as variants of following plants are studied: dual temperature plant with double feeding; dual-temperature plant with equilibrium column (booster); dual-temperature-dual-pressure plant. Attention is paid to the variant with equilibration column (booster), executed and tested at the State Committee for Nuclear Energy and to the dual-temperature-dual pressure plant which presents the highest efficiency. (author)

  3. Analysis of positional isotope exchange in ATP by cleavage of the βP-OγP bond. Demonstration of negligible positional isotope exchange by myosin

    International Nuclear Information System (INIS)

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

    1987-01-01

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

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

    Science.gov (United States)

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

    1981-12-01

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

  5. Gamma irradiation effects of 51Cr(III) isotope exchange in doped magnesium chromate - zinc chromate mixtures

    International Nuclear Information System (INIS)

    Mahfouz, R.M.

    1984-01-01

    Gamma irradiation effects of 51 Cr(III) isotope exchange in magnesium chromate - zinc chromate mixtures doped with 51 Cr(III) were investigated. It was found that γ irradiation has an oxidation effect and the percentage of exchanged 51 Cr(VI) increases with the increasing γ-ray dose. The data are explained in terms of mechanistic model involving metal and ligand vacancies exchange and substitution reactions. (author)

  6. Study of isotopic exchange reactors (1961); Etude des reacteurs d'echange isotopique (1961)

    Energy Technology Data Exchange (ETDEWEB)

    Grandcollot, P; Dirian, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    A study is made of the general case of the theory of first-order isotopic chemical exchange between a gaseous and a liquid phase in a reactor, starting from fundamental reaction kinetics data, and without making any limiting hypothesis concerning the value of the separation factor. The cases of counter-current reactors and of co-current reactors are considered successively. The general deuterium conservation equation requires the definition of the quotient of the reactor; the performances of this reactor are characterised by its overall efficiency. The idea of the ratio is introduced because it represents a convenient intermediary in the calculations. The search for an additive value for reactors in series leads logically to the defining of an exchange capacity, and a total efficiency, or number of theoretical reactors. This method of expressing the performances of a reactor is more general than the efficiency due to Murphee which only has a physical significance in the particular case of homogeneous liquid reactors. The relationships between these various quantities are established, and the representation due to Mc Cabe and Thiele is generalized. The reactor performances are linked to the first - order reaction kinetics by the transfer number. The relationships are given for a certain number of concrete cases. Finally the application of these calculations is given, together with the approximations necessary in the case where, because of the presence of several components in each phase, the exchange reaction no longer obeys a single kinetic law. (authors) [French] On examine dans le cas general la theorie d'un reacteur quelconque pour l'echange chimique isotopique du premier ordre entre une phase gazeuse et une phase liquide, a partir des donnees fondamentales sur la cinetique de la reaction, sans faire aucune hypothese limitative sur le cas des reacteurs a contre ourant, puis celui des reacteurs a co-courant. L'equation generale de conservation du deuterium

  7. Predicting the bioavailability of phosphorus in soil amended with phosphate rocks using isotopic exchange kinetics

    International Nuclear Information System (INIS)

    Mohammad Edwin Syah Lubis; Zaharah Abd Rahman; Sharifuddin Abd Hamid

    1997-01-01

    Investigations on plant responses to applications of various forms and rates of P fertilizers usually involve glasshouse and/or field experiments. This traditional procedure assumes that whatever the soil-fertilizer-plant system, increase in total P uptake by plant between no P treatment (control) and fertilizer treatment equals the plant P uptake from fertilizer. This study uses the isotopic exchange techniques in the laboratory to predict bioavailability of P fertilizers without the need to conduct glasshouse or field experiments. Serdang series soil (Typic Paleudult) was incubated with 7 sources of P fertilizers comprising of triple superhosphate (TSP) and phosphate rocks from North Carolina (NCPR), Algeria (APR), Tunisia (TPR), Jordan (JPR), Christmas Island (CIPR) and China (CPR) at the rates of 0, 2, 4, 6 and 8g Kg-' soil with 20% moisture content at room temperature in three replications. The soils were sampled at 1, 3, 6 and 9 months after incubation and isotopically exchangeable p determined by the method of Fardeau and Jappe (1976). Intensity, quantity and capacity factors of soil P were calculated and the residual availability of these fertilizers were predicted. Phosphorus in solution was highest in TSP treated soil for all treatments. Among the phosphate rocks, NCPR at rate 8g kg-' soil gave the highest value while, CPR at rate 2 gave the lowest value. Thus showing that these PRs have different reactivities in this soil, where NCPR, APR, TPR and JPR were the reactive PR, while CIPR and CPR were the unreactive ones. The isotopically exchangeable P at one minute (1) in the soil sampled 9 months after incubation was found to correlate very well with plant P uptake by oil palm seedlings grown under the same conditions. Calculations made on the percentage of P derived from these fertilizers up to a period of more than one year after application showed that the reactive PRs to have more residual P made available to plants than the unreactive PR

  8. The study of stability of Pt-SDB in isotopic exchange between tritium oxide and hydrogen

    International Nuclear Information System (INIS)

    Dan Guiping

    2008-06-01

    The stability of Pt-SDB on its catalytic activity and the Pt contained in Pt-SDB have been studied during three years in isotopic exchange between tritium oxide and hydrogen. The convert efficiency of the catalyst declined 10% in first two years and then it is 2% after another two years, when it is used interruptedly. The losing of Pt on Pt-SDB is separately 9.09% and 2.31% after it is washed 2000 hours by water and immersed in water 525 days. (authors)

  9. Selection of the process for the heavy water production using isotopic exchange amonia-hydrogen

    International Nuclear Information System (INIS)

    Guzman R, G.H.

    1980-01-01

    The utilization of the Petroleos Mexicanos ammonia plants for heavy water production by the isotopic exchange NH 3 -H 2 process is presented, in addition a description of the other heavy water production processes was presented. In the ammonia hydrogen process exist two possible alternatives for the operation of the system, one of them is to carry out the enrichment to the same temperature, the second consists in making the enrichment at two different temperatures (dual temperature process), an analysis was made to select the best alternative. The conclusion was that the best operation is the dual temperature process, which presents higher advantages according to the thermodynamics and engineering of the process. (author)

  10. Isotope exchange behaviour of nickel xanthate in presence of substituted anilines and isomeric picolines

    International Nuclear Information System (INIS)

    Naidu, G.R.K.; Naidu, P.R.

    1981-01-01

    The isotope exchange behaviour of nickel xanthate was investigated in the presence of aniline, N-methylaniline, N,N-dimethylaniline and three picoline isomers at 25 deg C. The results showed that the labelled free nickel(II) replaces inactive nickel(II) in the complex. Hence the complex is labile in the presence of all bases except β- and γ-picolines. The observed lability has been attributed to an adduct formation between the complex and the bases. The inert behaviour observed in the presence of β- and ν-picolines has been ascribed to the steric effect of the methyl groups on the adduct formation. (author)

  11. A trap activation model for hydrogen retention and isotope exchange in some refractory materials

    International Nuclear Information System (INIS)

    Brice, D.K.; Doyle, B.L.

    1982-01-01

    Our recently-developed Local Mixing Model (LMM) has been successful in describing and predicting the properties of hydrogen retention and isotope exchange for a variety of refractory materials. For some materials, however, the detailed predictions of the LMM are not observed. A Trap Activation Model (TAM) is proposed here to account for the observed departures from the LMM. Comparison of experimental room temperature saturation depth profiles for H + →Si with the predictions of TAM suggests that the hydrogen traps are multiple-vacancy complexes in this system. The observed profiles result from a beam-induced competition between trap creation/annihilation and H-trapping/detrapping. (orig.)

  12. Separation of iodine-131 from water using isotopic exchange with iodine-starch compound

    International Nuclear Information System (INIS)

    Ignatov, V.P.; Kolomejtseva, I.V.

    1990-01-01

    Conditions of iodine isotopic exchange with iodine-starch compound (ISC) were studied with the aim of compound utilizatoin for radioactive iodine separation from solution. It is shown that in pH range from 2 to 7 the degree of iodine extraction and coefficient of its distribution practically do not depend on pH, at pH>7 ISC destruction (decolorizing) starts and iodine extraction decreases. Rapid method of iodine separation from solution is suggested. The method can be used in radiochemical techniques. The degree of extraction equals 80 %, a higher degree of extraction can not be achieved owing to ISC formation peculiarities

  13. Advantages of chemical exchange-sensitive spin-lock (CESL) over chemical exchange saturation transfer (CEST) for hydroxyl- and amine-water proton exchange studies.

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-11-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, the sensitivity is not optimal and, more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the properties of CEST signals are compared with those of a CE-sensitive spin-lock (CESL) technique irradiating at the labile proton frequency. First, using a higher power and shorter irradiation in CE-MRI, we obtain: (i) an increased selectivity to faster CE rates via a higher sensitivity to faster CEs and a lower sensitivity to slower CEs and magnetization transfer processes; and (ii) a decreased in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Second, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with an asymmetric population approximation, which can be used for quantitative CE-MRI and validated by simulations of Bloch-McConnell equations and phantom experiments. Finally, the in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 = 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of intermediate exchange protons. Copyright © 2014 John Wiley & Sons, Ltd.

  14. Report: Information Meeting / Awareness of Actors on the Chemical Information Exchange Network (CIEN)

    International Nuclear Information System (INIS)

    Senghor, Cheikh

    2015-01-01

    As part of the implementation of the Stockholm Convention, Senegal has established a Chemical Information Exchange Network. The overall objective of this meeting was to identify the various actors involved in the management of chemicals information and to study the modalities for the implementation of the chemical information exchange network in Senegal.

  15. Isotopic study of water exchange between atmosphere and biosphere at different sites in Pakistan

    International Nuclear Information System (INIS)

    Fazil, M.; Ali, M.; Ahmad, M.; Latif, Z.; Butt, S.; Choudhry, M.A.; Qureshiu, R.M.

    2009-11-01

    Study of Isotopic behavior of water exchange between atmosphere and biosphere was initiated to understand the ties between these two spheres. This report presents the isotopic data of delta/sup 18/O and delta /sup 2/H in the water contents of leaves and stems in different plant species along with soil moisture. Non woody plants of wheat and grass along with soil from the surface and from the depth of 7 cm were collected during January 2005 to April 2005. Woody plants of many species were sampled from two sites near Islamabad and Lahore. Air moisture was also collected in the field. Moisture contents from these samples were extracted using the vacuum distillation method and analyzed for /sup 18/O and /sup 2/H Data depicts that the /sup 18/O and /sup 2/H of moisture in the leaves of non- woody and woody plants are much more enriched than their respective stems. This behavior is due to the evaporative enrichment trend originating from the soil moisture in the active root zone and also from the surface of the leaf. Degree of enrichment depends on the size of leaves, temperature, wind speed, stomatal resistance, soil chemistry and humidity. Significant evaporation effects in the moisture of grass stems are due to photosynthesis. Reflection of typical isotopic values of individual rain events is also observed in soil, plant water and atmospheric moisture, which can be used for studying water-use efficiency. Leaves of woody plants have relatively depleted/sup 18/O values during wet (monsoon) period mainly due to retardation of fractionation resulting from higher humidity. The stem samples do not show any significant variation in delta/sup 18/O indicating no evaporation from stems of big trees. Degree of enrichment of leave samples of woody plants also indicates the species- specific effects in oxygen and hydrogen isotopes during transpiration. Pine and Eucalyptus leaves show more variation in the isotopic contents as compared to other species. (author)

  16. Electrical, electrochemical and isotopic exchange measurements on lanthanum gallate based ceramics

    Energy Technology Data Exchange (ETDEWEB)

    Bronin, D.I.; Gorelov, V.P. [RAS, Ekaterinburg (Russian Federation). Inst. of High-Temperature Electrochemistry]|[Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany); Kuzin, B.L.; Kurumchin, E.Kh.; Vdovin, G.K.; Sokolova, Ju.V.; Beresnev, S.M. [RAS, Ekaterinburg (Russian Federation). Inst. of High-Temperature Electrochemistry; Keppeler, M.; Naefe, H.; Aldinger, F. [Max-Planck-Institut fuer Festkoerperforschung, Stuttgart (Germany)

    2000-07-01

    The solubility limits of Sr and Mg in La{sub 1-x}Sr{sub x}Ga{sub 1-y}Mg{sub y}O{sub 3-{delta}} (LSGM) and the electrical conductivity of LSGM and La{sub 1-x}Sr{sub x}Ga{sub 1-y-z}Mg{sub y}Co{sub z}O{sub 3-{delta}} (LSGMC) were studied. By electrochemical and isotopic exchange measurements on both LSGM material and on an LSGM pellet whose surface was modified by Co-doping, it was shown that the oxygen exchange rate between the solids and the surrounding gas phase is much higher in the case of the modified electrolyte material. A single fuel cell with an LSGM electrolyte was constructed and tested. (orig.)

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

    International Nuclear Information System (INIS)

    Fox, E.

    2009-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Fox, E

    2009-05-15

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

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

    International Nuclear Information System (INIS)

    Kaye, J.A.

    1992-01-01

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

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

    Science.gov (United States)

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

    2012-02-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-08-01

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

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

    International Nuclear Information System (INIS)

    Williams, Mike; Kookana, Rai

    2010-01-01

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

  3. Global changes and the air-sea exchange of chemicals

    International Nuclear Information System (INIS)

    1991-01-01

    Present and potential future changes to the global environment have important implications for marine pollution and for the air-sea exchange of both anthropogenic and natural substances. This report addresses three issues related to the potential impact of global change on the air-sea exchange of chemicals: Global change and the air-sea transfer of the nutrients nitrogen and iron. Global change and the air-sea exchange of gases. Oceanic responses to radiative and oxidative changes in the atmosphere. The deposition of atmospheric anthropogenic nitrogen has probably increased biological productivity in coastal regions along many continental margins. Atmospheric deposition of new nitrogen may also have increased productivity somewhat in mid-ocean regions. The projected future increases of nitrogen oxide emissions from Asia, Africa and South America will provide significant increases in the rate of deposition of oxidized nitrogen to the central North Pacific, the equatorial Atlantic, and the equatorial and central South Indian Oceans. Atmospheric iron may be an important nutrient in certain open regions. Future changes will likely occur if there are changing patterns of aridity and wind speed as a result of climate change. The most important future effects on surface ocean p CO2 will likely be caused by changes in ocean circulation. The pH of the ocean would decrease by ∼0.3 units for a doubling of p CO2 , reducing the capacity of the ocean to take up CO 2 . There is increasing evidence that dimethyl sulfide from the ocean is a source of cloud condensation nuclei and thus a factor controlling cloud albedo. By 2060 in the southern hemisphere reduction in total column stratospheric ozone from recent levels could reach 2 to 5% in the tropics, 10% at mid latitudes, and over 20% at 60 deg C. S. In this same time frame increases in ground-level effective UV-B radiation could reach 5%, 26% and 66%, at low, mid, and high latitudes in the southern hemisphere. Changes in

  4. Catalytic isotope exchange reaction between deuterium gas and water pre-adsorbed on platinum/alumina

    International Nuclear Information System (INIS)

    Iida, Itsuo; Kato, Junko; Tamaru, Kenzi.

    1976-01-01

    The catalytic isotope exchange reaction between deuterium gas and the water pre-adsorbed on Pt/Al 2 O 3 was studied. At reaction temperatures above 273 K, the exchange rate was proportional to the deuterium pressure and independent of the amount of adsorbed water, which suggests that the rate determining step is the supply of deuterium from the gas phase. Its apparent activation energy was 38 kJ mol -1 . Below freezing point of water, the kinetic behaviour was different from that above freezing point. At higher deuterium pressures the rate dropped abruptly at 273 K. Below the temperature the apparent activation energy was 54 kJ mol -1 and the exchange rate depended not on the deuterium pressure but on the amount of the pre-adsorbed water. At lower pressures, however, the kinetic behaviour was the same as the above 273 K, till the rate of the supply of deuterium from the gas phase exceeded the supply of hydrogen from adsorbed water to platinum surface. These results suggest that below 273 K the supply of hydrogen is markedly retarded, the state of the adsorbed water differing from that above 273 K. It was also demonstrated that when the adsorbed water is in the state of capillary condensation, the exchange rate becomes very small. (auth.)

  5. Isotope exchange between alkaline earth metal hydroxide and HTO water in the equilibrium state

    International Nuclear Information System (INIS)

    Imaizumi, H.; Gounome, J.; Kano, N.

    1997-01-01

    In order reveal to what extent tritium ( 3 H or T) can be incorporated into hydroxides, the isotope exchange reaction (OT-for-OH exchange reaction) between each alkaline earth metal hydroxide (M(OH) 2 ), where M means alkaline earth metal (M=Ca, Sr or Ba) and HTO water was observed homogeneously at 30 deg C under equilibrium after mixing. Consequently, the followings were obtained: a quantitative relation between the electronegativity of each M ion and the ability (of the M ion) incorporating OT - into the M hydroxide can be found and the ability is small when the temperature is high, the exchange rate for the OT-for-OH exchange reaction is small when the electronegativity of the M ion in the M hydroxide is great, as for the dissociation of HTO water, it seems that formula (HTO ↔ T + + OH - ) is more predominant than the formula (HTO ↔H + + OT - ) when the temperature is high and the method used in this work is useful to estimate the reactivity of a certain alkaline material. (author)

  6. 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

  7. Isotopic and chemical characterization of coal in Pakistan

    International Nuclear Information System (INIS)

    Qureshi, R.M.; Hasany, S.M.; Javed, T.; Sajjad, M.I.; Shah, Z.; Rehman, H.

    1993-11-01

    Stable carbon isotope ratios (delta/sup 13/C PDB) and toxic/trace element concentration levels are determined for Tertiary coal samples collected from seven coal fields in Pakistan. No systematic isotope effects are found in the process of coal liquefaction from peat to Tertiary lignites and sub bituminous coal. Similarly, no age effects are observed during the Tertiary regime. The observed variations in the carbon isotopic composition of coal obtained from 'Sharigh coal field' and the 'Sor-Range/Degari coal field' in Baluchistan are attributed to the depositional environments. More sampling of stable carbon isotope analysis are required to validate these observations. Significant concentrations of toxic elements such as S, Cr, Cd and Pb in Makarwal coal may pose environmental and engineering/operational problems for thermal power plants. (author)

  8. Characteristics of isotope-selective chemical reactor with gas-separating device

    International Nuclear Information System (INIS)

    Gorshunov, N.M.; Kalitin, S.A.; Laguntsov, N.I.; Neshchimenko, Yu.P.; Sulaberidze, G.A.

    1988-01-01

    A study was made on characteristics of separating stage, composed of isotope-selective chemical (or photochemical) reactor and membrane separating cascade (MSC), designated for separation of isotope-enriched products from lean reagents. MSC represents the counterflow cascade for separation of two-component mixtures. Calculations show that for the process of carton isotope separation the electric power expences for MSC operation are equal to 20 kWxh/g of CO 2 final product at 13 C isotope content in it equal to 75%. Application of the membrane gas-separating cascade at rather small electric power expenses enables to perform cascading of isotope separation in the course of nonequilibrium chemical reactions

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

    DEFF Research Database (Denmark)

    FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

    1992-01-01

    Isotope exchange reactions between S-35-labeled sulfur compounds were studied in anoxic estuarine sediment slurries at 21-degrees-C and pH 7.4-7.7. Two experiments labeled with radioactive elemental sulfur (S-35-degrees) and one labeled with radioactive sulfate ((SO42-)-S-35) were performed as time......% of the total S-35 was recovered in the SIGMA-HS- pool in less than 1.5 h. With no detectable SIGMA-HS- (less than 1-mu-M) in the slurry, 58% of the total S-35 was observed in the pyrite pool within 1.5 h. The FeS pool received up to 31% of all S-35 added. The rapid S-35 incorporation from S-35-degrees...... into SIGMA-HS- and FeS pools was explained by isotope exchange reactions. In contrast, there was evidence that the radioactivity observed in the 'pyrite pool' was caused by adhesion of the added S-35-degrees to the FeS2 grains. In all S-35-degrees-labeled experiments we also observed oxidation...

  10. Fractionation of sulfur isotopes in the chemical and biochemical oxidation of sulfide to sulfate

    International Nuclear Information System (INIS)

    Maass, I.; Wetzel, K.; Weise, G.; Heyer, J.

    1983-01-01

    The behaviour of sulfur isotopes in the chemical and biochemical oxidation of marcasite (FeS 2 ) to sulfate has been investigated in rest and shaker cultures at 30 0 C. The microbiological oxidation was carried out using a mixed culture of Thiobacillus. The results show a considerably faster formation of sulfate in the biochemical oxidation in comparison with the chemical oxidation. Isotope analyses of the formed sulfates indicate no or only very small isotope fractionations depending on experimental conditions. The highest enrichment of 32 S in the sulfate is 1.7 per mille. In accordance with the results of other authors it is concluded that in both chemical and biochemical weathering of sedimentary sulfides resulting in the formation of sulfates isotope effects are not of importance. (author)

  11. Advantages of paramagnetic chemical exchange saturation transfer (CEST) complexes having slow to intermediate water exchange properties as responsive MRI agents.

    Science.gov (United States)

    Soesbe, Todd C; Wu, Yunkou; Dean Sherry, A

    2013-07-01

    Paramagnetic chemical exchange saturation transfer (PARACEST) complexes are exogenous contrast agents that have great potential to further extend the functional and molecular imaging capabilities of magnetic resonance. As a result of the presence of a central paramagnetic lanthanide ion (Ln(3+) ≠ La(3+) , Gd(3+) , Lu(3+) ) within the chelate, the resonance frequencies of exchangeable protons bound to the PARACEST agent are shifted far away from the bulk water frequency. This large chemical shift, combined with an extreme sensitivity to the chemical exchange rate, make PARACEST agents ideally suited for the reporting of significant biological metrics, such as temperature, pH and the presence of metabolites. In addition, the ability to turn PARACEST agents 'off' and 'on' using a frequency-selective saturation pulse gives them a distinct advantage over Gd(3+) -based contrast agents. A current challenge for PARACEST research is the translation of the promising in vitro results into in vivo systems. This short review article first describes the basic theory behind PARACEST contrast agents, their benefits over other contrast agents and their applications to MRI. It then describes some of the recent PARACEST research results: specifically, pH measurements using water molecule exchange rate modulation, T2 exchange contrast caused by water molecule exchange, the use of ultrashort TEs (TE < 10 µs) to overcome T2 exchange line broadening and the potential application of T2 exchange as a new contrast mechanism for MRI. Copyright © 2012 John Wiley & Sons, Ltd.

  12. Measurement of liquid mixing characteristics in large-sized ion exchange column for isotope separation by stepwise response method

    International Nuclear Information System (INIS)

    Fujine, Sachio; Saito, Keiichiro; Iwamoto, Kazumi; Itoi, Toshiaki.

    1981-07-01

    Liquid mixing in a large-sized ion exchange column for isotope separation was measured by the step-wise response method, using NaCl solution as tracer. A 50 cm diameter column was packed with an ion exchange resin of 200 μm in mean diameter. Experiments were carried out for several types of distributor and collector, which were attached to each end of the column. The smallest mixing was observed for the perforated plate type of the collector, coupled with a minimum stagnant volume above the ion exchange resin bed. The 50 cm diameter column exhibited the better characteristics of liquid mixing than the 2 cm diameter column for which the good performance of lithium isotope separation had already been confirmed. These results indicate that a large increment of throughput is attainable by the scale-up of column diameter with the same performance of isotope separation as for the 2 cm diameter column. (author)

  13. Effects of different water storage procedures on the dissolved Fe concentration and isotopic composition of chemically contrasted waters from the Amazon River Basin.

    Science.gov (United States)

    Mulholland, Daniel S; Poitrasson, Franck; Boaventura, Geraldo R

    2015-11-15

    Although recent studies have investigated the Fe isotopic composition of dissolved, colloidal and particulate phases from continental and oceanic natural waters, few efforts have been made to evaluate whether water sample storage and the separation of different pore-size fractions through filtration can cause any change to the Fe isotopic compositions. The present study investigates the possible biases introduced by different water storage conditions on the dissolved Fe concentration and isotopic composition of chemically different waters. Water samples were collected from an organic-rich river and from mineral particulate-rich rivers. Filtered and unfiltered water samples were stored either at room temperature or frozen at -18°C in order to assess possible biases due to (i) different water storage temperature, and (ii) storage of bulk (unfiltered) vs filtered water. Iron isotope measurements were performed by Multicollector Inductively Coupled Plasma Mass Spectrometry with a Thermo Electron Neptune instrument, after Fe purification using anion-exchange resins. Our data reveal that bulk water storage at room temperature without filtration produces minor changes in the dissolved Fe isotopic composition of mineral particulate-rich waters, but significant isotopic composition changes in organic-rich waters. In both cases, however, the impact of the different procedures on the Fe concentrations was strong. On the other hand, the bulk water stored frozen without filtration produced more limited changes in the dissolved Fe concentrations, and also on isotopic compositions, relative to the samples filtered in the field. The largest effect was again observed for the organic-rich waters. These findings suggest that a time lag between water collection and filtration may cause isotopic exchanges between the dissolved and particulate Fe fractions. When it is not possible to filter the samples in the field immediately after collection, the less detrimental approach is to

  14. Application of tracer isotope in kinetic study of first order ion exchange reaction

    International Nuclear Information System (INIS)

    Lokhande, R.S.; Singare, P.U.

    1998-01-01

    Analysis of first order ion exchange reaction rates at different temperatures (27 deg- 48 degC) and particularly at low concentration of potassium iodide solution (electrolyte) ranging from 0.005 M to 0.040 M is carried out by application of radioactive tracer isotope 131 I. With increase in concentration of electrolyte, amount of iodide ion exchanged in millimoles increases. Specific reaction rates of ion exchange reaction are calculated for different temperatures and for different amount of ion exchange resins. It is observed that with increase in temperature, reaction rate increases but the increase is more pronounced for increase in amount of ion exchange resins. For 0.005 M solution of electrolyte, the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min -1 at 48 degC. For 0.005 M solution of electrolyte the reaction rate increases from 0.121 min -1 at 27 degC to 0.178 min 1 at 48 degC. For 0.005 M solution of electrolyte at 27 degC the reaction rate increases from 0.121 min -1 for 1.0 g of resin to 0.368 min -1 for 5.0 g of resin. From the reaction rates calculated at different temperatures, energy of activation in kJ/mole is calculated. It is observed that for 0.005 M solution of electrolyte, energy of activation is 4.62 kJ/mole which decreases to 2.87 kJ/mole for increase in concentration of electrolyte to 0.100 M. (author)

  15. Process for the exchange of hydrogen isotopes between streams of liquid water and gaseous halohydrocarbon and an apparatus therefor

    International Nuclear Information System (INIS)

    Symons, E.A.; Rolston, J.H.; Clermont, M.J.; Paterson, L.M.

    1983-01-01

    This invention provides a process for the exchange of hydrogen isotopes between streams of liquid water and gaseous halohydrocarbons comprising: (a) bringing into contact a water stream, a halohydrocarbon stream, and a catalytic porous anion exchange resin so that the isotope-deficient halohydrocarbon stream is enriched; (b) decomposing the halohydrocarbon stream photolytically into two gaseous streams, one enriched and the other deficient; (c) removing as a product the first, enriched stream; and (d) recycling the second stream for enrichment. An apparatus is also provided

  16. Natural Ni speciation in the Callovo-Oxfordian clay rocks: implications for potential 63Ni isotopic exchange and retention mechanisms

    International Nuclear Information System (INIS)

    Grangeon, S.; Tournassat, C.; Schaefer, T.; Lerouge, C.; Wille, G.; Giffaut, E.

    2010-01-01

    Document available in extended abstract form only. In the perspective of deep underground long-term nuclear waste storage, 63 Ni is considered as a priority radio-element to be studied. 63 Ni behaviour prediction is made difficult mainly because its geochemical behaviour is still subject to debate. For instance, the solubility of Ni simple compounds at high pH is ill-defined, and the knowledge on solubility control phases is still pending. Clay rocks such as Callovo-Oxfordian (COx) contain non negligible amounts of natural and stable isotopes of Ni. As a consequence, a good understanding of the natural speciation of Ni in the formation could help to understand 63 Ni controls in this environment, including long term isotopic exchange with naturally present Ni. We focused our study on the COx formation, where the Bure (France) ANDRA underground research laboratory is located. Speciation of naturally occurring Ni was studied by combining chemical, microscopic and spectrometric methods. Chemical methods consisted of total rock analyses and sequential extractions on various COx samples representative of the variability of the formation (from carbonate rich samples to clay rich samples). This method enabled quantifying the main Ni reservoirs. Physical methods were used to get a closer look at the Ni-bearing phases. Optical and scanning electron microscopy techniques were used to identify and isolate minerals from thin rock sections, originating from different geological horizons. Chemical results indicate that the mean Ni concentration in the Callovo-Oxfordian clay rock is of ∼30 ppm (10 -6 g/g). Identified Ni-bearing minerals were mainly primary minerals (biotite, chlorite, muscovite), calcite and pyrite; organic matter being also observed. Electron microprobe and X-ray fluorescence analyses were performed in order to quantify the amounts and variability of Ni contents in these different Callovo-Oxfordian components. Ni is occasionally present in primary minerals with

  17. 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)

  18. Uranium isotope exchange between gaseous UF6 and solid UF5

    International Nuclear Information System (INIS)

    Yato, Yumio; Kishimoto, Yoichiro; Sasao, Nobuyuki; Suto, Osamu; Funasaka, Hideyuki

    1996-01-01

    Based on a collision model, a new rate equation is derived for uranium isotope exchange between gaseous UF 6 and solid UF 5 by considering the number of UF 5 molecules on the solid surface to be dependent on time. The reaction parameters included in the equation are determined from the experimental data and compared with the previous ones. A remarkable agreement is found between the particle sizes of UF 5 estimated from the reaction parameter and from the direct observation with an electron microscope. The rate equation given in this work fully satisfies the related mass conservation and furthermore includes explicitly the terms related to the UF 6 density and the mean size of UF 5 particles, both of which are considered to cause an important effect on the reaction. This remarkable feature facilitates the simulation studies on this reaction under various conditions. The long term behavior of a simulated exchange reaction is studied under the condition considered to be close to that in a recovery zone of the MLIS process. The result indicates that the reaction is virtually limited to the solid surface under this conditions and thus the depletion of 235 UF 5 concentration averaged over the whole UF 5 particles is not significant even after 200 h of the exchange reaction

  19. Application of expert systems to heat exchanger control at the 100-megawatt high-flux isotope reactor

    International Nuclear Information System (INIS)

    Clapp, N.E. Jr.; Clark, F.H.; Mullens, J.A.; Otaduy, P.J.; Wehe, D.K.

    1985-01-01

    The High-Flux Isotope Reactor (HFIR) is a 100-MW pressurized water reactor at the Oak Ridge National Laboratory. It is used to produce isotopes and as a source of high neutron flux for research. Three heat exchangers are used to remove heat from the reactor to the cooling towers. A fourth heat exchanger is available as a spare in case one of the operating heat exchangers malfunctions. It is desirable to maintain the reactor at full power while replacing the failed heat exchanger with the spare. The existing procedures used by the operators form the initial knowledge base for design of an expert system to perform the switchover. To verify performance of the expert system, a dynamic simulation of the system was developed in the MACLISP programming language. 2 refs., 3 figs

  20. Analysis of 235U enrichment by chemical exchange in U(IV) - U(VI) system on anionite

    International Nuclear Information System (INIS)

    Raica, Paula; Axente, Damian

    2007-01-01

    Full text: A theoretical study about the 235 U enrichment by chemical exchange method in U(IV)-U(VI) system on anion-exchange resins is presented. The 235 U isotope concentration profiles along the band were numerically calculated using an accurate mathematical model and simulations were carried out for the situation of product and waste withdrawal and feed supply. By means of numerical simulation, an estimation of the migration time, necessary for a desired enrichment degree, was obtained. The required migration distance, the production of uranium 3 at.% 235 U per year and the plant configuration are calculated for different operating conditions. An analysis of the process scale for various experimental conditions is also presented. (authors)

  1. Isotope effects in interstellar molecules by chemical hyperfine interaction

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  2. Chemical and sulphur isotope compositions of pyrite in the ...

    Indian Academy of Sciences (India)

    sulphide mineralization and their chemical evo- lution in relative .... properties and chemical compositions. Electron ..... from the sulphide lode provide clues to the chang- ing fluid ..... Raymond O L 1996 Pyrite composition and ore geneis in.

  3. Kinetics and mechanism of photoaccelerated isotope exchange between U(VI) and U(IV) in oxalate solutions

    International Nuclear Information System (INIS)

    Shaban, I.S.; Owreit, M.F.; Nikitenko, S.I.

    1992-01-01

    A kinetic study of thermal and photoaccelerated U(IV)-U(VI) isotope exchange has been carried out in oxalate solutions at 11-40 deg C. The rate and quantum yield were determined as a function of U(IV), U(VI) and oxalate concentration, wavelength of incident light, temperature and absorbed dose of γ-radiation. The kinetic equations for thermal and photoaccelerated exchange have been obtained. It was assumed that the mechanism of exchange involves formation of U(V) as an intermediate, followed by slow exchange between U(V) and U(IV). The isokinetic dependence confirms the identity of limiting stages for thermal and photostimulated exchange. The upper component of photoexcited T 1 level of uranyl is supposed to be the most reactive in the process of U(V) generation. It was observed that the small doses of γ-radiation evoke the acceleration of isotope exchange, however, at D>100 krad the rate of exchange is reduced to the level of thermal exchange. (author) 8 refs.; 4 figs.; 2 tabs

  4. Isotopic exchange between 232Th and 234Th using ion exchange resins and its application for the radiochemical separation of thorium and europium

    International Nuclear Information System (INIS)

    Sepulveda Munita, C.J.A.; Atalla, L.T.

    1980-01-01

    The determination of thorium via the measurement of 233 Th activity (obtained by irradiating natural thorium with neutrons) may suffer the interference of various radioisotopes which may be also formed during irradiation, if their parent isotopes are present in the sample. Taking into account this possibility, another technique was chosen for the determination of thorium, based on isotopic exchange associated with ionic exchange. Conditions for the isotopic exchange between 234 Th in solution and 232 Th in the resin were optimized. It was verified that the behaviour of 233 Th and 234 Th is the same regarding isotopic exchange with 232 Th. 234 Th was chosen for the experiments since it has a longer half-life (24.1 days) than 233 Th (22.3 min), thus facilitating the performance of the work. As the major objective of this work is to separate thorium and europium isotopes, the behaviour of 152-154 Eu was studied in the same system used for thorium, envisaging a minimum retention of these radioisotopes in the resin. In order to establish the best conditions for separating 234-Th and 152/154-Eu, the following parameters were considered: the thorium concentration in the solution; the hydrochloric acid concentration in solution; the concentration of other elements in solution; the degree of cross-linking of the resin; the flow rate of the solution through the column. The other elements added to the elutant solution were: uranium, molybdenum, lanthanum, europium, ytterbium, bromine, cobalt, barium, manganese, indium, cesium and selenium. Europium was added so to dilute the 152/154-Eu tracer and avoid the retention of the latter in the resin. The other elements were added because they give rise to radioisotopes which interfere in the activation analysis of thorium when 233-Th activity is used and, the separation of these elements from thorium will also be subsequently studied by the method used in the present work. (C.L.B.) [pt

  5. Experimental evaluation of improved dual temperature hydrogen isotopic exchange reaction system

    International Nuclear Information System (INIS)

    Asakura, Yamato; Uchida, Shunsuke

    1984-01-01

    A proposed dual temperature hydrogen isotopic exchange reaction system between water and hydrogen gas is evaluated experimentally. The proposed system is composed of low temperature co-current reactors for reaction between water mists and hydrogen gas and high temperature co-current reactors for reaction between water vapor and hydrogen gas. Thus, operation is possible under atmospheric pressure with high reaction efficiency. Using the pilot test system which is composed of ten low temperature (30 0 C) reaction units and ten high temperature (200 0 C) reaction units, an experimental separation of deuterium from light water is carried out. The enrichment factor under steady state conditions, its dependency on operating time, and the reaction period necessary to obtain the steady state enrichment factor are determined experimentally and compared with calculations. It is shown that separation ability in a multistage reaction system can be estimated by numerical calculation using actual reaction efficiency in a unit reactor. (author)

  6. Theoretical study on platinum-catalyzed isotope exchange reaction mechanism of hydrogen and liquid water

    International Nuclear Information System (INIS)

    Hu Sheng; Wang Heyi; Luo Shunzhong

    2009-04-01

    Based on electron and vibration approximate means and the density function theory B3LYP, the ΔG degree and equilibrium pressures of adsorption and dissociation reactions of H 2 and water vapor on Pt surface have been calculated. The adsorption, dissociation and coadsorption actions of H 2 and water were analyzed. According to the ΔG degree, hydrogen molecule combines with metal atoms in single atom, and water vapor molecule has no tendency to dissociate on Pt surface. The dissociation of hydrogen molecule would hold back the direct adsorption of water vapor molecules on Pt surface. The structures of Pt-H (OH 2 ) n + (n=1, 2, 3) hydroniums were optimized. According to the mulliken overlap populations, Pt-H (OH 2 ) + is not stable or produced. Hydrogen isotope exchange occurs between hydration layer and D atoms which adsorb on Pt surface via intermediates (H 2 O) n D + (ads) (n≥2). (authors)

  7. Experimental studies on hydrogen isotopic deuterium from gas to liquid phase by catalytic exchange

    International Nuclear Information System (INIS)

    Luo Yangming; Wang Heyi; Liu Jun; Fu Zhonghua; Wang Changbin; Han Jun; Xia Xiulong; Tang Lei

    2005-01-01

    The experimental studies on hydrogen isotopic deuterium from gas to liquid phase were completed by mixed ratio 1:4 of Pt-SDB hydrophobic catalyst and hydrophilic packing. The influencing factors on number of transfer units (NTU) and transformation efficiencies of deuterium were researched. The results show that preferable NTU can be obtained by choosing suitable operational temperature and flux of exchange gas. The transformation rate increases with increasing liquid flux, but it cannot obviously be improved when liquid flux attains some level. The length of catalytic column has an obvious influence on transformation rate and 90% of transformation rate is obtained by 4 m column length at gas flux with 2 m 3 /h, liquid flux with 1-2 kg/h and 45 degree C. (author)

  8. Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra.

    Science.gov (United States)

    Roussis, Stilianos G; Proulx, Richard

    2003-03-15

    A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.

  9. Isotopic and chemical variation of organic nanoglobules in primitive meteorites

    Science.gov (United States)

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

    2013-05-01

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

  10. Isotope ratios and chemical fractionation of CO in Lynds 134

    International Nuclear Information System (INIS)

    Dickman, R.L.; Langer, W.D.

    1977-01-01

    Mahoney, McCutcheon and Shuter (1976) reported observations of the J = 1 → 0 transition of three isotopes of CO in the dust cloud Lynds 134 using the 4.6 m telescope at Aerospace Corporation. In this paper a new observation of 12 C 17 O is discussed and the question of the ratio 13 C 16 O/ 12 C 18 O across the dust cloud is considered further. (Auth.)

  11. Isotopic and chemical investigations of quaternary aquifer in sinai peninsula

    International Nuclear Information System (INIS)

    Sadek, M.A.; Ahmed, M.A.; Awad, M.A.

    2001-01-01

    The present study has been conducted to investigate the renewal activity and mineralization potential of the quaternary aquifer in Sinai peninsula using environmental isotopes and hydrochemistry. The quaternary aquifer is vital for development processes as it has a wide extension and shallow water table. The total dissolved salts vary greatly from one location to another and range widely between 510-7060 mg/1, reflecting all categories from fresh to saline water. The change in salinity all over Sinai can be attributed to variations in the rate of evaporation. Leaching and dissolution of terrestrial salts during floods as well as the effects of sea spray and saline water intrusion. The main sources of groundwater recharge are the infiltration of Local precipitation and surface runoff as well as lateral flow through hydraulic connection with fractured aquifers. Snow melt also contributes to aquifer recharge in some areas in the central part of southern Sinai. The environmental stable isotopic contents of the ground water in the quaternary aquifer in Sinai reflect the isotopic composition of rain water from continental and east Mediterranean precipitation and monsonal air mass which comes from Indian ocean as well as the seepage of partly evaporated floodwater. The southern samples are more suitable for drinking and irrigation purposes due to its lower salinity and sodium hazard

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

    Czech Academy of Sciences Publication Activity Database

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

    2017-01-01

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

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

    Science.gov (United States)

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

    2015-12-01

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

  14. Influence of organic carbon sources and isotope exchange processes between water and nitrate on the fractionation of the stable isotopes 15N/14N and 18O/16O in dissolved nitrate during microbial dentrification in groundwater

    International Nuclear Information System (INIS)

    Wunderlich, Anja A.L.

    2012-01-01

    Stable isotopes of nitrate are commonly used to determine sources and degradation of nitrate. In this study, nitrite oxidizing bacteria were found to promote an oxygen isotope exchange between water and nitrate under anoxic conditions. Also, different carbon sources were found to influence the enrichment of stable isotopes in nitrate during microbial denitrification. Both results refine the stable isotope model of nitrate in respect to nitrate source determination and microbial nitrate reduction.

  15. Isotope exchange between natural and anthropogenic Pb in the coastal waters of Singapore: exchange experiment, Kd model, and implications for the interpretation of coastal 210Pb data

    Science.gov (United States)

    Boyle, E. A.; Chen, M.; Zurbrick, C.; Carrasco, G. G.

    2015-12-01

    Observations from annually-banded corals and seawater samples show that marine lead (Pb) in the coastal waters of Singapore has an isotopic composition that does not match that of the anthropogenic aerosols in this region, unlike what is seen in most parts of the open ocean. The 206Pb/207Pb composition of Singaporean marine Pb is 1.18-1.20 whereas the local aerosols are 1.14-1.16. In order to explore this discrepancy further, we collected a large volume water from the Johor River estuary (flowing from Malaysia to the northern border of Singapore), added a distinct isotope spike (NBS981, 206Pb/207Pb =1.093) to an unfiltered sample, and followed the dissolved isotope composition of the mixture during the following two months. The initial dissolved Pb concentration was 18.3 pmol/kg with 206Pb/207Pb of 1.200. "Total dissolvable" Pb released after acidification of the in the unfiltered sample was 373 pmol/kg with 206Pb/207Pb of 1.199, indicating that there is a large particulate Pb reservoir with an isotopic composition comparable to regional crustal natural Pb. The isotope spike should have brought the dissolved 206Pb/207Pb to 1.162, but less than a day after isotope spiking, the dissolved Pb had risen to 1.181 and continued a slow increase to 1.197 over the next two months. This experiment demonstrates that Johor estuary particulate matter contains a large reservoir of exchangeable Pb that will modify the isotopic composition of deposited aeolian aerosol anthropogenic Pb. We have modeled the evolution of Pb and Pb isotopes in this experiment with a single Kd -type model that assumes that there are two or three different Pb reservoirs with different exchange time constants. This observation has implications for isotope equilibrium between high Pb/210Pb continental particles and low Pb/210Pb ocean waters - what is merely isotope equilibration may appear to be 210Pb scavenging.

  16. Study of isotopic exchange of radioactive calcium and cerium cations with y zeolites in aqueous and alcoholic solution

    Energy Technology Data Exchange (ETDEWEB)

    Guilloux, M

    1974-12-31

    Thesis. The isotopic exchange of y zeolite cations with calcium and cerium was studied. The experimental work was carried out utilizing the heterogeneous isotopic exchange between aqueous and alcoholic solutions of the cation considered and a zeolite powder containing a corresponding radioisotope. Aqueous phase exchanges demonstrate that a complex diffusion phenomenon is taking place which is capable of being decomposed into at least two distinct phases: a very slowly occurring phase representing 25 to 30% of the total exchange at ordinary temperatures and a very rapidly occurring phase. In alcoholic solutions, a rapid phase is always observed together with a slow diffusion phase although the exchange rates and diffusion coefficients may vary considerably with the nature and composition of the solvent. The results enable a hypothesis to be advanced on the ion exchange mechanism. The migration of the ions requires the crossing of two types of barrier: the large windows of the supercages (8A); the windows of the sodalite cages (2A). The two stages of the exchange kinetics can be related to these two types of barrier. (FR)

  17. Enrichment of 15N and 18O by chemical exchange reactions between nitrogen oxides (NO, NO2) and aqueous nitric acid

    International Nuclear Information System (INIS)

    Abrudean, M.; Axente, D.; Baldea, A.

    1981-01-01

    The enrichment of 15 N and 18 O by chemical exchange in the NO, NO 2 -H 2 O, HNO 3 system is described. A laboratory experimental plant and a cascade for producing the two isotopes has been used. The production plant consists of two exchange columns for 15 N separation and two 18 O separation columns feeded with nitrogen oxides, depleted of 15 N, from the top of the first 15 N separation column. The by-products nitric acid and sulphuric acid, both depleted of 15 N and 18 O, are of commercial interest. (author)

  18. Catalytic activity in reactions of isotopic exchange of carbon monoxide and adsorption properties of catalysts on zinc oxide base

    International Nuclear Information System (INIS)

    Mikheeva, T.M.; Kasatkina, L.A.; Volynkina, A.Ya.

    1987-01-01

    Activity of different zinc oxide samples in reaction of CO homomolecular isotopic exchnge (HMIE) ( 13 C 18 O+ 12 C 16 O= 13 C 16 O+ 12 C 18 O), CO adsorption on ZnO and isotopic exchange between adsorbed and gaseous CO are investigated. The most active is ZnO sample prepared from ZnCO 3 . Quantitative ratio between different with respect to surface strength molecules of adsorbed CO are experimentally determined. It is shown that by increase of ZnO time contact with CO the quantity of adsorbed CO(N σ/0 ), capable of fast exchange with a gaseous phase, is reduced and the quantity of slowly exchanged adsorbed CO is increased. Correlation between decrease of N σ/0 and decrease of CO HMIE with the catalyst holding time in CO medium is stated

  19. The isotopic and chemical evolution of Mount St. Helens

    Science.gov (United States)

    Halliday, A.N.; Fallick, A.E.; Dickin, A.P.; Mackenzie, A.B.; Stephens, W.E.; Hildreth, W.

    1983-01-01

    Isotopic and major and trace element analysis of nine samples of eruptive products spanning the history of the Mt. St. Helens volcano suggest three different episodes; (1) 40,000-2500 years ago: eruptions of dacite with ??{lunate}Nd = +5, ??{lunate}Sr = -10, variable ??18O, 206Pb/204Pb ??? 18.76, Ca/Sr ??? 60, Rb/Ba ??? 0.1, La/Yb ??? 18, (2) 2500-1000 years ago: eruptions of basalt, andesite and dacite with ??{lunate}Nd = +4 to +8, ??{lunate}Sr = -7 to -22, variable ??18O (thought to represent melting of differing mantle-crust reservoirs), 206Pb/204Pb = 18.81-18.87, variable Ca/Sr, Rb/Ba, La/Yb and high Zr, (3) 1000 years ago to present day: eruptions of andesite and dacite with ??{lunate}Nd = +6, ??{lunate}Sr = -13, ??18O ???6???, variable 206Pb/204Pb, Ca/Sr ??? 77, Rb/Ba = 0.1, La/Yb ??? 11. None of the products exhibit Eu anomalies and all are LREE enriched. There is a strong correlation between 87Sr/86Sr and differentiation indices. These data are interpreted in terms of a mantle heat source melting young crust bearing zircon and garnet, but not feldspar, followed by intrusion of this crustal reservoir by mantle-derived magma which caused further crustal melting and contaminated the crustal magma system with mafic components. Since 1000 years ago all the eruptions have been from the same reservoir which has displayed a much more gradual re-equilibration of Pb isotopic compositions than other components suggesting that Pb is being transported via a fluid phase. The Nd and Sr isotopic compositions lie along the mantle array and suggest that the mantle underneath Mt. St. Helens is not as depleted as MORB sources. There is no indication of seawater involvement in the source region. ?? 1983.

  20. Topology in isotopic multispace and origin of mantle chemical heterogeneities

    International Nuclear Information System (INIS)

    Allegre, C.J.; Hamelin, B.; Provost, A.; Dupre, B.

    1987-01-01

    In this paper we present a simple technique for multidimensional treatment of isotopic data, which allows a global and rigorous correlation between the various radiogenic tracers. This technique is based on the determination of eigenvectors of the data matrix, allowing a geometric description of the inertia ellipsoid corresponding to the cluster of experimental data points. The relationships between the various sets of samples can be analyzed using the projections on the main elongation planes. When processing the Pb-Sr-Nd data for the oceanic mantle (OIB+MORB) with this technique we find that at least four different end-members are needed to define the 'mantle array' which thus cannot be a plane surface. Samples from island arcs (IAB) show the contribution of a component clearly out of the oceanic domain and very similar to terrigenous sediments. Continental tholeiites (CFB) also show some sort of contamination (but distinct from that of IAB) by the continental crust. They also show a domain overlapping with that of the oceanic islands corresponding to the compositions of the 'Dupal anomaly'. Multispace analysis also permits a rigorous comparison of relationships between the various isotopic tracers. In particular, we demonstrate that a U-Pb fractionation independent from the correlated Sr-Nd, Th-U and Th-Sr ones does exist. Consequently, a three-dimensional analysis performed only with lead isotopes yields by itself the main information that can be inferred from the five Pb-Sr-Nd dimensions. Helium also yields independent information decoupled with respect to the other tracers, adding one fifth end-member (Loihi, Hawaii islands) to the OIB+MORB array. (orig.)

  1. Simulations of NMR pulse sequences during equilibrium and non-equilibrium chemical exchange

    International Nuclear Information System (INIS)

    Helgstrand, Magnus; Haerd, Torleif; Allard, Peter

    2000-01-01

    The McConnell equations combine the differential equations for a simple two-state chemical exchange process with the Bloch differential equations for a classical description of the behavior of nuclear spins in a magnetic field. This equation system provides a useful starting point for the analysis of slow, intermediate and fast chemical exchange studied using a variety of NMR experiments. The McConnell equations are in the mathematical form of an inhomogeneous system of first-order differential equations. Here we rewrite the McConnell equations in a homogeneous form in order to facilitate fast and simple numerical calculation of the solution to the equation system. The McConnell equations can only treat equilibrium chemical exchange. We therefore also present a homogeneous equation system that can handle both equilibrium and non-equilibrium chemical processes correctly, as long as the kinetics is of first-order. Finally, the same method of rewriting the inhomogeneous form of the McConnell equations into a homogeneous form is applied to a quantum mechanical treatment of a spin system in chemical exchange. In order to illustrate the homogeneous McConnell equations, we have simulated pulse sequences useful for measuring exchange rates in slow, intermediate and fast chemical exchange processes. A stopped-flow NMR experiment was simulated using the equations for non-equilibrium chemical exchange. The quantum mechanical treatment was tested by the simulation of a sensitivity enhanced 15 N-HSQC with pulsed field gradients during slow chemical exchange and by the simulation of the transfer efficiency of a two-dimensional heteronuclear cross-polarization based experiment as a function of both chemical shift difference and exchange rate constants

  2. Contributions of chemical exchange to T1ρ dispersion in a tissue model.

    Science.gov (United States)

    Cobb, Jared G; Xie, Jingping; Gore, John C

    2011-12-01

    Variations in T(1ρ) with locking-field strength (T(1ρ) dispersion) may be used to estimate proton exchange rates. We developed a novel approach utilizing the second derivative of the dispersion curve to measure exchange in a model system of cross-linked polyacrylamide gels. These gels were varied in relative composition of comonomers, increasing stiffness, and in pH, modifying exchange rates. Magnetic resonance images were recorded with a spin-locking sequence as described by Sepponen et al. These measurements were fit to a mono-exponential decay function yielding values for T(1ρ) at each locking-field measured. These values were then fit to a model by Chopra et al. for estimating exchange rates. For low stiffness gels, the calculated exchange values increased by a factor of 4 as pH increased, consistent with chemical exchange being the dominant contributor to T(1ρ) dispersion. Interestingly, calculated chemical exchange rates also increased with stiffness, likely due to modified side-chain exchange kinetics as the composition varied. This article demonstrates a new method to assess the structural and chemical effects on T(1ρ) relaxation dispersion with a suitable model. These phenomena may be exploited in an imaging context to emphasize the presence of nuclei of specific exchange rates, rather than chemical shifts. Copyright © 2011 Wiley Periodicals, Inc.

  3. On the enrichment of low-abundant isotopes of light chemical elements by gas centrifuges

    International Nuclear Information System (INIS)

    Borisevich, V.D.; Morozov, O.E.; Zaozerskiy, Yu.P.; Shmelev, G.M.; Shipilov, Yu.D.

    2000-01-01

    A brief review of the main areas for the application of the isotopes 15 N and 13 C is made. Separation of the nitrogen isotopes in a single gas centrifuge in the form of pure nitrogen, ammonia, and trifluoride of nitrogen as well as the carbon isotopes in the form of carbon dioxide has been studied by means of numerical simulation. The parameters of the centrifugal machine investigated were close to the parameters of the Iguassu machine. The dependence of the efficiency criterion versus the basic parameters of the separation process has been explored in the computational experiments. Comparisons of the calculated results with the experimental data have shown good agreement. The results obtained have demonstrated the possibility of using gas centrifuge technology to enrich successfully the low-abundant isotopes of light chemical elements

  4. Survey of knowledge of hazards of chemicals potentially associated with the advanced isotope separation processes

    International Nuclear Information System (INIS)

    Chester, R.O.; Kirkscey, K.A.; Randolph, M.L.

    1979-09-01

    Hazards of chemical potentially associated with the advanced isotope separation processes are estimated based on open literature references. The tentative quantity of each chemical associated with the processes and the toxicity of the chemical are used to estimate this hazard. The chemicals thus estimated to be the most potentially hazardous to health are fluorine, nitric acid, uranium metal, uranium hexafluoride, and uranium dust. The estimated next most hazardous chemicals are bromine, hydrobromic acid, hydrochloric acid, and hydrofluoric acid. For each of these chemicals and for a number of other process-associated chemicals the following information is presented: (1) any applicable standards, recommended standards and their basis; (2) a brief discussion to toxic effects including short exposure tolerance, atmospheric concentration immediately hazardous to life, evaluation of exposures, recommended control procedures, chemical properties, and a list of any toxicology reviews; and (3) recommendations for future research

  5. Survey of knowledge of hazards of chemicals potentially associated with the advanced isotope separation processes

    Energy Technology Data Exchange (ETDEWEB)

    Chester, R.O.; Kirkscey, K.A.; Randolph, M.L.

    1979-09-01

    Hazards of chemical potentially associated with the advanced isotope separation processes are estimated based on open literature references. The tentative quantity of each chemical associated with the processes and the toxicity of the chemical are used to estimate this hazard. The chemicals thus estimated to be the most potentially hazardous to health are fluorine, nitric acid, uranium metal, uranium hexafluoride, and uranium dust. The estimated next most hazardous chemicals are bromine, hydrobromic acid, hydrochloric acid, and hydrofluoric acid. For each of these chemicals and for a number of other process-associated chemicals the following information is presented: (1) any applicable standards, recommended standards and their basis; (2) a brief discussion to toxic effects including short exposure tolerance, atmospheric concentration immediately hazardous to life, evaluation of exposures, recommended control procedures, chemical properties, and a list of any toxicology reviews; and (3) recommendations for future research.

  6. The isotopic and chemical evolution of Mount St. Helens

    International Nuclear Information System (INIS)

    Halliday, A.N.; Fallick, A.E.; Dickin, A.P.; Mackenzie, A.B.; Stephens, W.E.

    1983-01-01

    Isotopic and major and trace element analysis of nine samples of eruptive products spanning the history of the Mt. St. Helens volcano suggest three different episodes; (1) 40,000-2500 years ago: eruptions of dacite with epsilonsub(Nd) = +5, epsilonsub(Sr) = -10, variable delta 18 O, 206 Pb/ 204 Pb approx.= 18.76, Ca/Sr approx.= 60, Rb/Ba- approx.= 0.1, La/Yb approx.= 18, (2) 2500-1000 years ago: eruptions of basalt, andesite and dacite with epsilonsub(Nd) = +4 to + 8, epsilonsub(Sr) = -7 to -22, variable delta 18 O (thought to represent melting of differing mantle-crust reservoirs), 206 Pb/ 204 Pb = 18.81-18.87, variable Ca/Sr, Rb/Ba, La/Yb and high Zr, (3) 1000 years ago to present day: eruptions of andesite and dacite with epsilonsub(Nd) = + 6, epsilonsub(Sr) = -13, delta 18 O approx.= 6per mille, variable 206 Pb/ 204 Pb, Ca/Sr approx.= 77, Rb/Ba = 0.1, La/Yb approx.= 11. None of the products exhibit Eu anomalies and all are LREE enriched. There is a strong correlation between 87 Sr/ 86 Sr and differentiation indices. These data are interpreted in terms of a mantle heat source melting young crust bearing zircon and garnet, but not feldspar, followed by intrusion of this crustal reservoir by mantle-derived magma which caused further crustal melting and contaminated the crustal magma system with mafic components. Since 1000 years ago all the eruptions have been from the same reservoir which has displayed a much more gradual re-equilibration of Pb isotopic compositions than other components suggesting that Pb is being transported via a fluid phase. The Nd and Sr isotopic compositions lie along the mantle array and suggest that the mantle underneath Mt. St. Helens is not as depleted as MORB sources. There is no indication of seawater involvement in the source region. (orig.)

  7. Deuterium in astrophysical ice analogues: Isotope exchange and IR detection sensitivity for HDO

    Science.gov (United States)

    Escribano, R. M.; Galvez, O.; Mate, B.; Herrero, V. J.

    2011-12-01

    Among D-bearing molecules, water is especially interesting from an astrophysical point of view. Although the deuterium content of water in astronomical environments is relatively small as compared with other molecules, it holds most valuable information, still largely undeciphered, on the dynamics of formation and evaporation of ice grain mantels in protostellar regions [1], and is crucial for the understanding of the formation of the Solar System and the Earth [2]. In this work, we have used the OD stretching bands of HDO and D2O molecules in various ice mixtures formed by vapor deposition on a cold substrate (see ref [3] for a description of the experimental set-up) to study the sensitivity of the IR technique for the detection of HDO in ice samples, and to monitor processes of H/D isotope exchange in these solids. It is found that the detection sensitivity is strongly dependent on the ice structure. The OD band is extremely broad and tends to disappear into the absorption continuum of H2O for low temperature amorphous samples. Detectable HDO/H2O ratios with this technique may range from a few per cent for amorphous samples to a few per thousand in crystalline ice. These relatively high upper limits and the appreciable dependence of the band shape on temperature, complicating the interpretation of data from many lines of sight, may question the usefulness of this technique. Isotopic H/D exchange in mixed ices of H2O/D2O is found to start at ~ 120 K and is greatly accelerated at 150 K, as crystallization proceeds in the ice. The process is mainly driven by proton transfer assisted by orientational defect mobility. Annealed amorphous samples are more favourable for isotope exchange than samples directly formed in the crystalline phase. The annealing process seems to lead to polycrystalline ice morphology with a higher defect activity. The present data emphasize the relevance of a depletion mechanism for D atoms in hydroxylic bonds in the solid state, recently

  8. Identifying stereoisomers by ab-initio calculation of secondary isotope shifts on NMR chemical shieldings.

    Science.gov (United States)

    Böhm, Karl-Heinz; Banert, Klaus; Auer, Alexander A

    2014-04-23

    We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2H)ethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T) level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

  9. Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings

    Directory of Open Access Journals (Sweden)

    Karl-Heinz Böhm

    2014-04-01

    Full Text Available We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2Hethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

  10. Enrichment: CRISLA [chemical reaction by isotope selective activation] aims to reduce costs

    International Nuclear Information System (INIS)

    Eerkens, J.W.

    1989-01-01

    Every year, more than $3 billion is spent on enriching uranium. CRISLA (Chemical Reaction by Isotope Selective Activation) uses a laser-catalyzed chemical reaction which, its proponents claim, could substantially reduce these costs. In CRISLA, an infrared CO laser illuminates the intracavity reaction cell (IC) at a frequency tuned to excite primarily UF 6 . When UF 6 and co-reactant RX are passed through the IC, the tuned laser photons preferentially enhance the reaction of UF 6 with RX ten-thousand-fold over the thermal reaction rate. Thus the laser serves as an activator and the chemical energy for separation is largely chemical. (author)

  11. Inversion of the calcium isotope separation at an ion exchanger resin by variation of the LiCl electrolyte concentration

    International Nuclear Information System (INIS)

    Heumann, K.G.; Kloeppel, H.; Sigl, G.

    1982-01-01

    The calcium isotope separation at a strongly acidic exchanger resin as a function of the concentration of a LiCl solution is investigated in column experiments. Whereas an enrichment of the heavier calcium isotopes in the solution phase is found with a 3 M LiCl solution, an inverse effect is obtained with 8 M and 12 M LiCl solutions. The separation effect epsilon for the 12 M solution is found to be the highest calcium enrichment in a system without a complexing agent. The results are compared with those for other electrolyte solutions and can be explained by the anion/cation interactions. (orig.)

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

    Science.gov (United States)

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

    2011-05-28

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

  13. Chemical and isotopic investigation of warm springs associated with normal faults in Utah

    Science.gov (United States)

    Cole, David R.

    1983-04-01

    Thermal springs associated with normal faults in Utah have been analyzed for major cations and anions, and oxygen and hydrogen isotopes. Springs with measured temperatures averaging greater than 40°C are characterized by Na + K- and SO 4 + Cl-rich waters containing 10 3 to 10 4 mg/l of dissolved solids. Lower temperature springs, averaging less than 40°C, are more enriched in Ca + Mg relative to Na + K. Chemical variations monitored through time in selected thermal springs are probably produced by mixing with non-thermal waters. During the summer months at times of maximum flow, selected hot springs exhibit their highest temperatures and maximum enrichments in most chemical constituents. Cation ratios and silica concentrations remain relatively constant through time for selected Utah thermal springs assuring the applicability of the geothermometer calculations regardless of the time of year. Geothermometer calculations utilizing either the quartz (no steam loss), chalcedony or Mg-corrected Na/K/Ca methods indicate that most thermal springs in Utah associated with normal faults have subsurface temperatures in the range of 25 to less than 120°C. This temperature range suggests fluid circulation is restricted to depths less than about three kilometers assuming an average thermal gradient of about 40°C/km. Thermodynamic calculations suggest that most thermal springs are oversaturated with respect to calcite, quartz, pyrophyllite, (Fe, Mg)-montmorillonite, microcline and hematite, and undersaturated with respect to anhydrite, gypsum, fluorite and anorthite. Chalcedony and cristobalite appear to be the only phases consistently at or near saturation in most waters. Theoretical evaluation of mixing on mineral saturation trends indicates that anhydrite and calcite become increasingly more undersaturated as cold, dilute groundwater mixes with a hot (150°C), NaCl-rich fluid. The evolution of these thermal waters issuing from faults appears to be one involving the

  14. A PC-based system for simulation of processes in the isotopic exchange column of a cryogenic pilot plant

    International Nuclear Information System (INIS)

    Retevoi, Carmen Maria; Stefan, Liviu; Baltateanu, Ovidiu; Stefan, Iuliana

    2001-01-01

    The technology developed at the Institute of Cryogenics and Isotope Separations is based on catalytic isotope exchange between water and hydrogen gas both carrying various isotopes of hydrogen: normal hydrogen, deuterium, and tritium. This isotope exchange is followed by cryogenic distillation to separate the various isotopes of hydrogen gas. The detritiation process was simulated using water as working fluid, with a small content of deuterium and a gaseous mixture of hydrogen and deuterium. Isotopic separation of hydrogen is very important for nuclear plants utilizing the CANDU reactor concept. Tritiated water is extracted from the moderator of the reactor and the tritium is removed in order to reduce the radiation levels from the reactor. One of the most important steps in this process is the catalytic isotope exchange between tritiated water and hydrogen gas. In the 'Catalytic isotope exchange' system, tritium transfer occurs from the liquid phase (tritiated heavy water) into the gaseous phase (hydrogen) in an isotope exchange column. The column is packed with alternating layers of two types of catalysts: an ordered B7 type of phosphorous bronze to catalyze the equilibration between liquid and gaseous water and a PT/C/PTFE catalyst to catalyze the reaction between water vapor and hydrogen gas. The corresponding reactions are (DTO) L + (D 2 O) V ↔ (D 2 O) L + (DTO) V and (DTO) V + (D 2 ) G ↔ (D 2 O) V + (DT)G. The design of the process requires a constant catalytic exchange temperature that must be maintained at a value of 90 deg.C. To achieve this, the plant is equipped with electrical heat exchangers for heating the gas (hydrogen) and the heavy water. The control is achieved using an array of sensors and controllers. The sensors used for monitoring the process are type J thermocouples. The temperature control is achieved by controlling the electrical power fed to the heaters. Besides sensing the fluid temperatures at various points, we also monitor the

  15. Contributions of chemical and diffusive exchange to T1ρ dispersion.

    Science.gov (United States)

    Cobb, Jared Guthrie; Xie, Jingping; Gore, John C

    2013-05-01

    Variations in local magnetic susceptibility may induce magnetic field gradients that affect the signals acquired for MR imaging. Under appropriate diffusion conditions, such fields produce effects similar to slow chemical exchange. These effects may also be found in combination with other chemical exchange processes at multiple time scales. We investigate these effects with simulations and measurements to determine their contributions to rotating frame (R1ρ ) relaxation in model systems. Simulations of diffusive and chemical exchange effects on R1ρ dispersion were performed using the Bloch equations. Additionally, R1ρ dispersion was measured in suspensions of Sephadex and latex beads with varying spin locking fields at 9.4 T. A novel analysis method was used to iteratively fit for apparent chemical and diffusive exchange rates with a model by Chopra et al. Single- and double-inflection points in R1ρ dispersion profiles were observed, respectively, in simulations of slow diffusive exchange alone and when combined with rapid chemical exchange. These simulations were consistent with measurements of R1ρ in latex bead suspensions and small-diameter Sephadex beads that showed single- and double-inflection points, respectively. These observations, along with measurements following changes in temperature and pH, are consistent with the combined effects of slow diffusion and rapid -OH exchange processes. Copyright © 2012 Wiley Periodicals, Inc.

  16. Treatment of radioactive wastewaters by chemical precipitation and ion exchange

    International Nuclear Information System (INIS)

    Robinson, S.M.; Begovich, J.M.; Brown, C.H. Jr.; Campbell, D.O.; Collins, E.D.

    1987-01-01

    Precipitation and ion exchange methods are being developed at Oak Ridge National Laboratory to decontaminate wastewaters containing small amounts of 90 Sr and 137 Cs while minimizing waste generation. Distribution coefficients have been determined for strontium and cesium as functions of Ca, Na, and Mg concentrations from bench- and pilot-scale data for ion exchange resins and zeolites using actual wastewaters. Models have been used to estimate the total amount of waste that would be generated at full-scale operation. Based on these data, four process flowsheets are being tested at full-scale. 14 refs., 8 figs., 7 tabs

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  18. Kinetic study of the isotopic exchange of Na+ and Zn2+ ions on iron and chromium titanates

    International Nuclear Information System (INIS)

    Zakaria, E.S.; Ali, I.M.; Aly, H.F.

    2004-01-01

    Iron(III) (FeTi) and chromium (III) titanates (CrTi) were prepared as cation exchange materials in a granular form. The rate of the isotopic exchange of Na + /*Na + and Zn 2+ /*Zn 2+ between aqueous solution and iron(III) and chromium(III) titanates in Na + or Zn 2+ form has been carried out radiometrically in the 25-60 deg C temperature range. The exchange rate is controlled by a particle diffusion mechanism and experimental and theoretical approaches have been used to obtain the rate of diffusion through the spherical particles of the exchangers. The values of self diffusion (D-bar) of Na + and Zn 2+ ions were measured at different operation conditions, particle size, reaction temperatures and drying temperatures of the matrix. The values of kinetic and thermodynamic parameters were calculated and their significance discussed. (author)

  19. Monitoring of chemical and isotopic composition of the Euphrates river in Syria

    International Nuclear Information System (INIS)

    Kattan, Z.

    2008-11-01

    The ratios of stable isotopes ( 18 O and 2 H), tritium content, together with the chemical composition of major ions of the Euphrates and Balikh (Euphrates tributary) Rivers, and the groundwaters of four wells drilled close to the Euphrates River course, were measured on a monthly basis. The Euphrates River water was monitored at twelve stations along its course in Syria during the period from January 2004 to December 2006, whereas those of the Balikh and groundwaters were only investigated during 2005. Although, the spatial variations of heavy stable isotope concentrations are moderated with respect to other large rivers in the world, the concentrations of these isotopes increase generally downstream the Euphrates River, with a sharp enrichment at Al-Assad Lake. This sharp increase could be explained by the effect of direct evaporation from the river and its tributaries; and the effect of drainage return flows of irrigation waters, isotopically more enriched. Enrichment of stable isotopes in the Euphrates River water was used as a direct indicator of evaporation. Based on an experimental evaporation result of a Euphrates water sample and the integral enrichment of heavy stable isotopes in the Euphrates River system, the amount of water losses by evaporation from Al-Assad Lake was estimated to be about 1.26 to 1.62 billion m''3, according to 18 O and deuterium ( 2 H), respectively. This amount represents about 12-16% of the renewable surface water resources in the country. (author)

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

    Science.gov (United States)

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

    2015-07-27

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

  1. Some results on the isotope studies of water exchange in boreal raised bogs

    International Nuclear Information System (INIS)

    Sirin, A.A.; Vlasova, L.S.; Polyakov, V.A.; Trofimova, A.E.

    2002-01-01

    Raised bogs are rather common and one of the most exciting mire types of the boreal zone. They receive water and nutrients from precipitation and pore water stored in their domes (up to 10 m in height) is spaced above levels of regional ground water or streams draining them. Peatland hydrologists have long assumed that fluid flow occurs mainly in a peat layer near to the surface and water transport is negligible in deeper layers. The 'acrotelm/catotelm' paradigm on active and inert horizons for the peat above and below the lowest water level is still widely spread in peatland hydrology. However, recent studies have shown that deep water movement is much more dynamic in raised bogs than was previously thought. Based on geochemical studies and numerical simulations even temporal reverse of the vertical direction of water fluid flow through the peat as connected to climate fluctuations was assumed. Relying on isotope studies we consider only the mounded strata of the raised bogs to have relatively active water exchange. The study included two raised bogs, representing different local hydrological conditions (underlain by outwash sands and moraine clay) at the Zapadnaya Dvina Peatland Field Station of the Forest Research Institute located 400 km west of Moscow. Peatlands, among which raised bogs dominate, constitute >30% of the area, and maximum peat thickness exceeds 7 m

  2. Oxygen isotopic exchange occurring during dry thermal oxidation of 6H SiC

    Energy Technology Data Exchange (ETDEWEB)

    Vickridge, I.C. E-mail: vickridge@gps.jussieu.fr; Tromson, D.; Trimaille, I.; Ganem, J.-J.; Szilagyi, E.; Battistig, G

    2002-05-01

    SiC is a large band gap semiconductor, promising for high power and high frequency devices. The thermal oxide is SiO{sub 2} however the growth rates of thermal oxide on SiC are substantially slower than on Si, and different along the polar directions (<0 0 0 1-bar> and <0 0 0 1> in the hexagonal polytypes). Thorough understanding of the oxide growth mechanisms may give us new insights into the nature of the SiO{sub 2}/SiC interface, crucial for device applications. We have determined growth kinetics for ultra-dry thermal oxidation of 6H SiC at 1100 deg. C for pressures from 3 to 200 mbar. At 3 mbar, the lowest pressure studied, the oxide growth rates along the two polar directions are virtually the same. At higher pressures growth is faster on the carbon-terminated (0 0 0 1-bar) face. After consecutive oxidations at 1100 deg. C and 100 mbar in {sup 18}O{sub 2} and {sup 16}O{sub 2} gases, {sup 18}O depth profiles show significant isotopic exchange and oxygen movement within the oxide during oxidation.

  3. Production and chemical isolation procedure of positron-emitting isotopes of arsenic for environmental and medical applications

    Science.gov (United States)

    Ellison, P. A.; Barnhart, T. E.; Engle, J. W.; Nickles, R. J.; DeJesus, O. T.

    2012-12-01

    The positron-emitting isotopes of arsenic have unique potential for imaging research in medical and environmental applications. The production and purification of radioarsenic from proton-irradiated natural GeO2 targets is reported. The separation procedure utilizes precipitation and anion exchange separation steps. Two anion exchange procedures were investigated. An overall arsenic decay-corrected separation yield of 80% was obtained.

  4. Predicting trace metal solubility and fractionation in Urban soils from isotopic exchangeability

    International Nuclear Information System (INIS)

    Mao, L.C.; Young, S.D.; Tye, A.M.; Bailey, E.H.

    2017-01-01

    Metal-salt amended soils (MA, n = 23), and historically-contaminated urban soils from two English cities (Urban, n = 50), were investigated to assess the effects of soil properties and contaminant source on metal lability and solubility. A stable isotope dilution method, with and without a resin purification step, was used to measure the lability of Cd, Cu, Ni, Pb and Zn. For all five metals in MA soils, lability (%E-values) could be reasonably well predicted from soil pH value with a simple logistic equation. However, there was evidence of continuing time-dependent fixation of Cd and Zn in the MA soils, following more than a decade of storage under air-dried conditions, mainly in high pH soils. All five metals in MA soils remained much more labile than in Urban soils, strongly indicating an effect of contaminant source on metal lability in the latter. Metal solubility was predicted for both sets of soil by the geochemical speciation model WHAM-VII, using E-value as an input variable. For soils with low metal solution concentrations, over-estimation of Cd, Ni and Zn solubility was associated with binding to the Fe oxide fraction while accurate prediction of Cu solubility was dependent on humic acid content. Lead solubility was most poorly described, especially in the Urban soils. Generally, slightly poorer estimation of metal solubility was observed in Urban soils, possibly due to a greater incidence of high pH values. The use of isotopically exchangeable metal to predict solubility is appropriate both for historically contaminated soils and where amendment with soluble forms of metal is used, as in toxicological trials. However, the major limitation to predicting solubility may lie with the accuracy of model input variables such as humic acid and Fe oxide contents where there is often a reliance on relatively crude analytical estimations of these variables. Trace metal reactivity in urban soils depends on both soil properties and the original source material

  5. Deactivation of hydrophobic catalysts for a hydrogen isotope exchange: Application of the time-on-stream theory

    International Nuclear Information System (INIS)

    Choi, Heui-Joo; Lee, Han Soo; Ahn, Do-Hee; Kim, Jeong-Guk; Kim, Wi-soo; Sohn, SoonHwan

    2005-01-01

    A recycle reactor was built for the purpose of characterizing newly developed hydrophobic catalysts for a hydrogen isotope exchange. The catalytic rate constants of two types of hydrophobic catalysts were measured at a 100% relative humidity. The catalytic rate constants were measured at 60 deg C for 28 days and both the catalysts showed very high initial catalytic rate constants. The measured deactivation profile showed that the catalytic rate constants of both the catalysts were almost identical for 28 days. The deactivation of the catalysts was modelled based upon the time-on-stream theory. The deactivation profiles of the catalysts were estimated by using the model for a period of three years. The results showed that both the catalysts had a good exchange capacity for hydrogen isotopes and they could be applicable to a tritium removal facility that will be built at the Wolsong nuclear power plants in the near future

  6. Dependence of chlorine isotope separation in ion exchange chromatography on the nature and concentration of the eluent

    International Nuclear Information System (INIS)

    Heumann, K.G.; Baier, K.

    1980-01-01

    In a heterogeneous electrolyte system of a strongly basic anion exchanger and solutions of NaBF 4 or NaClO 4 we established the influence of the nature and concentration of the eluent in chromatographic experiments on chlorine isotope separation. Results show that when the elctrolyte concentration is increased the degree of isotope separation decreases. With NaBF 4 the separation factor is greater than with NaClO 4 under conditions which are otherwise the same. For electrolyte solutions containing ClO 4 -, NO 3 - and BF 4 - there is a linear relation between the separation factor of the chlorine isotopes and the logarithm of the heat of anion hydration of the elution electrolyte. (orig.)

  7. Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

    Directory of Open Access Journals (Sweden)

    Alberta Silvestri

    2017-01-01

    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  8. Boninite petrogenesis: Chemical and Nd-Sr isotopic constraints

    International Nuclear Information System (INIS)

    Cameron, W.E.; Walker, D.A.; McCulloch, M.T.

    1983-01-01

    Major and trace element abundances and Nd and Sr isotopic compositions have been determined for boninites from the Bonin Islands, Cape Vogel (Papua New Guinea) and New Caledonia and for similar lavas from Cyprus and New Zealand. SiO 2 , CaO, incompatible element abundances and epsilonsub(Nd) values are shown to vary systematically with the degree of light rare earth element (LREE) enrichment. Lasub(N)/Ybsub(N) varies from 5.4 to 0.3. The range of epsilonsub(Nd) values is from +8.0 to +1.9. These features are interpreted in terms of mixing of two components: a LREE-depleted magma, derived by partial melting of an already-depleted peridotite source, and a hydrous. LREE-enriched fluid. If La for the fluid is taken as 100 x chondrites, REE abundances observed in boninites can be reproduced by 1-15% addition of the LREE-enriched component. Using a LREE-depleted component inferred from the Cyprus samples (Lasub(N)/Ybsub(N)=0.10), the LREE-enriched component for Tertiary boninites has been calculated to have a Lasub(N)/Ybsub(N) approx.= 20. The LREE-depleted component contains most of the CaO, Sc, HREE and TiO 2 , and has an epsilonsub(Nd) of >= +8. The enriched component contains H 2 O and most of the Zr, Nb and LREE, and has an epsilonsub(Nd) ranging from +6 to at least -5. Origins for the LREE-enriched fluid include derivation from mantle sources similar to those proposed for ocean islands or, more likely, from subducted oceanic or continental crust in island-arc settings. (orig.)

  9. Isotopic and chemical studies of geothermal waters of Northern Areas in Pakistan

    Energy Technology Data Exchange (ETDEWEB)

    Dildar Hussain, S; Ahmad, M; Akram, W; Sajjad, M I [Pakistan Inst. of Nuclear Science and Technology, Islamabad (Pakistan); Gonfiantini, R [International Atomic Energy Agency, Vienna (Austria). Isotope Hydrology Section; Tasneem, M A

    1995-02-01

    Northern Areas is one of the major thermal fields of Pakistan with more than two dozen known hot springs having discharge temperature ranging from 35 deg. C to 94 deg. C. Isotopic and chemical techniques applied to study the geothermal fields show that thermal waters are of meteoric origin and can be classified as Na-HCO{sub 3}, Na-SO{sub 4} and mixed type on the basis of their chemical contents. At some places cooling of thermal waters seems to be due to steam separation whereas mixing with fresh cold water is prominent at the remaining sites. The temperatures estimated by isotopic and chemical geothermometers for the two major fields i.e. Tatta Pani and Murtazabad are 83-257 deg. C and 65-296 deg. C respectively. (author). 24 refs, 11 figs, 3 tabs.

  10. The Need for Systematic Naming Software Tools for Exchange of Chemical Information

    Directory of Open Access Journals (Sweden)

    Andrey Yerin

    1999-09-01

    Full Text Available The availability of systematic names can enable the simple textual exchange of chemical structure information. The exchange of molecular structures in graphical format or connection tables has become well established in the field of cheminformatics and many structure drawing tools exist to enable this exchange. However, even with the availability of systematic naming rules, software tools to allow the generation of names from structures, and hopefully the reversal of these systematic names back to the original chemical structure, have been sorely lacking in capability and quality. Here we review the need for systematic naming as well as some of the tools and approaches being taken today in this area.

  11. Constraints on continental crustal mass loss via chemical weathering using lithium and its isotopes

    Science.gov (United States)

    Rudnick, R. L.; Liu, X. M.

    2012-04-01

    The continental crust has an "intermediate" bulk composition that is distinct from primary melts of peridotitic mantle (basalt or picrite). This mismatch between the "building blocks" and the "edifice" that is the continental crust points to the operation of processes that preferentially remove mafic to ultramafic material from the continents. Such processes include lower crustal recycling (via density foundering or lower crustal subduction - e.g., relamination, Hacker et al., 2011, EPSL), generation of evolved melts via slab melting, and/or chemical weathering. Stable isotope systems point to the influence of chemical weathering on the bulk crust composition: the oxygen isotope composition of the bulk crust is distinctly heavier than that of primary, mantle-derived melts (Simon and Lecuyer, 2005, G-cubed) and the Li isotopic composition of the bulk crust is distinctly lighter than that of mantle-derive melts (Teng et al., 2004, GCA; 2008, Chem. Geol.). Both signatures mark the imprint of chemical weathering on the bulk crust composition. Here, we use a simple mass balance model for lithium inputs and outputs from the continental crust to quantify the mass lost due to chemical weathering. We find that a minimum of 15%, a maximum of 60%, and a best estimate of ~40% of the original juvenile rock mass may have been lost via chemical weathering. The accumulated percentage of mass loss due to chemical weathering leads to an average global chemical weathering rate (CWR) of ~ 1×10^10 to 2×10^10 t/yr since 3.5 Ga, which is about an order of magnitude higher than the minimum estimates based on modern rivers (Gaillardet et al., 1999, Chem. Geol.). While we cannot constrain the exact portion of crustal mass loss via chemical weathering, given the uncertainties of the calculation, we can demonstrate that the weathering flux is non-zero. Therefore, chemical weathering must play a role in the evolution of the composition and mass of the continental crust.

  12. Homogeneous activation of molecular hydrogen: on the development of effective catalysts for isotopic exchange in protolytic media

    International Nuclear Information System (INIS)

    Sakharovskij, Yu.A.

    1987-01-01

    Comparison of different catalytic systems for hydrogen isotopic exchange with protolytic solvent based on activation enthalpy and entropy values is carried out. Particular attention is paid to the effect of ligand environment of complex forming metallic central ion and solvent composition on free activation energy and stability of catalytic system. A conclusion is drawn on impossibility of absolutely stable and high-temperature catalyst in an isolated system

  13. Quantitation of chemical exchange rates using pulsed-field-gradient diffusion measurements

    International Nuclear Information System (INIS)

    Andrec, Michael; Prestegard, James H.

    1997-01-01

    A new approach to the quantitation of chemical exchange rates is presented, and its utility is illustrated with application to the exchange of protein amide protons with bulk water. The approach consists of a selective-inversion exchange HMQC experiment in which a short spin echo diffusion filter has been inserted into the exchange period. In this way, the kinetics of exchange are encoded directly in an apparent diffusion coefficient which is a function of the position of the diffusion filter in the pulse sequence. A detailed theoretical analysis of this experiment indicates that, in addition to the measurement of simple exchange rates, the experiment is capable of measuring the effect of mediated exchange, e.g. the transfer of magnetization from bulk water to an amide site mediated by an internal bound water molecule or a labile protein side-chain proton in fast exchange with bulk water. Experimental results for rapid water/amide exchange in acyl carrier protein are shown to be quantitatively consistent with the exchange rates measured using a selective-inversion exchange experiment

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-03-15

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

  16. Chromatographic speciation of Cr(III)-species, inter-species equilibrium isotope fractionation and improved chemical purification strategies for high-precision isotope analysis

    DEFF Research Database (Denmark)

    Larsen, Kirsten Kolbjørn; Wielandt, Daniel Kim Peel; Schiller, Martin

    2016-01-01

    Chromatographic purification of chromium (Cr), which is required for high-precision isotope analysis, is complicated by the presence of multiple Cr-species with different effective charges in the acid digested sample aliquots. The differing ion exchange selectivity and sluggish reaction rates of ...

  17. Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity.

    Science.gov (United States)

    Carter, James F; Yates, Hans S A; Tinggi, Ujang

    2015-01-28

    This paper presents a data set derived from the analysis of bottled and canned ciders that may be used for comparison with suspected counterfeit or substitute products. Isotopic analysis of the solid residues from ciders (predominantly sugar) provided a means to determine the addition of C4 plant sugars. The added sugars were found to comprise cane sugar, high-fructose corn syrup, glucose, or combinations. The majority of ciders from Australia and New Zealand were found to contain significant amounts of added sugar, which provided a limited means to distinguish these ciders from European ciders. The hydrogen and oxygen isotopic compositions of the whole ciders (predominantly water) were shown to be controlled by two factors, the water available to the parent plant and evaporation. Analysis of data derived from both isotopic and chemical analysis of ciders provided a means to discriminate between regions and countries of manufacture.

  18. Current status of uranium enrichment by way of chemical exchange reactions

    International Nuclear Information System (INIS)

    El Basyouny, A.; Bechthold, H.C.; Knoechel, A.; Vollmer, H.J.

    1985-04-01

    For this report, conference proceedings, patents and other types of literature have been collected to present an account of the current status of uranium enrichment by way of chemical exchange reactions. The report further presents a new concept along with the relevant process strategy developed by the authors. The principal process of the new concept is a chemical exchange process with crown ethers, complexed or free, playing an important part in the reactions. The authors also describe their experiments carried out for establishing suitable chemical systems. (orig./PW) [de

  19. Modeling of the Process of Three-Isotope (H, D, T) Exchange Between Hydrogen Gas and Water Vapour on Pt-SDBC Catalyst over a Wide Range of Deuterium Concentration

    International Nuclear Information System (INIS)

    Fedorchenko, O.A.; Alekseev, I.A.; Tchijov, A.S.; Uborsky, V.V.

    2005-01-01

    The large scale studies of Combined Electrolysis and Catalytic Exchange (CECE) process in Petersburg Nuclear Physics Institute showed a complicated influence of various factors on the process caused by the presence of two simultaneous isotope exchange sub processes: counter-current phase exchange (between liquid water and water vapour) and co-current catalytic exchange (between hydrogen gas and water vapour). A laboratory scale set-up of glass made apparatuses was established in such a way that it allows us to study phase and catalytic exchange apart. A computer model of the set-up has been developed.The catalytic isotope exchange model formulation is presented. A collection of reversible chemical reactions is accompanied by diffusion of the gaseous reactants and reaction products in the pores of catalyst carrier. This has some interesting features that are demonstrated. Thus it was noted that the flow rates ratio (gas to vapour - λ = G/V) as well as the concentrations of reactants exert influence on the process efficiency

  20. Isotopic and Chemical Evidence for Primitive Aqueous Alteration in the Tagish Lake Meteorite

    Science.gov (United States)

    Sakuma, Keisuke; Hidaka, Hiroshi; Yoneda, Shigekazu

    2018-01-01

    Aqueous alteration is one of the primitive activities that occurred on meteorite parent bodies in the early solar system. The Tagish Lake meteorite is known to show an intense parent body aqueous alteration signature. In this study, quantitative analyses of the alkaline elements and isotopic analyses of Sr and Ba from acid leachates of TL (C2-ungrouped) were performed to investigate effects of aqueous alteration. The main purpose of this study is to search for isotopic evidence of extinct 135Cs from the Ba isotopic analyses in the chemical separates from the Tagish Lake meteorite. Barium isotopic data from the leachates show variable 135Ba isotopic anomalies (ε = ‑2.6 ∼ +3.6) which correlatewith 137Ba and 138Ba suggesting a heterogeneous distribution of s- and r-rich nucleosynthetic components in the early solar system. The 87Rb–87Sr and 135Cs–135Ba decay systems on TL in this study do not provide any chronological information. The disturbance of the TL chronometers is likely a reflection of the selective dissolution of Cs and Rb given the relatively higher mobility of Cs and Rb compared to Ba and Sr, respectively, during fluid mineral interactions.

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

    Science.gov (United States)

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

    2011-12-01

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

  2. Chemical and isotopic properties of groundwater along the coastal plain of the aqaba gulf, (EG)

    International Nuclear Information System (INIS)

    Awad, M.A.A

    1999-01-01

    Isotopic and hydrochemical studies were undertaken along the coastal plain of aqaba gulf in taba, dahab and sharm El-Sheikh to ascertain the role of precipitation (via floods), local water and sea water intrusion as replenishment sources for available groundwater resources in these areas. From the isotopic point of view, it can be concluded that groundwater in nuweiba wells appears to have been recharged from continental and mediterranean participation, while in dahab wells and sharm El-Sheikh Nubian well, recent precipitation via monsoonal air masses which comes from indian ocean plays a considerable role in recharging of these wells. In Taba wells, seepage of partly evaporated flood water represents the main source of their recharge. The fractured nature of the studied area has an effect on the occurrence of groundwater. The variation in chemical water type is due to leaching of terrestrial salts and impact of marine faces (i.e. evaporites and sea spray). Sea water intrusion via over pumping and/ or during tide and ebb duration shows an affect-to some extent-on the chemical composition of some localized wells. Construction of meteorological stations in scattered sites all over sinai is necessary to collect rainwater and floods samples periodically, to study the modification of the isotopic composition of rainwater by processes which occur before groundwater recharge using environmental isotopes

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

    Science.gov (United States)

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

    2008-09-21

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

  4. Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries

    Science.gov (United States)

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

    2018-01-01

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

  5. Chemical Exchange Saturation Transfer (CEST): what is in a name and what isn’t?

    Science.gov (United States)

    van Zijl, Peter C.M.; Yadav, Nirbhay N.

    2011-01-01

    Chemical exchange saturation transfer (CEST) imaging is a relatively new MRI contrast approach in which exogenous or endogenous compounds containing either exchangeable protons or exchangeable molecules are selectively saturated and, after transfer of this saturation, detected indirectly through the water signal with enhanced sensitivity. The focus of this review is on basic MR principles underlying CEST and similarities to and differences with conventional magnetization transfer contrast (MTC). In CEST MRI, transfer of magnetization is studied in mobile compounds instead of semisolids. Similar to MTC, CEST has contributions of both chemical exchange and dipolar cross-relaxation, but the latter can often be neglected if exchange is fast. Contrary to MTC, CEST imaging requires sufficiently slow exchange on the MR time scale to allow selective irradiation of the protons of interest. As a consequence, magnetic labeling is not limited to radio-frequency saturation but can be expanded with slower frequency-selective approaches such as inversion, gradient dephasing and frequency labeling. The basic theory, design criteria, and experimental issues for exchange transfer imaging are discussed. A new classification for CEST agents based on exchange type is proposed. The potential of this young field is discussed, especially with respect to in vivo application and translation to humans. PMID:21337419

  6. Application of isotopic and chemical methods to the study of hydrological problems in Brazilian northeastern areas

    International Nuclear Information System (INIS)

    Ponte, J.H.

    1979-01-01

    Hydrological studies are reported with samples of ground water from several region of northern - and northeastern Brazil: Marajo Island (State of Para), State of Piaui, Ceara and Rio Grande do Norte. A description is given of the utilization of chemical and isotopic methods, in particular measurements of tritium concentration and 14 C- counting techniques for the determination of the origin and residence time of water. (I.C.R.) [pt

  7. Ion exchange and adsorption in nuclear chemical engineering

    International Nuclear Information System (INIS)

    Schultz, W.W.; Wheelwright, E.J.; Godbee, H.; Mallory, C.W.; Burney, G.A.; Wallace, R.M.

    1983-01-01

    The nuclear industry involves a number of operations. Uranium ore must first be mined and the uranium recovered from the ore, purified, and concentrated. After the uranium has been enriched and fabricated into fuel elements, it is placed in nuclear reactors where it produces energy, fission products, and transmutation products. Finally, if the fuel cycle is completed, the uranium and useful transmutation products are recovered and separated from each other as well as from the fission products. The uranium may be recycled or used elsewhere, while most of the fission products become waste. Ion exchange finds use in nearly every part of the nuclear fuel cycle; these uses are the subject of this paper

  8. The effect of natural weathering on the chemical and isotopic composition of biotites

    International Nuclear Information System (INIS)

    Clauer, N.; Bonnot-Courtois, C.

    1982-01-01

    The effect of progressive natural weathering on the isotopic (Rb-Sr, K-Ar, deltaD, delta 18 O) and chemical (REE, H 2 O + ) compositions of biotite has been studied on a suite of migmatitic biotites from the Chad Republic. During the early stages of weathering the Rb-Sr system is strongly affected, the hydrogen and oxygen isotope compositions change markedly, the minerals are depleted in light REE, the water content increases by a factor of two, and the K-Ar system is relatively little disturbed. During intensive weathering the K-Ar system is more strongly disturbed than the Rb-Sr system. Most of the isotopic and chemical modifications take place under nonequilibrium conditions and occur before newly formed kaolinite and/or smectite can be detected. These observations suggest that (a) 'protominerals' may form within the biotite structure during the initial period of weathering, and (b) only when chemical equilibrium is approached in the weathering profile are new minerals able to form. (author)

  9. Environmental isotopes, chemical composition and groundwater sources in Al-Maghara area, Sinai, Egypt

    International Nuclear Information System (INIS)

    Nada, A.A.; Awad, M.A.; Froehlich, K.; El Behery, M.

    1991-01-01

    Groundwater samples collected from a number of localities, in Al-Maghara area, north central part of Sinai, were subject to various chemical and isotopic analysis. The purpose of the study is to determine whether the groundwaters are recently recharged or not in order to adopt an efficient water management policy. The hydrochemical results indicate that they are mainly of primary marine origin, dilution of this water by meteoric water changes its chemical composition to be mixed water type, which has the major chemical components: KCl, NaCl, Na 2 SO 4 , MgSO 4 , Mg(HCO 3 ) 2 and Ca(HCO 3 ) 2 . The tritium content confirm the meteoric water recharge recently especially for wells with high tritium content. The stable environmental isotopic composition of the groundwater reflects the isotopic composition of precipitation and flooding with some evaporation enrichment prior to infiltration. There is also mixing with palaeowater (water recharge in the past cooler climate periods), by leaking through faulting in the area. (orig.) [de

  10. The thermodynamics of heat- and mass exchange in chemical engineering. Vol. 1. 2. rev. ed.

    International Nuclear Information System (INIS)

    Matz, G.

    1979-01-01

    The second and completely revised edition of the approved textbook 'The thermodynamics of heat- and mass exchange in chemical engineering' is devoted to students of technical and natural science disciplines as well as to practicians and scientists, which are confronted with thermodynamical problems of chemical engineering. Starting from the different phases and properties of matter, the first and the second law of thermodynamics are discussed together with many applications. After an introduction of the equilibrium state, the general principle of similarity for heat- and mass exchange is discussed, considering in particular the heat- and mass exchange in the counter flow between two phases. In a final chapter, the heat- and mass exchange between the vapor- and liquid phase is discussed, with special emphasis on problems as evaporation and drying. (orig./HK) [de

  11. Phosphorus Use Efficiency for Symbiotic Fixation Nitrogen in Voandzou (Vigna Subterranea) Using Isotopic Exchange Method in Rhizotron

    Energy Technology Data Exchange (ETDEWEB)

    Andriamananjara, A.; Rabeharisoa, L. [Laboratoire des Radio-isotopes, Universite d' Antananarivo, Antananarivo (Madagascar); Masse, D. [Institut de Recherche pour le Developpement, UMR Eco and Sols, Montpellier, (France); Amenc, L.; Pernot, C.; Drevon, J. J. [Institut National de la Recherche Agronomique, UMR Eco and Sols, Montpellier, (France); Morel, C. [INRA-ENITA, Villenave d' Ornon (France)

    2013-11-15

    Low bioavailability of nitrogen and phosphorus is one of the main constraints in the acid soils with high P-fixing capacity. Plants adapt to low nutrient availability through various biological and physico-chemical mechanisms. Since genetic variation of N{sub 2} fixation exists in numerous legume species, optimization of symbiotic nitrogen fixation (SNF) under P deficiency could be a way to the replenishment of soil fertility in tropical soils. As the genetic potential of crops like Vigna subterranea (Bambara groundnut or voandzou) is little studied, although its agronomic potential is interesting for the farmers of Africa, a physiological study through legume screening for N{sub 2} fixation was performed with 54 cultivars from Madagascar, Niger and Mali, inoculated with the reference strain of Bradyrhizobium sp. Vigna CB756 in hydroponic culture under P deficiency and sufficiency (30 and 75 {mu}mol KH{sub 2}PO{sub 4} plant{sup -1} week {sup -1}, respectively), corresponding respectively to 28 and 70 mg P kg{sup -1} of soil. Large variability of nodulation and plant biomass was found among cultivars. These two parameters were generally correlated and the slope of the plant biomass regression as a function of nodulation was considered as an indicator of the efficiency in use of the rhizobial symbiosis. For the two cultivars most tolerant to P deficiency, V1 and V4 from Madagascar, the increase in use efficiency of the rhizobial symbiosis under P deficiency was linked with an increase in nodulated root O{sub 2} consumption linked to N{sub 2} fixation, and in phytase gene expression observed on the nodule sections by in situ RT- PCR. As the complexity of P compartments makes it difficult to assess the P bioavailability in the plant rhizosphere, an isotopic {sup 32}P exchange method was carried out in a rhizotron in order to assess the direct effect of the roots on P mobilization in rhizosphere soil, comparing V1 and V4 with 28 or 70 mg P kg{sup -1} of soil. Throughout

  12. Negative chemical ionization GC/MS determination of nitrite and nitrate in seawater using exact matching double spike isotope dilution and derivatization with triethyloxonium tetrafluoroborate.

    Science.gov (United States)

    Pagliano, Enea; Meija, Juris; Sturgeon, Ralph E; Mester, Zoltan; D'Ulivo, Alessandro

    2012-03-06

    The alkylation of nitrite and nitrate by triethyloxonium tetrafluoroborate allows determination of their ethyl esters by headspace gas chromatography/mass spectrometry (GC/MS). In the present study, significant improvement in analytical performance is achieved using negative chemical ionization providing detection limits of 150 ng/L for NO(2)(-) and 600 ng/L for NO(3)(-), an order of magnitude better than those achieved using electron impact ionization. The derivatization procedure was optimized and alkaline conditions adopted to minimize conversion of nitrite to nitrate (determined to be 0.07% at 100 mg/L NO(2)(-)) and to avoid the exchange of oxygen between the analytes and the solvent (water). Quantitation entails use of isotopically enriched standards (N(18)O(2)(-) and (15)NO(3)(-)), which also permits monitoring of potential conversion from nitrite to nitrate during the analysis (double spike isotope dilution).

  13. Process for the exchange of hydrogen isotopes between streams of liquid water and gaseous halohydrocarbon and an apparatus therefor

    International Nuclear Information System (INIS)

    Symons, E. A.; Clermont, M. J.; Paterson, L. M.; Rolston, J. H.

    1985-01-01

    Hydrogen isotope (e.g. deuterium) exchange from liquid water to a gaseous halohydrocarbon (e.g. fluoroform, CF 3 H-CF 3 D) is obtained at an operating temperature in the range 0 0 to 100 0 C. using a catalytically active mass comprising a porous anion exchange resin in the hydroxide ion form and enriched gaseous halohydrocarbon stream is decomposed by isotope selective photo-decomposition into a first, gaseous stream enriched in the hydrogen isotope, which is removed as a product, and a depleted gaseous halohydrocarbon stream, which is recirculated for enrichment again. The catalytically active mass may, for example, be in the form of resin particles suspended in a fluidized bed or packed as resin particles between sheets wound into a roll. One of the sheets may be corrugated and have open interstices to form a packing in a column which permits countercurrent gas and liquid flow past the resin. Preferably the wound sheets are hydrophilic to retard flooding by the liquid water. The liquid water stream may contain dimethyl sulfoxide (DMSO) added as co-solvent

  14. Features of adsorbed chemical elements and their isotopes distribution in iodine air filters AU-1500 of nuclear power plant

    International Nuclear Information System (INIS)

    Neklyudov, I.M.; Dovbnya, A.N.; Dikiy, N.P.; Ledenyov, O.P.; Lyashko, Yu.V.

    2013-01-01

    The main aim of research is to investigate the physical features of spatial distribution of the adsorbed chemical elements and their isotopes in the granular filtering medium in the iodine air filters of the type of AU-1500 in the forced-exhaust ventilation at the nuclear power plant. The ?-activation analysis method is applied to accurately characterize the distribution of the adsorbed radioactive chemical elements and their isotopes in the granular filtering medium in the AU-1500 iodine air filter after its long term operation at the nuclear power plant. The typical spectrum of the detected chemical elements and their isotopes in the AU-1500 iodine air filter, which was exposed by the irradiation of bremsstrahlung gamma-quantum producing by the accelerating electrons in the tantalum target, are obtained. The spatial distributions of the detected chemical element 127 I and some other chemical elements and their isotopes in the layer of absorber, which was made of the cylindrical coal granules of the type of SKT-3, in the AU-1500 iodine air filter are also researched. The possible influences by the standing wave of air pressure in the iodine air filter on the spatial distribution of the chemical elements and their isotopes in the iodine air filter are discussed. The comprehensive analysis of obtained research results on the distribution of the adsorbed chemical elements and their isotopes in the absorber of iodine air filter is performed.

  15. Anglo-Saxon animal husbandry techniques revealed though isotope and chemical variations in cattle teeth

    International Nuclear Information System (INIS)

    Evans, J.A.; Tatham, S.; Chenery, S.R.; Chenery, C.A.

    2007-01-01

    The Sr concentration and isotope composition of tooth enamel from domesticated animals from two neighbouring Anglo-Saxon settlements, at Empingham (6-7th century) and Ketton (10-12th century) in Rutland, central England, are compared both with each other, and with associated human populations. Data from the Empingham II site form discrete fields in Sr concentration and isotope composition space for cattle, pig and sheep with a partial overlap of the human and pig fields. By contrast there is significant overlap in all the animal and human data fields from the Ketton site. The differences in data distribution between the two sites are attributed to animal husbandry techniques, as the surface geology of the two areas is very similar, implying geological factors are an unlikely cause of the difference. It is suggested that the grazing and feeding patterns of animals at the Empingham II site were controlled and restricted, whereas at the Ketton site the animals grazed and foraged freely over a common area. Strontium isotope variation within cattle molars from the two settlements show marked differences that reflect the nature of their feeding and rearing. The enamel from a cattle molar from the Empingham II site has a well-defined, systematic variation of Sr isotope composition with Sr concentration, whereas no such patterns exist in a comparable cattle molar from Ketton. Chemical and O isotope variations in the cattle tooth from Empingham II show sympathetic variation of Sr and Ba concentrations with Sr isotope composition from cusp to cervix. The cusp has higher Sr and Ba concentrations log (Sr/Ca) ratio of -3.1 and 87 Sr/ 86 Sr ratio of 0.71151 where as the cervical region of the enamel has log (Sr/Ca) = -3.3 and 87 Sr/ 86 Sr = 0.71061

  16. Anglo-Saxon animal husbandry techniques revealed though isotope and chemical variations in cattle teeth

    Energy Technology Data Exchange (ETDEWEB)

    Evans, J.A. [NERC Isotope Geosciences Laboratory, BGS, Keyworth, Nottingham NG12 5GG (United Kingdom)], E-mail: je@nigl.nerc.ac.uk; Tatham, S. [School of Archaeology and Ancient History, University of Leicester, Leicester LE1 7RH (United Kingdom); Chenery, S.R. [British Geological Survey, Keyworth, Nottingham NG12 5GG (United Kingdom); Chenery, C.A. [NERC Isotope Geosciences Laboratory, BGS, Keyworth, Nottingham NG12 5GG (United Kingdom)

    2007-09-15

    The Sr concentration and isotope composition of tooth enamel from domesticated animals from two neighbouring Anglo-Saxon settlements, at Empingham (6-7th century) and Ketton (10-12th century) in Rutland, central England, are compared both with each other, and with associated human populations. Data from the Empingham II site form discrete fields in Sr concentration and isotope composition space for cattle, pig and sheep with a partial overlap of the human and pig fields. By contrast there is significant overlap in all the animal and human data fields from the Ketton site. The differences in data distribution between the two sites are attributed to animal husbandry techniques, as the surface geology of the two areas is very similar, implying geological factors are an unlikely cause of the difference. It is suggested that the grazing and feeding patterns of animals at the Empingham II site were controlled and restricted, whereas at the Ketton site the animals grazed and foraged freely over a common area. Strontium isotope variation within cattle molars from the two settlements show marked differences that reflect the nature of their feeding and rearing. The enamel from a cattle molar from the Empingham II site has a well-defined, systematic variation of Sr isotope composition with Sr concentration, whereas no such patterns exist in a comparable cattle molar from Ketton. Chemical and O isotope variations in the cattle tooth from Empingham II show sympathetic variation of Sr and Ba concentrations with Sr isotope composition from cusp to cervix. The cusp has higher Sr and Ba concentrations log (Sr/Ca) ratio of -3.1 and {sup 87}Sr/{sup 86}Sr ratio of 0.71151 where as the cervical region of the enamel has log (Sr/Ca) = -3.3 and {sup 87}Sr/{sup 86}Sr = 0.71061.

  17. 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.

  18. Chemical and environmental isotope study of the basaltic aquifer systems of Yarmouk Basin (Syria)

    International Nuclear Information System (INIS)

    Kattan, Z.

    1994-08-01

    The water in the fissured basalt aquifer system, the Upper Jurassic aquifer of the Yarmouk Basin and the atmospheric precipitation have been investigated using chemical and environmental isotope techniques. The groundwaters flowing through the different aquifers are differentiated by their chemical ratios and their isotopic compositions. The evolution of chemical facies of groundwater from the recharge area towards the basin outlet is characterized by increasing of sodium and magnesium contents as a result of silicate leaching. The stable isotope compositions of precipitation and mountainous spring waters match the Mediterranean Meteoric Water Line, while the groundwaters from the central zone and from the major springs of the Yarmouk Basin are mixtures of freshwater, which is isotopically depleted and salty groundwater of Laja plateau area. The interpretations of tritium and radiocarbon ( 14 C) data indicate that the recharge zones of the groundwater in the Yarmouk Basin occur on the high-land of more than 1000 m of altitude. The residence time of the mountainous springs is short (of about 40 years or less). However, water ages corrected by Vogel's concept and Gonfiantini's Model show, in general, a range from 1000 to 11000 years for the central zone groundwater. The groundwater moves from the Mt. Hermon and Mt. Arab towards the central zone and from the north-east (i.e. the Laja plateau) towards south-west (i.e. the major springs). The radiometric flow velocities range from 20 to 60 m/year within the central zone, while the flow velocities from both sides of Mt. Hermon and Mt. Arab are lower (1-7 m/year). (author). 43 refs., 37 figs., 6 tabs

  19. Soil solution phosphorus turnover: derivation, interpretation, and insights from a global compilation of isotope exchange kinetic studies

    Science.gov (United States)

    Helfenstein, Julian; Jegminat, Jannes; McLaren, Timothy I.; Frossard, Emmanuel

    2018-01-01

    The exchange rate of inorganic phosphorus (P) between the soil solution and solid phase, also known as soil solution P turnover, is essential for describing the kinetics of bioavailable P. While soil solution P turnover (Km) can be determined by tracing radioisotopes in a soil-solution system, few studies have done so. We believe that this is due to a lack of understanding on how to derive Km from isotopic exchange kinetic (IEK) experiments, a common form of radioisotope dilution study. Here, we provide a derivation of calculating Km using parameters obtained from IEK experiments. We then calculated Km for 217 soils from published IEK experiments in terrestrial ecosystems, and also that of 18 long-term P fertilizer field experiments. Analysis of the global compilation data set revealed a negative relationship between concentrations of soil solution P and Km. Furthermore, Km buffered isotopically exchangeable P in soils with low concentrations of soil solution P. This finding was supported by an analysis of long-term P fertilizer field experiments, which revealed a negative relationship between Km and phosphate-buffering capacity. Our study highlights the importance of calculating Km for understanding the kinetics of P between the soil solid and solution phases where it is bioavailable. We argue that our derivation can also be used to calculate soil solution turnover of other environmentally relevant and strongly sorbing elements that can be traced with radioisotopes, such as zinc, cadmium, nickel, arsenic, and uranium.

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

    Science.gov (United States)

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

    2018-04-19

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

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  2. Quantification of iopamidol multi-site chemical exchange properties for ratiometric chemical exchange saturation transfer (CEST) imaging of pH

    International Nuclear Information System (INIS)

    Sun, Phillip Zhe; Longo, Dario Livio; Hu, Wei; Xiao, Gang; Wu, Renhua

    2014-01-01

    pH-sensitive chemical exchange saturation transfer (CEST) MRI holds great promise for in vivo applications. However, the CEST effect depends on not only exchange rate and hence pH, but also on the contrast agent concentration, which must be determined independently for pH quantification. Ratiometric CEST MRI normalizes the concentration effect by comparing CEST measurements of multiple labile protons to simplify pH determination. Iopamidol, a commonly used x-ray contrast agent, has been explored as a ratiometric CEST agent for imaging pH. However, iopamidol CEST properties have not been solved, determination of which is important for optimization and quantification of iopamidol pH imaging. Our study numerically solved iopamidol multi-site pH-dependent chemical exchange properties. We found that iopamidol CEST MRI is suitable for measuring pH between 6 and 7.5 despite that T 1 and T 2 measurements varied substantially with pH and concentration. The pH MRI precision decreased with pH and concentration. The standard deviation of pH determined from MRI was 0.2 and 0.4 pH unit for 40 and 20 mM iopamidol solution of pH 6, and it improved to be less than 0.1 unit for pH above 7. Moreover, we determined base-catalyzed chemical exchange for 2-hydrooxypropanamido (k sw = 1.2*10 pH−4.1 ) and amide (k sw = 1.2*10 pH−4.6 ) protons that are statistically different from each other (P < 0.01, ANCOVA), understanding of which should help guide in vivo translation of iopamidol pH imaging. (paper)

  3. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    Energy Technology Data Exchange (ETDEWEB)

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N. [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany); Glugla, M.; Shu, W.; Willms, S. [ITER Organization, Saint-Paul-lez-Durance (France)

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  4. Isotope exchange kinetic of phosphorus in soils from Pernambuco State -Brazil; Cinetica de diluicao isotopica de fosforo em solos de Pernambuco

    Energy Technology Data Exchange (ETDEWEB)

    Figueiredo, F J.B. de

    1989-12-01

    The applicability of isotopic exchange kinetics of {sup 32} p to characterize phosphorus available to plants and to diagnose the reactivity of soil-fertilizer-P in six soils from Pernambuco is described. This methodology was compared with anion exchange resin, isotopic exchange equilibrium methods (E-value and L-value) and P absorption by plants. The first greenhouse experiment had the following treatments: (1) with P and, (2) with addition of 43.7 mg P/Kg of soil, incubated for O, 42 and 84 days before seeding. The kinetic of isotopic exchange (KIE), resin-P and E-value were determined before seeding and after harvesting pearl millet grown for 42 days. Results indicated that the KIE parameters rated the soils more efficiently, in terms of available P and soil-fertilizer-P reactivity, than resin-P, E-value and L-value. (author). 38 refs, 2 figs, 18 tabs.

  5. A study on the deactivation and stability of hydrophobic catalyst for hydrogen isotope exchange

    International Nuclear Information System (INIS)

    Sohn, Soon Hwan

    2006-02-01

    The hydrophobic catalyst has been prepared by deposition of platinum on porous styrene divinylbenzene copolymers(Pt/SDBC) and at the same time a separated type catalytic reactor has been developed for the Wolsong tritium removal facility(WTRF). Several tests carried out to obtain the experimental performance data of the Pt/SDBC with a recycle reactor system. The long-term stability was also measured with the Pt/SDBC catalyst immersed in water for a long time. The long-term deactivations of the Pt/SDBC catalyst were evaluated quantitatively by mathematical models. The simple mathematical models were presented to evaluate the uniform poisoning and shell progressive poisoning to be occurred simultaneously during the hydrogen isotope exchange between hydrogen gas and liquid water in the Liquid Phase Catalytic Exchange(LPCE) column. The uniform poisoning was well characterized by a time on stream theory and then the deactivation parameters were determined from the experimental performance data. The impurity poisoning was derived by a shell progressive model with two-layer mass transfer. The water vapor condensation was a main cause of the reversible uniform poisoning for the Pt/SDBC catalyst. The values of the decay rate constant (K d ) and order of the decay reaction(m) were of 2 and 4, respectively, based on the experimental data. It indicated that the decay might be attributable to pore mouth poisoning. From the long-term stability of the catalyst immersed in water, there was no intrinsic decay of catalyst activity due to water logging to the catalyst. The activity decreased by only 7% over 18 months, which was equivalent to a catalyst half-life longer than 15 years. On the basis of the above deactivation parameters, the values for k c /k co with Thiele modulus=20 after 3 years and 10 years of operation were expected about 19% and 15% of the initial activity, respectively, while the values for k c /k co with Thiele modulus=100 were of about 22% and 18%, respectively

  6. On Neglecting Chemical Exchange Effects When Correcting in Vivo 31P MRS Data for Partial Saturation

    Science.gov (United States)

    Ouwerkerk, Ronald; Bottomley, Paul A.

    2001-02-01

    Signal acquisition in most MRS experiments requires a correction for partial saturation that is commonly based on a single exponential model for T1 that ignores effects of chemical exchange. We evaluated the errors in 31P MRS measurements introduced by this approximation in two-, three-, and four-site chemical exchange models under a range of flip-angles and pulse sequence repetition times (TR) that provide near-optimum signal-to-noise ratio (SNR). In two-site exchange, such as the creatine-kinase reaction involving phosphocreatine (PCr) and γ-ATP in human skeletal and cardiac muscle, errors in saturation factors were determined for the progressive saturation method and the dual-angle method of measuring T1. The analysis shows that these errors are negligible for the progressive saturation method if the observed T1 is derived from a three-parameter fit of the data. When T1 is measured with the dual-angle method, errors in saturation factors are less than 5% for all conceivable values of the chemical exchange rate and flip-angles that deliver useful SNR per unit time over the range T1/5 ≤ TR ≤ 2T1. Errors are also less than 5% for three- and four-site exchange when TR ≥ T1*/2, the so-called "intrinsic" T1's of the metabolites. The effect of changing metabolite concentrations and chemical exchange rates on observed T1's and saturation corrections was also examined with a three-site chemical exchange model involving ATP, PCr, and inorganic phosphate in skeletal muscle undergoing up to 95% PCr depletion. Although the observed T1's were dependent on metabolite concentrations, errors in saturation corrections for TR = 2 s could be kept within 5% for all exchanging metabolites using a simple interpolation of two dual-angle T1 measurements performed at the start and end of the experiment. Thus, the single-exponential model appears to be reasonably accurate for correcting 31P MRS data for partial saturation in the presence of chemical exchange. Even in systems where

  7. Stability of Zircon and Its Isotopic Ratios in High-Temperature Fluids: Long-Term (4 months Isotope Exchange Experiment at 850°C and 50 MPa

    Directory of Open Access Journals (Sweden)

    Ilya N. Bindeman

    2018-05-01

    Full Text Available Stability of zircon in hydrothermal fluids and vanishingly slow rates of diffusion identify zircon as a reliable recorder of its formation conditions in recent and ancient rocks. Debate, however, persists on how rapidly oxygen and key trace elements (e.g., Li, B, Pb diffuse when zircon is exposed to silicate melt or hot aqueous fluids. Here, we report results of a nano- to micrometer-scale investigation of isotopic exchange using natural zircon from Mesa Falls Tuff (Yellowstone treated with quartz-saturated, isotopically (18O, D, 7Li, and 11B labeled water with a nominal δ18O value of +450%0 over 4 months at 850°C and 50 MPa. Frontside (crystal rim inwards δ18O depth profiling of zircon by magnetic sector SIMS shows initially high but decreasing 18O/16O over a ~130 nm non-Fickian profile, with a decay length comparable to the signal from surficial Au coating deposited onto zircon. In contrast, backside (crystal interior outwards depth profiling on a 2-3 μm thick wafer cut and thinned from treated zircon by focused ion beam (FIB milling lacks any significant increase in 18O/16O during penetration of the original surface layer. Near-surface time-of-flight (TOF-SIMS frontside profiles of uncoated zircon from 4-month and 1-day-long experiments as well as untreated zircons display similar enrichments of 18O over a distance of ~20 nm. All frontside 18O profiles are here interpreted as transient surface signals from nm-thick surface enrichment or contamination unrelated to diffusion. Likewise, frontside depth profiling of H, Li, and B isotopes are similar for long- and short-duration experiments. Additionally, surface U-Pb dating of zircon from the 4-month experiment returned U-Pb ages by depth profiling with ~1 μm penetration that were identical to untreated samples. Frontside and backside depth-profiling thus demonstrate that diffusive 18O enrichment in the presence of H2O is much slower than predicted from experiments in Watson and Cherniak

  8. Changes in Chemical and Isotopic Composition of Groundwater During a Long Term Pumping Test in Brestovica Karst Aquifer

    Energy Technology Data Exchange (ETDEWEB)

    Mezga, K.; Urbanc, J. [Geological Survey of Slovenia, Department of Hydrogeology, Ljubljana (Slovenia)

    2013-07-15

    A pumping test of the Klarici water supply near Brestovica was performed in August 2008, in order to determine the karst groundwater resource capacity. Groundwater was pumped for a month with a total capacity of 470 L/s. During the experiment, sampling for chemical and isotopic composition of groundwater and surface water was carried out. Intensive pumping in dry meteorological conditions caused a lowering of the water table and changes in the chemical and isotopic composition of pumped water. Local meteoric waters are infiltrated into the aquifer at a lower mean altitude; therefore the {delta}{sup 18}O is enriched with the heavy oxygen isotope. The duration of pumping resulted in changes in the isotopic composition of oxygen due to a greater impact of the intergranular Soca River aquifer on the karst aquifer. On the basis of isotope composition it was possible to quantify the impact of the Soca River on the karst aquifer. (author)

  9. Isotope effects on chemical shifts in tautomeric systems with double proton transfer. Citronin

    International Nuclear Information System (INIS)

    Hansen, P.E.; Langgard, M.; Bolvig, S.

    1998-01-01

    Primary and secondary deuterium isotope effects on 1 H and 13 C chemical shifts are measured in citrinin, a tautomeric compound with an unusual doubly intramolecularly hydrogen bonded structure. The isotope effects are to a large extent dominated by equilibrium contributions and deuteration leads to more of the deuterated enol forms rather than the deuterated acid form. 1 H 13 C and 17 O nuclear shieldings are calculated using density functional ab initio methods. A very good correlation between calculated nuclear shieldings and experimental 1 H and 13 C chemical shifts is obtained. The tautomeric equilibrium can be analyzed based on the isotope effects on B-6 and C-8 carbons and shows an increase in the o-quinone form on lowering the temperature. Furthermore, upon deuteration the largest equilibrium shift is found for deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration at OH-8 and the shift in the tautomeric equilibrium upon deuteration is increasing at lower temperature. (author)

  10. Chemical analyses and calculation of isotopic compositions of high-burnup UO{sub 2} fuels and MOX fuels

    Energy Technology Data Exchange (ETDEWEB)

    Matsumura, Tetsuo; Sasahara, Akihiro [Central Research Inst. of Electric Power Industry, Tokyo (Japan)

    2001-08-01

    Chemical analysis activities of isotopic compositions of high-burnup UO{sub 2} fuels and MOX fuels in CRIEPI and calculation evaluation are reviewed briefly. C/E values of ORIGEN2, in which original libraries and JENDL-3.2 libraries are used, and other codes with chemical analysis data are reviewed and evaluated. Isotopic compositions of main U and Pu in fuels can be evaluated within 10% relative errors by suitable libraries and codes. Void ratio is effective parameter for C/E values in BWR fuels. JENDL-3.2 library shows remarkable improvement compared with original libraries in isotopic composition evaluations of FP nuclides. (author)

  11. New Zealand guidelines for the collection of groundwater samples for chemical and isotopic analyses

    International Nuclear Information System (INIS)

    Rosen, M.R.; Cameron, S.G.; Reeves, R.R.; Taylor, C.B.

    1999-01-01

    Chemical and isotopic analyses of groundwater are important tools for differentiating between the natural composition and human-induced contaminants of groundwater. A comprehensive suite of inorganic water chemical analyses is necessary to characterise waters. The geology of New Zealand is diverse, so it is impractical to characterise a ''typical'' groundwater chemical composition. Each aquifer system should be evaluated individually because the major dissolved species contain useful information about the pathways of water through the soil zone into the aquifer. Analyses of major ions such as chloride, nitrate, potassium and sulphate often give indication of septic systems and agricultural contamination. The minor ions, while most are not considered contaminants, are often indicators of human activity. Iron and manganese are good indicators of Eh potential, which is an important control on the mobility of many heavy metals. The inexpensive inorganic chemical analytical suite should be used as a guide to advisability of more expensive contaminant testing. The purpose of this manual is to provide consistent groundwater sampling guidelines for use throughout New Zealand. Sinton's (1998) guide to groundwater sampling techniques provided a sound basis for the accurate collection of groundwater samples. However Sinton did not address sampling materials and techniques for the collection of samples for ultra trace component analysis or the collection of environmental isotope samples. These important aspects of groundwater sampling have been included in this updated manual. (author). 30 refs., 12 figs., 5 tabs., 1 appendix

  12. Data acquisition and quantitative analysis of stable hydrogen isotope in liquid and gas in the liquid phase catalytic exchange process

    International Nuclear Information System (INIS)

    Choi, H. J.; Lee, H. S.; Kim, K. R.; Cheong, H. S.; Ahn, D. H.; Lee, S. H.; Paek, S. W.; Kang, H. S.; Kim, J. G.

    2001-01-01

    A pilot plant for the Liquid Phase Catalytic Exchange process was built and has been operating to test the hydrophobic catalyst developed to remove the tritium generated at the CANDU nuclear power plants. The methods of quantitative analysis of hydrogen stable isotope were compared. Infrared spectroscopy was used for the liquid samples, and gas chromatography with hydrogen carrier gas showed the best result for gas samples. Also, a data acquisition system was developed to record the operation parameters. This record was very useful to investigate the causes of the system trip

  13. Isotopic exchange in a neutron-irradiated mixed-valence compound: Tl3(I) Tl(III)Cl6

    International Nuclear Information System (INIS)

    Fernandez Valverde, S.; Duplatre, G.

    1977-01-01

    The initial distribution of Tl(I) and Tl(III) species, and its change on heating, have been investigated in solid thermal neutron-irradiated Th 4 Cl 6 . An initial ratio of 5/1 for 204 Tl(I)/ 204 Tl(III) is found and this remains constant for integral gamma-doses of 3 to 12 MRad. The variation of the 204 Tl(III) fraction with temperature is found identical to that observed in labelled Tl 4 Cl 6 for which a genuine isotopic exchange has previously been described. It is concluded that the recoil species are rapidly converted, after the recoil processes, into stable ions

  14. Preparation of Pt-SDB hydrophobic catalyst used in H2-H2O isotope exchange reaction

    International Nuclear Information System (INIS)

    Li Junhua; Kang Yi; Ruan Hao; Dou Qincheng; Han Yande; Hu Shilin

    2001-01-01

    The preparation of Pt-SDB hydrophobic catalyst is studied, in which platinum as active metal and polystyrene divinylbenzene (SDB) as the carrier. Hydrogen isotope exchange reaction is carried out with Pt-SDB catalyst in counter-current in the trickle bed. The effect of preparing condition on the activity of catalyst is discussed. The results show that the excellent catalyst is obtained by reduced at the temperature of 200 degree C over 8 hours. Hydrophobic catalyst is high activity and stability as the amount of platinum content is 3%, the platinum can reach the economic use with the content of (1-2)%

  15. Molecular MRI using exogenous enzymatic sensors and endogenous chemical exchange contrast

    OpenAIRE

    Taylor, Alexander John

    2016-01-01

    Molecular magnetic resonance imaging (MRI) methods have the potential to provide detailed information regarding cellular and molecular processes at small scales within the human body. Nuclear signals from chemical samples can be probed using specialised MRI techniques, to highlight molecular contrast from particular enzymes or metabolites. The aim of the work described in this thesis is to investigate both exogenous and endogenous contrast mechanisms using fluorine MRI and chemical exchange s...

  16. Physico-chemical reactions in the underground movement of radioactive isotopes

    International Nuclear Information System (INIS)

    Gailledreau, C.

    The physico-chemical state of the radioelements moving underground can influence considerably their migration velocity. In the case of 90 Sr--held on by monmorillonites, apatites, activated aluminum oxide--the occurrence of electronegative colloids, sorbing selectively 90 Sr results in an immediate break-through of this isotope. This phenomenon has been demonstrated in the case of the calcite phosphate reaction. A high pH is generally favorable to 90 Sr sorption (apatite, aluminum oxide). The occurrence of Ca 2+ ions acts very unfavorably on 90 Sr sorption by minerals specifics of this isotope (apatite, aluminum oxide). The same thing occurs with organic matters 137 Cs sorption, attributed to illitic clays, is little sensitive to the nature of the solution. Ruthenium-106 seems to move underground chiefly as a nitrosylruthenium hydroxide complex. This complex would be weakly sorbed on soil colloids by London--Van der Waals forces

  17. Chemical and Isotopic Study of the Groundwater of Jeffara Plain of Medenine and Tataouine (Southern Tunisia)

    International Nuclear Information System (INIS)

    Trabelsi, R.; Kalled, M; Zouari, K.; Abidi, B.; Yahyaoui, H.

    2007-01-01

    The study area constitutes the major part of the plain of Jeffara, located at the south-east of Tunisia. This plain is characterized by an arid climate with rare and irregular pluviometry. The hydrochemical approach is used to define the chemical characteristics of the water in these aquifer systems. Indeed, the water salinity varies between 0.6g/? and 9g/?, and increases from the Daher mountains in the west to the Mediterranean Sea. The groundwaters are homogeneous and characterized by a Cl-(SO 4 ) and Na-(Ca-Mg) water type. The isotopic approach shows that the carbone-14 activities, measured in groundwater, evolve in the same direction of groundwater flow. These activities suggest a recent recharge area in eastern piedmont of the Dahar mountains, as well as the zone of the Sahel Abebsa and Zeuss-Koutine. The isotopic values confirm, also, the communication between the various major levels through the existing faults and discontinuities in this area

  18. Chemical investigations of isotope separation on line target units for carbon and nitrogen beams

    CERN Document Server

    Franberg, H; Gäggeler, H W; Köster, U

    2006-01-01

    Radioactive ion beams (RIBs) are of significant interest in a number of applications. Isotope separation on line (ISOL) facilities provide RIB with high beam intensities and good beam quality. An atom that is produced within the ISOL target will first diffuse out from the target material. During the effusion towards the transfer line and into the ion source the many contacts with the surrounding surfaces may cause unacceptable delays in the transport and, hence, losses of the shorter-lived isotopes. We performed systematic chemical investigations of adsorption in a temperature and concentration regime relevant for ISOL targets and ion source units, with regard to CO/sub x/ and NOmaterials are potential construction materials for the above-mentioned areas. Off-line and on-line tests have been performed using a gas thermochromatography setup with radioactive tracers. The experiments were performed at the production of tracers for atmospheric chemistry (PROTRAC) facility at the Paul Schener Institute in Villigen...

  19. Environmental isotopes, chemical composition and groundwater recharge in ataqa-north galala region, Egypt

    International Nuclear Information System (INIS)

    Shohaib, R.EL-SH.; Nada, A.; Safie El-Din, A.

    1991-01-01

    Groundwater samples collected from a number of localities in ataqa-north galala region were subjected to various chemical and isotopic analyses. The seasonal fluctuations in hydrochemical composition reveal that the marin Mg Cl 2 type is dominant in the aquifer through-out the year. The Ca Cl 2 water type of marine origin appears in January in wells W 3 and W 7 which lie close to sukhna fault. Recharge to the aquifer is reflected by fluctuation in the water level and fluctuations of the hydrochemical composition of the water. The results of the isotopic content of the water samples indicate that the connate marine water has been subjected to dilution and mixing by the meteoric water invasion since the pliestocene pluvial period (paleowater) and recent meteoric water precipitation. The bulk of the stored water ( about 80%) is paleowater and the recent water (20%) are percolate ones derived from the rain-fall at high latitudes.4 fig. 1 tab

  20. A study of chemical equilibrium of tri-component mixtures of hydrogen isotopes

    International Nuclear Information System (INIS)

    Cristescu, Ioana; Cristescu, I.; Peculea, M.

    1998-01-01

    In this paper we present a model for computing the equilibrium constants for chemical reactions between hydrogen's isotopes as function of temperature. The equilibrium constants were expressed with the aid of Gibbs potential and the partition function of the mixture. We assessed the partition function for hydrogen's isotopes having in view that some nuclei are fermions and other bosons. As results we plotted the values of equilibrium constants as function of temperature. Knowing these values we determined the deuterium distribution on species (for mixture H 2 -HD-D 2 ) as function of total deuterium concentration and the tritium distribution on species (for mixtures D 2 -DT-T 2 and H 2 -HT-T 2 ) as function of total tritium concentration. (authors)

  1. Thermal and chemical stabilities of some synthesized inorganic ion exchange materials

    International Nuclear Information System (INIS)

    EI-Naggar, I.M.; Abou-Mesalam, M.M.; El-Shorbagy, M.M.; Shady, S.A.

    2006-01-01

    Chromium and cerium titanate as inorganic ion exchange materials were synthesized by the reaction of potassium chromate or ammonium eerie nitrate with titanium tetrachloride with molar ratio equal unity. The crystal system of both chromium and cerium titanates were determined and set to be monoclinic and orthorhombic system's, respectively. The chemical composition of both chromium and cerium titanates was determined by X-ray fluorescence technique and based on the data obtained with other different techniques. A molecular formula for chromium and cerium titanates as Cr 2 Ti 12 O 27 . 13H 2 O and Ce 2 Ti 3 O 10 . 7.46H 2 O, respectively, was proposed. Thermal stabilities of both ion exchangers were investigated at different heating temperatures. Also the stability of chromium and cerium titanates for chemical attack was studied in different media. The data obtained showed high thermal and chemical stabilities of chromium and cerium titanate ion exchangers compared with the same group of ion exchange materials. The ion exchange capacities of chromium and cerium titanates at different heating temperature were also investigated

  2. Thermal and chemical stabilities of some synthesized inorganic ion exchange materials

    International Nuclear Information System (INIS)

    El-Naggar, I.M.; Abou-Mesalam, M. M.; El-Shorbagy, M.M.; Shady, S.A.

    2005-01-01

    Chromium and cerium titanate as inorganic ion exchange materials were synthesized by the reaction of potassium chromate or ammonium ceric nitrate with titanium tetrachloride with molar ratio equal unity. The crystal system of both chromium and cerium titanates were determined and set to be monoclinic and orthorhombic systems, respectively. The chemical composition of both chromium and cerium titanates were determined by X-ray fluorescence technique and based on the data obtained with other different techniques. We can proposed molecular formula for chromium and cerium titanates as Cr 2 Ti 1 2O27. 13H 2 O and Ce 2 ThO10. 7.46 H 2 O, respectively. Thermal stability of both ion exchangers was investigated at different heating temperatures. Also the stability of chromium and cerium titanates for chemical attack was studied in different media. The data obtained showed high thermal and chemical stabilities of chromium and cerium titanate ion exchangers compared to the same group of ion exchange materials. The ion exchange capacities of chromium and cerium titanates at different heating temperature were investigated

  3. Characterization of Chemical Exchange Using Relaxation Dispersion of Hyperpolarized Nuclear Spins.

    Science.gov (United States)

    Liu, Mengxiao; Kim, Yaewon; Hilty, Christian

    2017-09-05

    Chemical exchange phenomena are ubiquitous in macromolecules, which undergo conformational change or ligand complexation. NMR relaxation dispersion (RD) spectroscopy based on a Carr-Purcell-Meiboom-Gill pulse sequence is widely applied to identify the exchange and measure the lifetime of intermediate states on the millisecond time scale. Advances in hyperpolarization methods improve the applicability of NMR spectroscopy when rapid acquisitions or low concentrations are required, through an increase in signal strength by several orders of magnitude. Here, we demonstrate the measurement of chemical exchange from a single aliquot of a ligand hyperpolarized by dissolution dynamic nuclear polarization (D-DNP). Transverse relaxation rates are measured simultaneously at different pulsing delays by dual-channel 19 F NMR spectroscopy. This two-point measurement is shown to allow the determination of the exchange term in the relaxation rate expression. For the ligand 4-(trifluoromethyl)benzene-1-carboximidamide binding to the protein trypsin, the exchange term is found to be equal within error limits in neutral and acidic environments from D-DNP NMR spectroscopy, corresponding to a pre-equilibrium of trypsin deprotonation. This finding illustrates the capability for determination of binding mechanisms using D-DNP RD. Taking advantage of hyperpolarization, the ligand concentration in the exchange measurements can reach on the order of tens of μM and protein concentration can be below 1 μM, i.e., conditions typically accessible in drug discovery.

  4. Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time

    Science.gov (United States)

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

    2017-01-01

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

  5. Rapid and quantitative chemical exchange saturation transfer (CEST) imaging with magnetic resonance fingerprinting (MRF).

    Science.gov (United States)

    Cohen, Ouri; Huang, Shuning; McMahon, Michael T; Rosen, Matthew S; Farrar, Christian T

    2018-05-13

    To develop a fast magnetic resonance fingerprinting (MRF) method for quantitative chemical exchange saturation transfer (CEST) imaging. We implemented a CEST-MRF method to quantify the chemical exchange rate and volume fraction of the N α -amine protons of L-arginine (L-Arg) phantoms and the amide and semi-solid exchangeable protons of in vivo rat brain tissue. L-Arg phantoms were made with different concentrations (25-100 mM) and pH (pH 4-6). The MRF acquisition schedule varied the saturation power randomly for 30 iterations (phantom: 0-6 μT; in vivo: 0-4 μT) with a total acquisition time of ≤2 min. The signal trajectories were pattern-matched to a large dictionary of signal trajectories simulated using the Bloch-McConnell equations for different combinations of exchange rate, exchangeable proton volume fraction, and water T 1 and T 2 relaxation times. The chemical exchange rates of the N α -amine protons of L-Arg were significantly (P exchange using saturation power method. Similarly, the L-Arg concentrations determined using MRF were significantly (P exchange rate was well fit (R 2  = 0.9186) by a base catalyzed exchange model. The amide proton exchange rate measured in rat brain cortex (34.8 ± 11.7 Hz) was in good agreement with that measured previously with the water exchange spectroscopy method (28.6 ± 7.4 Hz). The semi-solid proton volume fraction was elevated in white (12.2 ± 1.7%) compared to gray (8.1 ± 1.1%) matter brain regions in agreement with previous magnetization transfer studies. CEST-MRF provides a method for fast, quantitative CEST imaging. © 2018 International Society for Magnetic Resonance in Medicine.

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  7. Volcanic degassing at Somma-Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Caliro, S. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy)]. E-mail: caliro@ov.ingv.it; Chiodini, G. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy); Avino, R. [Osservatorio Vesuviano sezione di Napoli dell' Istituto, Nazionale Geofisica Vulcanologia, Via Diocleziano 328, 80124 Naples (Italy); Cardellini, C. [Dipartimento di Scienze della Terra, Universita di Perugia (Italy); Frondini, F. [Dipartimento di Scienze della Terra, Universita di Perugia (Italy)

    2005-06-15

    A geochemical model is proposed for water evolution at Somma-Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological-volcanological setting of the volcano forces the waters infiltrating at Somma-Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO{sub 2} groundwaters. Reaction path modelling applied to this conceptual model, involving gas-water-rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO{sub 2} transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO{sub 2} emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO{sub 2} diffusely degassed from the crater area.

  8. Volcanic degassing at Somma-Vesuvio (Italy) inferred by chemical and isotopic signatures of groundwater

    International Nuclear Information System (INIS)

    Caliro, S.; Chiodini, G.; Avino, R.; Cardellini, C.; Frondini, F.

    2005-01-01

    A geochemical model is proposed for water evolution at Somma-Vesuvio, based on the chemical and isotopic composition of groundwaters, submarine gas emission and chemical composition of the dissolved gases. The active degassing processes, present in the highest part of the volcano edifice, strongly influence the groundwater evolution. The geological-volcanological setting of the volcano forces the waters infiltrating at Somma-Vesuvio caldera, enriched in volcanic gases, to flow towards the southern sector to an area of high pCO 2 groundwaters. Reaction path modelling applied to this conceptual model, involving gas-water-rock interaction, highlights an intense degassing process in the aquifer controlling the chemical and isotopic composition of dissolved gases, total dissolved inorganic C (TDIC) and submarine gas emission. Mapping of TDIC shows a unique area of high values situated SSE of Vesuvio volcano with an average TDIC value of 0.039 mol/L, i.e., one order of magnitude higher than groundwaters from other sectors of the volcano. On the basis of TDIC values, the amount of CO 2 transported by Vesuvio groundwaters was estimated at about 150 t/d. This estimate does not take into account the fraction of gas loss by degassing, however, it represents a relevant part of the CO 2 emitted in this quiescent period by the Vesuvio volcanic system, being of the same order of magnitude as the CO 2 diffusely degassed from the crater area

  9. Analysis of ping-pong reaction mechanisms by positional isotope exchange. Application to galactose-1-phosphate uridyltransferase

    International Nuclear Information System (INIS)

    Hester, L.S.; Raushel, F.M.

    1987-01-01

    A new positional isotope exchange method has been developed that can be used for the analysis of enzyme-catalyzed reactions which have ping-pong kinetic mechanisms. The technique can be used to measure the relative rates of ligand dissociation from enzyme-product complexes. Enzyme is incubated with the labeled substrate and an excess of the corresponding unlabeled product. The partitioning of the enzyme-product complex back toward free enzyme is determined from the rate of positional isotope exchange within the original labeled substrate. The partitioning of the enzyme-product complex forward toward free enzyme is determined from the rate of formation of totally unlabeled substrate. It has been shown that the ratio of the two rates provides a lower limit for the release of product from the enzyme-product complex. The technique has been applied to the reaction catalyzed by galactose-1-phosphate uridyltransferase. The lower limit for the release of glucose 1-phosphate from the uridyl-enzyme relative to the maximal velocity of the reverse reaction was determined to be 3.4 +/- 0.5

  10. Chemical compositions and lead isotope ratios of ancient lead-barium glasses found in Japan

    International Nuclear Information System (INIS)

    Yamasaki, Kazuo.

    1991-01-01

    Six lead-barium glasses found in the archaeological sites of the Yayoi period in the northern part of Kyushu, Japan were chemically analysed and their lead isotope ratios were determined. These data agreed with those of the glasses of the Pre-Han period found in China, suggesting the presence of possible trade between China in the Pre-Han Period (ca. fourth-third centuries B.C.) and Japan in the earlier Yayoi period (ca. first century B.C.). (author)

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

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

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

  12. An isotopic method to distinguish between ion exchange and adsorption of diazonium cations of zeolites

    International Nuclear Information System (INIS)

    Mohl, M.; Fejes, P.; Horvath, G.

    1984-01-01

    The ion exchange isotherms of two different diazonium cations have been determined on synthetic mordenite and faujasite using 22 Na as radiotracer. Under similar conditions (but with no radiotracer) the isotherms were followed spectrophotometrically so that a comparison between the amounts of ion exchanged and adsorbed cations can be made. (author)

  13. Lithium isotope effects in cation exchange chromatography of lithium lactate in water-dimethyl sulfoxide and water-acetone mixed solvent media

    International Nuclear Information System (INIS)

    Oi, Takao; Kondoh, Akiko; Ohno, Etsuko; Hosoe, Morikazu

    1993-01-01

    Lithium isotope separation by ion exchange displacement chromatography of lithium lactate in water-dimethyl sulfoxide (DMSO) and water-acetone mixed solvent media at 25 C was explored. In both the water-DMSO and water-acetone system, the single stage isotope separation factor (S) was a convex function of the mixing ratio of the solvents in the external solution phase; S had its maximum value of 1.00254 at water: DMSO=25:75 v/v and 1.00182 at water: acetone=75:25 v/v. Strong correlations of S with solvent partitions between the solution and the exchanger phases were found in both systems, which was qualitatively explainable by considering the lithium isotope distributions between the two phases based on the fundamental lithium isotope effects and the relative affinities of water, DMSO and acetone towards the lithium ion. (orig.)

  14. Associated chemical and carbon isotopic composition variations in diamonds from Finsch and Premier kimberlite, South Africa

    International Nuclear Information System (INIS)

    Deines, P.

    1984-01-01

    The carbon isotopic composition of 66 inclusion-containing diamonds from the Premier kimberlite, South Africa, 93 inclusion-containing diamonds and four diamonds of two diamond-bearing peridotite xenoliths from the Finsch kimberlite, South Africa was measured. The data suggest a relationship between the carbon isotopic composition of the diamonds and the chemical composition of the associated silicates. For both kimberlites similar trends are noted for diamonds containing peridotite-suite inclusions (P-type) and for diamonds containing eclogite-suite inclusions (E-type): Higher delta 13 C P-type diamonds tend to have inclusions lower in SiO 2 , Al 2 O 3 , Cr 2 O 3 , MgO, Mg/(Mg + Fe) and higher in FeO and CaO. Higher delta 13 C E-type diamonds tend to have inclusions lower in SiO 2 , Al 2 O 3 , MgO, Mg/(Mg + Fe), Na 2 O, K 2 O, TiO 2 and higher in CaO, Ca/(Ca + Mg). Consideration of a number of different models that have been proposed for the genesis of kimberlites, their zenoliths and diamonds shows that they are all consistent with the conclusion that in the mantle, regions exist that are characterized by different mean carbon isotopic compositions. (author)

  15. Investigation of short-lived neutron-rich palladium and silver isotopes after fast chemical separation from fission fragments

    International Nuclear Information System (INIS)

    Bruechle, W.

    1976-01-01

    In this paper, chemical separation processes are described permitting fast and neat isolation of short-lived palladium and silver nuclides from fusion product mixtures. The process for palladium is based on the stability of palladium diethyldithiophosphate. From fission products of the reactions 238 U(n,f) and 249 Cf(nth,f), the following palladium niclides could be studied for the first time by gamma spectroscopy: 1.66 min 113 Pd, 2.45 min 114 Pd, 29 sec sup(115a)Pd, 54 sec sup(115b)Pd, 12.5 sec 116 Pd. 113 Pd could also be indentified according to the reaction 116 Cd(n,α) 113 Pd. The separation of silver is based on the fast isotopic exchange on AgCl. With this process, the following nuclides have been separated from fission product mixtures and studied by gamma spectroscopy: 70 sec sup(113m)Ag, 5.0 sec 114 Ag, 19.2 sec sup(115m)Ag, 2.65 min sup(116g)Ag, 10.5 sec sup(116m)Ag, 1.3 min sup(117g)Ag, 6.0 sec sup(117m)Ag, 4.0 sec 118 Ag. (orig./WL) [de

  16. The chemical and isotopic differentiation of an epizonal magma body: Organ Needle pluton, New Mexico

    Science.gov (United States)

    Verplanck, P.L.; Farmer, G.L.; McCurry, M.; Mertzman, S.A.

    1999-01-01

    Major and trace element, and Nd and Sr isotopic compositions of whole rocks and mineral separates from the Oligocene, alkaline Organ Needle pluton (ONP), southern New Mexico, constrain models for the differentiation of the magma body parental to this compositionally zoned and layered epizonal intrusive body. The data reveal that the pluton is rimmed by lower ??(Nd) (~-5) and higher 87Sr/86Sr (~0.7085) syenitic rocks than those in its interior (??(Nd) ~ 2, 87Sr/86Sr ~0.7060) and that the bulk compositions of the marginal rocks become more felsic with decreasing structural depth. At the deepest exposed levels of the pluton, the ??(Nd)~-5 lithology is a compositionally heterogeneous inequigranular syenite. Modal, compositional and isotopic data from separates of rare earth element (REE)-bearing major and accesory mineral phases (hornblende, titanite, apatite, zircon) demonstrate that this decoupling of trace and major elements in the inequigranular syenite results from accumulation of light REE (LREE)-bearing minerals that were evidently separated from silicic magmas as the latter rose along the sides of the magma chamber. Chemical and isotopic data for microgranular mafic enclaves, as well as for restite xenoliths of Precambrian granite wall rock, indicate that the isotopic distinction between the marginal and interior facies of the ONP probably reflects assimilation of the wall rock by ??(Nd) ~-2 mafic magmas near the base of the magma system. Fractional crystallization and crystal liquid separation of the crystally contaminated magma at the base and along the margins of the chamber generated the highly silicic magmas that ultimately pooled at the chamber top.

  17. Predicting the solubility and lability of Zn, Cd, and Pb in soils from a minespoil-contaminated catchment by stable isotopic exchange

    Science.gov (United States)

    Marzouk, E. R.; Chenery, S. R.; Young, S. D.

    2013-12-01

    The Rookhope catchment of Weardale, England, has a diverse legacy of contaminated soils due to extensive lead mining activity over four centuries. We measured the isotopically exchangeable content of Pb, Cd and Zn (E-values) in a large representative subset of the catchment soils (n = 246) using stable isotope dilution. All three metals displayed a wide range of %E-values (c. 1-100%) but relative lability followed the sequence Cd > Pb > Zn. A refinement of the stable isotope dilution approach also enabled detection of non-reactive metal contained within suspended sub-micron (dilution, in a diverse range of soil ecosystems within the catchment of an old Pb/Zn mining area. Assess the controlling influences of soil properties on metal lability and develop predictive algorithms for metal lability in the contaminated catchment based on simple soil properties (such as pH, organic matter (LOI), and total metal content). Examine the incidence of non-isotopically-exchangeable metal held within suspended colloidal particles (SCP-metal) in filtered soil solutions (<0.22 μm) by comparing E-values from isotopic abundance in solutions equilibrated with soil and in a resin phase equilibrated with the separated solution. Assess the ability of a geochemical speciation model, WHAM(VII), to predict metal solubility using isotopically exchangeable metal as an input variable.

  18. Quantitative analysis of deuterium using the isotopic effect on quaternary {sup 13}C NMR chemical shifts

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Tamim A., E-mail: tamim.darwish@ansto.gov.au [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); Yepuri, Nageshwar Rao; Holden, Peter J. [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); James, Michael [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2016-07-13

    Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual {sup 1}H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D{sub 2}O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary {sup 13}C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing {sup 13}C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve {sup 13}C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ({sup 1}H, {sup 2}H) resolves closely separated quaternary {sup 13}C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. - Graphical abstract: The relative intensities of quaternary {sup 13}C {"1H,"2H} resonances are equal despite the different relaxation delays, allowing the relative abundance of the different deuterated isotopologues to be calculated using NMR fast

  19. Groundwater recharge studies using isotope-chemical techniques in wadi gharandal, sinai peninsula(E G))

    International Nuclear Information System (INIS)

    Awad, M.A.A.; Salem, W.M.; Ezzeldin

    1999-01-01

    Wadi Gharandal lies on southwestern part of sinai peninsula with its outlets into the Gulf of suez. Eight groundwater samples were collected from quaternary aquifer in wadi gharandal to identify the sources of replenishment and evaluation of its water quality. The variation in chemical composition of water samples is due to water-rock interaction and the effect of sea spray. The distribution of chemical species in the examined groundwater samples is controlled by geography and climate conditions prevailing in the area of study. The salinity increase towards the gulf of suez. The isotopic data indicate that precipitation and floods are considered to be the main sources of recharge in this area. The investigated groundwater samples are found to be suitable for irrigation purposes based on sodium adsorption ratio (SAR) and unsuitable for domestic usages due to high salinity and hardness values

  20. Chemical or electrochemical techniques, followed by ion exchange, for recycle of textile dye wastewater.

    Science.gov (United States)

    Raghu, S; Ahmed Basha, C

    2007-10-22

    This paper examines the use of chemical or electrocoagulation treatment process followed by ion-exchange process of the textile dye effluent. The dye effluent was treated using polymeric coagulant (cationic dye-fixing agent) or electrocoagulation (iron and aluminum electrode) process under various conditions such as various current densities and effect of pH. Efficiencies of COD reduction, colour removal and power consumption were studied for each process. The chemical or electrochemical treatment are indented primarily to remove colour and COD of wastewater while ion exchange is used to further improve the removal efficiency of the colour, COD, Fe concentration, conductivity, alkalinity and total dissolved solids (TDS). From the results chemical coagulation, maximum COD reduction of about 81.3% was obtained at 300 mg/l of coagulant whereas in electrocoagulation process, maximum COD removal of about 92.31% (0.25 A/dm2) was achieved with energy consumption of about 19.29 k Wh/kg of COD and 80% (1A/dm(2)) COD removal was obtained with energy consumption of about 130.095 k Wh/kg of COD at iron and aluminum electrodes, respectively. All the experimental results, throughout the present study, have indicated that chemical or electrocoagulation treatment followed by ion-exchange methods were very effective and were capable of elevating quality of the treated wastewater effluent to the reuse standard of the textile industry.

  1. Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

    International Nuclear Information System (INIS)

    Vaniman, D.T.; Whelan, J.F.

    1994-01-01

    Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-δ 13 C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate ''plug.'' In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment

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

    OpenAIRE

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

    2008-01-01

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the c...

  3. Labelling of long chain fatty acids by non isotopic nucleophilic halogen exchange

    International Nuclear Information System (INIS)

    Hallaba, E.; Al-Suhybani, A.A.; Zaki, F.S.

    1985-01-01

    The parameters of two exchange methods for preparing pure 97% labelled 17-Br-HDA in acetone and in benzene with dry NaI in a closed system are described. In aprotic solvents the need for a phase transfer catalyst up to 50 μg is necessary to dissolve the dry NaI. The use of aqueous medium in the exchange is totally prohibited. Energies of activation are calculated for both reactions. (author)

  4. Proton exchange between oxymethyl radical and acids and bases: semiempirical quantum-chemical study

    Directory of Open Access Journals (Sweden)

    Irina Pustolaikina

    2016-12-01

    Full Text Available The reactions with proton participation are widely represented in the analytical, technological and biological chemistry. Quantum-chemical study of the exchange processes in hydrogen bonding complexes will allow us to achieve progress in the understanding of the elementary act mechanism of proton transfer in hydrogen bonding chain as well as the essence of the acid-base interactions. Oxymethyl radical •CH2ОН is small in size and comfortable as a model particle that well transmits protolytic properties of paramagnetic acids having more complex structure. Quantum-chemical modeling of proton exchange reaction oxymethyl radical ∙CH2OH and its diamagnetic analog CH3OH with amines, carboxylic acids and water was carried out using UAM1 method with the help of Gaussian-2009 program. QST2 method was used for the search of transition state, IRC procedure was applied for the calculation of descents along the reaction coordinate. The difference in the structure of transition states of ∙CH2OH/ CH3OH with bases and acids has been shown. It has been confirmed that in the case of bases, consecutive proton exchange mechanism was fixed, and in the case of complexes with carboxylic acids parallel proton exchange mechanism was fixed. The similarity in the reaction behavior of paramagnetic and diamagnetic systems in the proton exchange has been found. It was suggested that the mechanism of proton exchange reaction is determined by the structure of the hydrogen bonding cyclic complex, which is, in turn, depends from the nature of the acid-base interactions partners.

  5. Chemical exchange effects during refocusing pulses in constant-time CPMG relaxation dispersion experiments

    International Nuclear Information System (INIS)

    Myint, Wazo; Ishima, Rieko

    2009-01-01

    In the analysis of the constant-time Carr-Purcell-Meiboom-Gill (CT-CPMG) relaxation dispersion experiment, chemical exchange parameters, such as rate of exchange and population of the exchanging species, are typically optimized using equations that predict experimental relaxation rates recorded as a function of effective field strength. In this process, the effect of chemical exchange during the CPMG pulses is typically assumed to be the same as during the free-precession. This approximation may introduce systematic errors into the analysis of data because the number of CPMG pulses is incremented during the constant-time relaxation period, and the total pulse duration therefore varies as a function of the effective field strength. In order to estimate the size of such errors, we simulate the time-dependence of magnetization during the entire constant time period, explicitly taking into account the effect of the CPMG pulses on the spin relaxation rate. We show that in general the difference in the relaxation dispersion profile calculated using a practical pulse width from that calculated using an extremely short pulse width is small, but under certain circumstances can exceed 1 s -1 . The difference increases significantly when CPMG pulses are miscalibrated

  6. Concept development of exchange liquid regeneration

    International Nuclear Information System (INIS)

    Mader, D.L.

    1985-08-01

    Concepts are described for regeneration of the intermediate liquid used for isotope exchange in indirect laser isotope separation processes where the laser operates on a process gas distinct from the feed stream. The specific case of regeneration of an exchange liquid consisting of water, sodium hydroxide, and dimethyl sulfoxide for a process to separate deuterium from hydrogen using laser irradiation of trifluoromethane gas is developed. A water feed stream is converted to steam which rises in a chemical process column where it redeuterates a descending flow of exchange liquid without causing significant changes in its chemical composition

  7. Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

    International Nuclear Information System (INIS)

    Marx, D.

    1959-11-01

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

  8. Improved adiabatic calculation of muonic-hydrogen-atom cross sections. I. Isotopic exchange and elastic scattering in asymmetric collisions

    International Nuclear Information System (INIS)

    Cohen, J.S.; Struensee, M.C.

    1991-01-01

    The improved adiabatic representation is used in calculations of elastic and isotopic-exchange cross sections for asymmetric collisions of pμ, dμ, and tμ with bare p, d, and t nuclei and with H, D, and T atoms. This formulation dissociates properly, correcting a well-known deficiency of the standard adiabatic method for muonic-atom collisions, and includes some effects at zeroth order that are normally considered nonadiabatic. The electronic screening is calculated directly and precisely within the improved adiabatic description; it is found to be about 30% smaller in magnitude than the previously used value at large internuclear distances and to deviate considerably from the asymptotic form at small distances. The reactance matrices, needed for calculations of molecular-target effects, are given in tables

  9. Isotope exchange experiments on TEXTOR and TORE SUPRA using Ion Cyclotron Wall Conditioning and Glow Discharge Conditioning

    International Nuclear Information System (INIS)

    Wauters, T.; Douai, D.; Lyssoivan, A.; Philipps, V.; Bremond, S.; Freisinger, M.; Kreter, A.; Lombard, G.; Marchuk, O.; Mollard, P.; Paul, M.K.; Pegourie, B.; Reimer, H.; Sergienko, G.; Tsitrone, E.; Vervier, M.; Van Wassenhove, G.; Wuenderlich, D.; Van Schoor, M.; Van Oost, G.

    2011-01-01

    This contribution reports on isotope exchange studies with both Ion Cyclotron Wall Conditioning (ICWC) and Glow Discharge Conditioning (GDC) in TEXTOR and TORE SUPRA. The discharges have been carried out in H 2 , D 2 (ICWC and GDC) and He/H 2 mixtures (ICWC). The higher reionization probability in ICWC compared to GDC, following from the 3 to 4 orders of magnitude higher electron density, leads to a lower pumping efficiency of wall desorbed species. GDC has in this analysis (5-10) times higher removal rates of wall desorbed species than ICWC, although the wall release rate is 10 times higher in ICWC. Also the measured high retention during ICWC can be understood as an effect of the high reionization probability. The use of short RF pulses (∼1 s) followed by a larger pumping time significantly improves the ratio of implanted over recovered particles, without severely lowering the total amount of removed particles.

  10. Uranium sorption to natural substrates-insights provided by isotope exchange, selective extraction and surface complexation modelling approaches

    International Nuclear Information System (INIS)

    Waite, T.D.; Payne T.E.; Davis, J.A.

    1993-01-01

    An extensive experimental program has been conducted over the last three years into the interaction of U(VI) with both single oxides and clays and complex natural substrates from the weathered zone in the vicinity of a uranium ore body in northern Australia. While iron oxides have frequently been considered to account for much of the uptake on such natural substrates, the results of laboratory open-quotes pH edgeclose quotes studies and of isotope exchange and selective extraction studies suggest that other phases must also play a significant role in controlling the partitioning of U(VI) between solid and solution phases. Supporting studies on kaolinite, the dominant clay in this system, provide insight into the most appropriate method of modelling the interaction of U(VI) with these natural substrates. The problems still remaining in adequately describing sorption of radionuclides and trace elements to complex natural substrates are discussed

  11. Double agents and secret agents: the emerging fields of exogenous chemical exchange saturation transfer and T2-exchange magnetic resonance imaging contrast agents for molecular imaging.

    Science.gov (United States)

    Daryaei, Iman; Pagel, Mark D

    2015-01-01

    Two relatively new types of exogenous magnetic resonance imaging contrast agents may provide greater impact for molecular imaging by providing greater specificity for detecting molecular imaging biomarkers. Exogenous chemical exchange saturation transfer (CEST) agents rely on the selective saturation of the magnetization of a proton on an agent, followed by chemical exchange of a proton from the agent to water. The selective detection of a biomarker-responsive CEST signal and an unresponsive CEST signal, followed by the ratiometric comparison of these signals, can improve biomarker specificity. We refer to this improvement as a "double-agent" approach to molecular imaging. Exogenous T 2 -exchange agents also rely on chemical exchange of protons between the agent and water, especially with an intermediate rate that lies between the slow exchange rates of CEST agents and the fast exchange rates of traditional T 1 and T 2 agents. Because of this intermediate exchange rate, these agents have been relatively unknown and have acted as "secret agents" in the contrast agent research field. This review exposes these secret agents and describes the merits of double agents through examples of exogenous agents that detect enzyme activity, nucleic acids and gene expression, metabolites, ions, redox state, temperature, and pH. Future directions are also provided for improving both types of contrast agents for improved molecular imaging and clinical translation. Therefore, this review provides an overview of two new types of exogenous contrast agents that are becoming useful tools within the armamentarium of molecular imaging.

  12. Critical exponents of a fluid mixture in the presence of isotope exchange: Isobutyric acid/D2O

    International Nuclear Information System (INIS)

    Gulari, E.; Chu, B.; Woermann, D.

    1980-01-01

    Experiments on phase diagrams and critical opalescence of a fluid mixture, isobutyric acid in D 2 O, indicate that the presence of isotope exchange reactions can change the critical behavior of such a system from that of a simple binary fluid mixture. Appreciable amounts of additional species due to isotope exchange distort the coexistence curve, shift the critical solution concentration y/sub c/ away from the concentration (y/sub I/*) where the maximal phase separation temperature T/sub p/,max occurs, and make the critical exponents γ and ν in the one-phase region (T>T/sub c/) different from those of the coexisting two-phase region (T 0 C differing from y/sub I/*=0.310 at T/sub p/,max=45.11 0 C. In the one-phase region, γ=1.25, ν=0.633, and xi 0 =3.13 A, in excellent agreement with γ=1.24 and ν=0.633 of simple fluid systems. However, in the coexisting two-phase region, the critical exponents appear to be renormalized with γ/sub x/ =1.39, ν/sub x/approx. =0.76, and xi 0 approx. =0.6 A. These results are in agreement with the renormalized critical exponents γ/sub x/=1.40 +- 0.02 and ν/sub x/ =0.73 +- 0.04 near the plait point of a ternary liquid mixture: ethanol--water--chloroform

  13. High Precision Stable Isotope Measurements of Caribic Aircraft CO{sub 2} Samples: Global Distribution and Exchange with the Biosphere

    Energy Technology Data Exchange (ETDEWEB)

    Assonov, S. S. [Max Planck Institute for Chemistry, Mainz (Germany); Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium); Brenninkmeijer, C. A.M.; Schuck, T. J. [Max Planck Institute for Chemistry, Mainz (Germany); Taylor, P. [Joint Research Centre, Institute for Reference Materials and Measurements (JRC-IRMM), European Commission, Geel (Belgium)

    2013-07-15

    In 2007-2009 JRC-IRMM, in collaboration with the project CARIBIC (Civil Aircraft for Regular Investigation of the atmosphere Based on an Instrument Container, www.caribicatmospheric. com), conducted systematic measurements aimed to study the global distribution of CO{sub 2} isotopic composition. A large data set for the upper troposphere-lowermost stratosphere and free troposphere was obtained. For the first time it is demonstrated how CO{sub 2} isotope signals reflect global scale variability in air mass origin. Tight correlations observed arise either from stratosphere/troposphere mixing or from mixing of background air and air masses affected by CO{sub 2} sources and sinks, over long distances and throughout the seasons. The high quality {delta}{sup 18}O(CO{sub 2}) data prove to be a useful tracer reflecting long range CO{sub 2} transport and also CO{sub 2} exchange with land biosphere and soils. The data provide a benchmark for future comparisons and are available for modelling studies. (author)

  14. Contribution of chemical and isotopic tools to the knowledge of the Carboniferous limestone aquifer - final report

    International Nuclear Information System (INIS)

    Gourcy, L.; Crastes de Paulet, F.

    2012-05-01

    Based on two sampling, analysis and interpretation campaigns, this study aimed at revealing hydro-chemical phenomena occurring within the Carboniferous and interactions between water and rock (ionic exchanges, oxido-reduction, dissolution, precipitation...), at characterizing underground flows (origins, circulation timing, mixing of different waters...), at identifying sources and at understanding phenomena related to the occurrence of high contents of sulphates (SO 4 ) in some drilling in the Carboniferous. The report presents the adopted methodology (analysis of underground and ground waters, selection of sampling points) and comments the obtained results

  15. Contribution to the study of proteins and peptides structure by hydrogen isotopic exchange

    International Nuclear Information System (INIS)

    Nabedryk-Viala, Eliane.

    1978-01-01

    Development of hydrogen exchange measurement methods to study the structure and the molecular interaction of globular protein molecules in aqueous solution (ribonuclease A, cytochrome c, coupling factors of chloroplasts), in peptide hormones in trifluoroethanol solution (angiotensin II, corticotropin) and in proteins of membranes (rhodopsin) [fr

  16. Quantification of tritium ''heels'' and isotope exchange mechanisms in La-Ni-Al tritides

    International Nuclear Information System (INIS)

    Wermer, J.R.

    1992-01-01

    Formation of tritium heels in LANA (LaNi 5-x Al x ) 0.30 (x=0.30) and 0.75 tritides was quantified; size of the heel is dependent on storage and processing conditions. Absorption-desorption cycling of the tritide beds mitigates formation of the tritium heel and can reduce its size. The higher pressure material LANA 0.30 showed slower heel formation than LANA 0.75; this allows more tritium to be removed at the maximum processing temperature. In plant application, LANA 0.30 beds are used as compressors; except during compressor operation, their aging will be very slow. Tritium heel removal by D exchange was demonstrated. Absorption-desorption cycling during an exchange cycle does not improve the exchange efficiency. Residual tritium can be removed to very low levels. For a tritide bed scheduled for removal from the process, a final tritium level can be estimated based on the number of D exchange cycles. 13 refs, 8 figs, 6 tabs

  17. Oxygen isotope exchange kinetics between coexistent minerals and water in the Ertaibei granite pluton, northern Xinjiang

    Institute of Scientific and Technical Information of China (English)

    刘伟; 李志安; 赵志忠

    1996-01-01

    Coexistent minerals quartz, feldspar and biotite vary widely in δ18O value and display remarkable 18O/16O disequilibrium relations in the Ertaibei granite pluton, northern Xinjiang. The 18O/16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic water are evaluated by the mass balance consideration. The results show that the 18O/16O exchange reaction is not necessarily accompanied by what geologists describe as petrological and mineralogiesl alteration effects, indicating that the exchange reaction occurs at a comparatively high temperature during subsolidus cooling of magmas. Exchange mechanism is mainly controlled by diffusion. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Ertaibei pluton lived for 0.8-3 Ma, with a fluid flow rate of 3 × 10-14 mol · s-1 and water/rock (W/R) ratio of 0.79 - 3.08. Flow path and initial heterogeneity of the exotic metamorphic fluid are modelled with the δ1

  18. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    Science.gov (United States)

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

    2014-01-01

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

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

    International Nuclear Information System (INIS)

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

    1986-01-01

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

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

    NARCIS (Netherlands)

    Velde, van der I.R.

    2015-01-01

    Summary Thesis ‘Studying biosphere-atmosphere exchange of CO2 through

    carbon-13 stable isotopes’

    Ivar van der Velde

    Making predictions of future climate is difficult, mainly due to large uncertainties in the carbon cycle. The rate at which carbon is stored in the oceans and

  1. One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

    International Nuclear Information System (INIS)

    Gober, J.R.

    1988-01-01

    The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional 31 P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K eq , the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process could be realized

  2. Preparation of H3-labelled methyl ethers of saturated fatty acids by heterogeneous catalytic isotope exchange in solution with gaseous tritium

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Myasoedov, N.F.

    1980-01-01

    A simple method of preparing 3 H-labelled methyl ethers of saturated fatty acids in the dioxane solution using the method of isotopic heterogenous catalytic exchange with gaseous tritium, is suggested. 3 H-labelled natural fatty acids (C 12 -C 18 ) are prepared by alkaline hydrolysis [ru

  3. Chemical and isotopic compositions of water and dissolved sulfate from shallow wells on Vulcano Island, Aeolian Archipelago, Italy

    Energy Technology Data Exchange (ETDEWEB)

    Cortecci, G.; Dinelli, E.; Boschetti, T. [University of Bologna (Italy). Dept. of Earth and Geological Environmental Sciences; Bolognesi, L. [International Institute for Geothermal Research, Pisa (Italy); Ferrara, G. [University of Pisa (Italy). Dept. of Earth Sciences

    2001-02-01

    Twenty-two cold and thermal waters from shallow wells sampled in June 1995 in the Vulcano Porto area, Vulcano Island, were analyzed for major and minor chemical constituents, oxygen and hydrogen isotopes and tritium contents, and sulfur isotopes in the dissolved sulfate. The sulfur isotopic composition of the dissolved sulfate ranges between + 0.6 and + 6.5 per mille (mean + 3.7{+-}1.7 per mille), and is interpreted as deriving mainly from fumarolic SO{sub 2} undergoing oxidation in deep and shallow aquifers, with possible minor contributions from oxidation of H{sub 2}S. Dissolution of secondary anhydrite may have been a minor source of the isotopically heavy aqueous sulfate in the cold groundwaters. The chemical and isotopic features of the waters support previous interpretative hydrologic models of Vulcano Porto, which comprise a number of aquifers fed basically by two major end-members, i.e. meteoric water and crater-type fumarolic inputs, the latter in the form of absorbed emissions or condensate. These data, along with the sulfur isotopes of aqueous sulfate, exclude involvement of seawater in the recharge of the groundwater system of the island. (author)

  4. Identification of recharge sources of groundwater in the Joganjigawa Fan, Toyama, using isotopic and chemical data

    International Nuclear Information System (INIS)

    Mizutani, Yoshihiko; Sakurai, Kazuhiro

    1988-01-01

    The Joganjigawa Fan, an area of rice farming of 50 km 2 lies to the southeast of Toyama city and was formed in the Late Quarternary by terrestrial gravel deposition by the Joganji River. To identify sources of water in shallow aquifers (maximum depth 100 m) beneath the fan, studies of hydrogen and oxygen isotopes in the ground and surface waters of the fan have been made. Major rivers flowing onto the fan are from higher-altitude catchments (maximum altitude 3000 m) and have lower δ 18 D and δO values than rainfall on the fan. The isotopic measurements indicate that the aquifers are mainly recharged by infiltration of the irrigation water, which is derived from the Joganji River, and local precipitations from the surface. In narrow areas along the Jinzu and its tributary the Kumano Rivers, the aquifers are locally recharged from the Jinzu and Kumano Rivers, respectively. Chemical data support this identification of sources of water in the aquifers. (author)

  5. Chemical and isotopic methods for characterization of pollutant sources in rain water

    International Nuclear Information System (INIS)

    Verma, M.P.

    1996-01-01

    The acid rain formation is related with industrial pollution. An isotopic and chemical study of the spatial and temporary distribution of the acidity in the rain gives information about the acidity source. The predominant species in the acid rain are nitrates and sulfates. For the rain monitoring is required the determination of the anion species such as HCO 3 , Cl, SO 4 , NO 3 and p H. So it was analyzed the cations Na + , K + , Ca 2+ and Mg 2+ to determine the quality analysis. All of them species can be determined with enough accuracy, except HCO 3 by modern equipment such as, liquid chromatograph, atomic absorption, etc. The HCO 3 concentration is determined by traditional methods like acid-base titration. This work presents the fundamental concepts of the titration method for samples with low alkalinity (carbonic species), for rain water. There is presented a general overview over the isotopic methods for the characterization of the origin of pollutant sources in the rain. (Author)

  6. Application of isotope-labelled compounds in the study of the chemical stability of pesticides

    International Nuclear Information System (INIS)

    Roesseler, M.; Luther, D.; Abendroth, H.C.; Koch, H.

    1980-01-01

    The user of pesticides requires specific biological modes of action from the corresponding commercial products. Impurities and degradation products may cause uncontrollable toxicological reactions. Profound knowledge of the chemical stability of the effective substance in question and its formulations under storage conditions as well as under those of analytical sample preparation and detection is required. Radioisotope labelled effective substances dimethoate and 1-butyl-amino-cyclohexane-phosphonic acid dibutyl ester are used to study storage stability of the pure effective substance and its formulations; effects of selected impurities, such as technical by-products, moisture or water content, binding or carrier materials, organic solvents, chemical stabilizers and other formulation components on storage properties; temperature dependence of storage stability; selection of suitable analytical techniques for quantitative determination of the effective substance without interference effects from any by-product; reduction of the necessary analytical expense; disclosure of sources of error in the application of usual analytical techniques; improvement of possibilities of an immediate and clearer discrimination between types and amounts of compounds in a chemical system consisting of one pesticide and its degradation or reaction products at the beginning and at the end of an experimental or reaction period. Radiochemical analytical techniques, such as radio thin-layer chromatography (also combined with liquid scintillation counting), radio gas chromatography, autoradiography and isotope dilution analysis were used. Results are discussed, especially of experiments on dimethoate and its technical by-products

  7. Chemical Ligation of Folded Recombinant Proteins: Segmental Isotopic Labeling of Domains for NMR Studies

    Science.gov (United States)

    Xu, Rong; Ayers, Brenda; Cowburn, David; Muir, Tom W.

    1999-01-01

    A convenient in vitro chemical ligation strategy has been developed that allows folded recombinant proteins to be joined together. This strategy permits segmental, selective isotopic labeling of the product. The src homology type 3 and 2 domains (SH3 and SH2) of Abelson protein tyrosine kinase, which constitute the regulatory apparatus of the protein, were individually prepared in reactive forms that can be ligated together under normal protein-folding conditions to form a normal peptide bond at the ligation junction. This strategy was used to prepare NMR sample quantities of the Abelson protein tyrosine kinase-SH(32) domain pair, in which only one of the domains was labeled with 15N Mass spectrometry and NMR analyses were used to confirm the structure of the ligated protein, which was also shown to have appropriate ligand-binding properties. The ability to prepare recombinant proteins with selectively labeled segments having a single-site mutation, by using a combination of expression of fusion proteins and chemical ligation in vitro, will increase the size limits for protein structural determination in solution with NMR methods. In vitro chemical ligation of expressed protein domains will also provide a combinatorial approach to the synthesis of linked protein domains.

  8. Transfer Rate Edited experiment for the selective detection of Chemical Exchange via Saturation Transfer (TRE-CEST)

    Science.gov (United States)

    Friedman, Joshua I.; Xia, Ding; Regatte, Ravinder R.; Jerschow, Alexej

    2015-07-01

    Chemical Exchange Saturation Transfer (CEST) magnetic resonance experiments have become valuable tools in magnetic resonance for the detection of low concentration solutes with far greater sensitivity than direct detection methods. Accurate measures of rates of chemical exchange provided by CEST are of particular interest to biomedical imaging communities where variations in chemical exchange can be related to subtle variations in biomarker concentration, temperature and pH within tissues using MRI. Despite their name, however, traditional CEST methods are not truly selective for chemical exchange and instead detect all forms of magnetization transfer including through-space NOE. This ambiguity crowds CEST spectra and greatly complicates subsequent data analysis. We have developed a Transfer Rate Edited CEST experiment (TRE-CEST) that uses two different types of solute labeling in order to selectively amplify signals of rapidly exchanging proton species while simultaneously suppressing 'slower' NOE-dominated magnetization transfer processes. This approach is demonstrated in the context of both NMR and MRI, where it is used to detect the labile amide protons of proteins undergoing chemical exchange (at rates ⩾ 30 s-1) while simultaneously eliminating signals originating from slower (∼5 s-1) NOE-mediated magnetization transfer processes. TRE-CEST greatly expands the utility of CEST experiments in complex systems, and in-vivo, in particular, where it is expected to improve the quantification of chemical exchange and magnetization transfer rates while enabling new forms of imaging contrast.

  9. Transfer Rate Edited experiment for the selective detection of Chemical Exchange via Saturation Transfer (TRE-CEST).

    Science.gov (United States)

    Friedman, Joshua I; Xia, Ding; Regatte, Ravinder R; Jerschow, Alexej

    2015-07-01

    Chemical Exchange Saturation Transfer (CEST) magnetic resonance experiments have become valuable tools in magnetic resonance for the detection of low concentration solutes with far greater sensitivity than direct detection methods. Accurate measures of rates of chemical exchange provided by CEST are of particular interest to biomedical imaging communities where variations in chemical exchange can be related to subtle variations in biomarker concentration, temperature and pH within tissues using MRI. Despite their name, however, traditional CEST methods are not truly selective for chemical exchange and instead detect all forms of magnetization transfer including through-space NOE. This ambiguity crowds CEST spectra and greatly complicates subsequent data analysis. We have developed a Transfer Rate Edited CEST experiment (TRE-CEST) that uses two different types of solute labeling in order to selectively amplify signals of rapidly exchanging proton species while simultaneously suppressing 'slower' NOE-dominated magnetization transfer processes. This approach is demonstrated in the context of both NMR and MRI, where it is used to detect the labile amide protons of proteins undergoing chemical exchange (at rates⩾30s(-1)) while simultaneously eliminating signals originating from slower (∼5s(-1)) NOE-mediated magnetization transfer processes. TRE-CEST greatly expands the utility of CEST experiments in complex systems, and in-vivo, in particular, where it is expected to improve the quantification of chemical exchange and magnetization transfer rates while enabling new forms of imaging contrast. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Chemical and isotopic investigations of runoff in a mountainous watershed, Venezuelan Andes (Rio Bocono)

    International Nuclear Information System (INIS)

    Cornieles, M.; Moreau, A.; Valles, V.; Travi, Y.

    1999-01-01

    The Rio Bocono watershed, located in the Western part of Venezuela on the South western side of Andes is considered by the 'Ministerio de1 Ambiente y de los Recursos Naturales Renovables' (MARN) as a priority zone for environmental management. The studies of relation between flow, dissolved elements and solid transport are essential to estimate soil degradation and sediment deposition which provokes loss of depth in the dam reservoir at the Southern margin of the basin. Because of the large surface which reach 1540 km 2 , the lack of equipment and the flash flood character of the river do not enable the flow mechanisms and transit times to be determined using usual hydrologic methods; therefore this problem has been approached by the way of chemical and isotopic investigation

  11. Isotopic and chemical aspects of nitrate in the groundwater of the Springbok Flats

    Energy Technology Data Exchange (ETDEWEB)

    Heaton, T H.E.

    1985-10-01

    Increases in the concentration of nitrate in groundwater are becoming a world-wide problem and are commonly ascribe to one or more of three factors associated with modern farming methods: increased fertilization, increased animal waste and increased cultivation. A combined isotopic ( VN/ UN) and chemical study of the high nitrate groundwater in the basalts of the Springbok Flats (Transvaal, South Africa) indicates that the third factor is the only important source of nitrate. Nitrification of the 'black turf' soils, accelerated by the expansion of cultivation, has resulted in most of the shallow groundwater having nitrate concentrations higher than the 'maximum allowable' limit for domestic water supply and the concentrations are still increasing. Modification of farming practices has been suggested in some countries, as a means of controlling both the increase in groundwater nitrate and the attendant decrease in soil fertility.

  12. Isotopic and chemical aspects of nitrate in the groundwater of the Springbok Flats

    International Nuclear Information System (INIS)

    Heaton, T.H.E.

    1985-01-01

    Increases in the concentration of nitrate in groundwater are becoming a world-wide problem and are commonly ascribe to one or more of three factors associated with modern farming methods: increased fertilization, increased animal waste and increased cultivation. A combined isotopic ( 15 N/ 14 N) and chemical study of the high nitrate groundwater in the basalts of the Springbok Flats (Transvaal, South Africa) indicates that the third factor is the only important source of nitrate. Nitrification of the 'black turf' soils, accelerated by the expansion of cultivation, has resulted in most of the shallow groundwater having nitrate concentrations higher than the 'maximum allowable' limit for domestic water supply and the concentrations are still increasing. Modification of farming practices has been suggested in some countries, as a means of controlling both the increase in groundwater nitrate and the attendant decrease in soil fertility

  13. Deuterium/hydrogen isotope exchange on beryllium and beryllium nitride; Deuterium/Wasserstoff-Isotopenaustausch an Beryllium und Berylliumnitrid

    Energy Technology Data Exchange (ETDEWEB)

    Dollase, Petra; Eichler, Michael; Koeppen, Martin; Dittmar, Timo; Linsmeier, Christian [Forschungszentrum Juelich GmbH, Institut fuer Energie- und Klimaforschung - Plasmaphysik (Germany)

    2016-07-01

    In the fusion experiments JET and ITER, the first wall is made up of beryllium. The use of nitrogen is discussed for radiative cooling in the divertor. This can react with the surface of the first wall to form beryllium nitride (Be{sub 3}N{sub 2}). The hydrogen isotopes deuterium and tritium, which react in the fusion reaction to helium and a neutron, are used as fuel. Since the magnetic confinement of the plasma is not perfect, deuterium and tritium ions are also found on the beryllium wall and can accumulate there. This should be avoided due to the radioactivity of tritium. Therefore the isotope exchange with deuterium is investigated to regenerate the first wall. We investigate the isotopic exchange of deuterium and protium in order to have not to work with radioactive tritium. The ion bombardment is simulated with an ion source. With voltages up to a maximum of 5 kV, deuterium and protic hydrogen ions are implanted in polycrystalline Be and Be{sub 3}N{sub 2}. The samples are then analyzed in situ using X-ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). Subsequently, samples prepared under the same conditions are characterized ex-situ by means of nuclear reaction analysis (NRA). [German] In den Fusionsexperimenten JET und ITER besteht die erste Wand im Hauptraum aus Beryllium (Be). Zur Strahlungskuehlung im Divertor wird der Einsatz von Stickstoff diskutiert. Dieser kann mit der Oberflaeche der ersten Wand zu Berylliumnitrid (Be{sub 3}N{sub 2}) reagieren. Als Brennstoff werden die Wasserstoffisotope Deuterium und Tritium eingesetzt, die in der Fusionsreaktion zu Helium und einem Neutron reagieren. Da der magnetische Einschluss des Plasmas nicht perfekt ist, treffen auch Deuterium- und Tritiumionen auf die Berylliumwand auf und koennen sich dort anreichern. Das soll aufgrund der Radioaktivitaet von Tritium unbedingt vermieden werden. Daher wird zur Regenerierung der ersten Wand der Isotopenaustausch mit Deuterium untersucht. Wir

  14. Chemical and Isotopic Tracers of Groundwater Sustainability: an Overview of New Science Directions

    Science.gov (United States)

    Bullen, T.

    2002-12-01

    Groundwater sustainability is an emerging concept that is rapidly gaining attention from both scientists and water resource managers, particularly with regard to contamination and degradation of water quality in strategic aquifers. The sustainability of a groundwater resource is a complex function of its susceptibility to factors such as intrusion of poor-quality water from diverse sources, lack of sufficient recharge and reorganization of groundwater flowpaths in response to excessive abstraction. In theory the critical limit occurs when degradation becomes irreversible, such that remediative efforts may be fruitless on a reasonable human time scale. Chemical and isotopic tracers are proving to be especially useful tools for assessment of groundwater sustainability issues such as characterization of recharge, identification of potential sources, pathways and impacts of contaminants and prediction of how hydrology will change in response to excessive abstraction. A variety of relatively cost-efficient tracers are now available with which to assess the susceptibility of groundwater reserves to contamination from both natural and anthropogenic sources, and may provide valuable monitoring and regulatory tools for water resource managers. In this overview, the results of several ongoing groundwater studies by the U.S. Geological Survey will be discussed from the perspective of implications for new science directions for groundwater sustainability research that can benefit water policy development. A fundamental concept is that chemical and isotopic tracers used individually often provide ambiguous information, and are most effective when used in a rigorous "multi-tracer" context that considers the complex linkages between the hydrology, geology and biology of groundwater systems.

  15. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    Science.gov (United States)

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

  16. Iodine isotopes and radiation safety

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  17. Chemical exchange in novel spirobicyclic zwitterionic Janovsky complexes using dynamic 1H NMR spectroscopy.

    Science.gov (United States)

    Culf, A S; Cuperlović-Culf, M; Ouellette, R J

    2009-02-01

    Highly coloured Janovsky complexes have been known for over 120 years, being used in many colourimetric analytical procedures. In this present study, two novel and stable nitrocyclohexadienyl spirobicyclic, zwitterionic Janovsky anionic hydantoin sigma-complexes, rac-1,3-diisopropyl-6-nitro-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (1) and 1,3-diisopropyl-2,4-dioxo-1,3-diazaspiro[4.5]deca-6,9-dien-8-ylideneazinate, ammonium internal salt (2) have been prepared and characterised by NMR, electrospray ionization mass spectrometry (ESI-MS) and UV/visible methods. For the p-mononitro-substituted complex (2), we discovered chemical exchange behaviour using 1D saturation transfer and 2D exchange spectroscopy (EXSY) (1)H NMR techniques. The coalescence temperature was determined to be 62 degrees C in d(3)-acetonitrile. Analysis of these data provided a Gibbs free energy of activation, DeltaG double dagger, of + 67 kJ mole(-1), a rate constant, k, coalescence of 220 Hz and an equilibrium constant, K(eqm), of 0.98 as estimates of the exchange process in this solvent. Of the two mechanisms proposed for this fluxional behaviour, ring opening to a substituted benzene or proton exchange, a further theoretical modelling study of 1D (1)H NMR spectra was able to confirm that simple proton exchange between the two nitrogen sites of the hydantoin ring provided an accurate simulation of the observed experimental evidence. Interestingly, the o,p-dinitro-substituted complex (1) did not show any chemical exchange behaviour up to 150 degrees C in d(3)-acetonitrile (to 75 degrees C) and d(6)-dimethyl sulfoxide (DMSO). Molecular modelling at the MM2 level suggests that steric collisions of an N-acyl isopropyl substituent of the hydantoin ring with the ortho-nitro group of the spirofused cyclohexadienyl ring prevents the proposed proton exchange mechanism occurring in this case. 2008 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.

  18. Possibilities of chemical isolation of element 106 from aqueous solutions according to the model experiments with short lived tungsten isotopes

    International Nuclear Information System (INIS)

    Szeglowski, Z.; Bruchertseifer, H.; Brudanin, V.B.

    1993-01-01

    A rapid method for continuous separation of short-lived tungsten isotopes from the lanthanides has been developed. It consists in transforming nuclear reaction products from the target by an aerosol jet to an absorber where the KCl particulates are dissolved in 0.2 M HF and percolating the product solution through three successively linked columns filled with ion exchange resins Dowex 50X8 (cationite), Dowex 1X8 (anionite) and again Dowex 50X8. 3 refs

  19. Development of styrene divinyl benzene catalyst in isotopic exchange reaction of water and hydrogen

    International Nuclear Information System (INIS)

    Morishita, Teizo; Noda, Shigeyuki; Tan, Tsutomu; Noguchi, Hiroshi

    1982-01-01

    Styrene divinyl benzene copolymer (SDBC) is hydrophobic, and porous with large specific surface area. Utilizing these properties, the SDBC was used for the carrier of catalyst in water-hydrogen exchange reaction process, and the hydrophobic platinum catalyst with very high performance was able to be developed. However, the SDBC is usually fine particles smaller than 1 mm, and is not suitable as the filling catalyst for exchange reaction towers. Therefore, in this study, using only platinum as a catalyst metal, the improvement of the property of carriers was emphatically examined, and platinum bearing was proved with an optical or electron microscope. As the result, it was found that the SDBC catalyst showed high activity practically usable as the hydrophobic catalyst for heavy water or tritium exchange reaction. The characteristics of SDBC are explained. The manufacturing processes of the catalyst by making SDBC carriers with fine particles and letting them bear platinum are described. The results of the trial manufacture of spherical, extrusion-formed and honeycomb carrier catalysts are reported. Platinum must be dispersed over the large specific surface area of SDBC carriers. (Kako, I.)

  20. New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

    Science.gov (United States)

    Ferreira-Aparicio, Paloma

    2009-09-01

    The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

  1. Re-Os Isotopic Constraints on the Chemical Evolution and Differentiation of the Martian Mantle

    Science.gov (United States)

    Brandon, Alan D.; Walker, Richard J.

    2002-01-01

    The (187)Re-187Os isotopic systematics of SNC meteorites, thought to be from Mars, provide valuable information regarding the chemical processes that affected the Martian mantle, particularly with regard to the relative abundances of highly siderophile elements (HSE). Previously published data (Birck and Allegre 1994, Brandon et al. 2000), and new data obtained since these studies, indicate that the HSE and Os isotopic composition of the Martian mantle was primarily set in its earliest differentiation history. If so, then these meteorites provide key constraints on the processes that lead to variation in HSE observed in not only Mars, but also Earth, the Moon and other rocky bodies in the Solar System. Processes that likely have an effect on the HSE budgets of terrestrial mantles include core formation, magma ocean crystallization, development of juvenile crust, and the addition of a late veneer. Each of these processes will result in different HSE variation and the isotopic composition of mantle materials and mantle derived lavas. Two observations on the SNC data to present provide a framework for which to test the importance of each of these processes. First, the concentrations of Re and Os in SNC meteorites indicate that they are derived from a mantle that has similar concentrations to the Earth's mantle. Such an observation is consistent with a model where a chondritic late veneer replenished the Earth and Martian mantles subsequent to core formation on each planet. Alternative models to explain this observation do exist, but will require additional data to test the limitations of each. Second, Re-Os isotopic results from Brandon et al. (2000) and new data presented here, show that initial yos correlates with variations in the short-lived systems of (182)Hf- (182)W and (142)Sm-142Nd in the SNC meteorites (epsilon(sub W) and epsilon(sub 142Nd)). These systematics require an isolation of mantle reservoirs during the earliest differentiation history of Mars, and

  2. Isotope exchange of molecular oxygen with oxygen of La0,7Sr0,3CoO3-δ

    International Nuclear Information System (INIS)

    Vdovin, G.K.; Kuzin, B.L.; Kurumchin, Eh.Kh.

    1991-01-01

    The exchange rate of the oxygen in La 0,7 Sr 0,3 CoO 3-δ has been measured by an isotopic exchange method at temperatures 620-1250 K and pressures 1.6-10 torr. The activation energy and the dependence of the exchange rate on pressures in gas have been defined. It is suggested that the knees on the temperature dependences of the exchange rate are attributed to the appearance of Co 2+ ions on the surface of the sample at elevated temperature as new centres of the exchange reaction. The activation energies of the adsorption and desorption processes on the La 0,7 Sr 0,3 CoO 3-δ surface have been estimated

  3. Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

    Science.gov (United States)

    Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

    2018-02-01

    Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in

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

    Science.gov (United States)

    Hamuro, Yoshitomo

    2017-03-01

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

  5. Chemical, physical and isotopic characterization of U3Si2, for nuclear forensics purposes

    International Nuclear Information System (INIS)

    Rosa, Daniele Scarpim

    2011-01-01

    In the early 1990's, the first illicit trafficking of nuclear and radioactive materials was observed mainly in Europe. A decade marked by numerous cases of seizures of these materials. As a result, these events have become the subject of criminal forensic investigations and develop from there, nuclear forensics. In Brazil there are no illicit trafficking official records of nuclear material, however, is widely known the extraction and illegal transportation of radioactive geological materials, and the materials pieces attachment used as shielding for radioactive sources. One of the main tools used in nuclear forensics is the nuclear materials databases establishment. These documents must contain the most information as possible about the physical, chemical and nuclear material seized, allowing the identification of their origin, manufacturing process or age. Thus, it sets characteristic composition standards of each material, called 'chemical signatures' (chemical finger print). In this work nuclear forensic protocol was adopted as well as the three stages of assessment suggested by International Atomic Energy Agency (IAEA) in identifying the origin of uranium silicide (U 3 Si 2 ). Assays were performed in order to make physical, chemical and isotopic characterization of the studied materials and compared the data with those obtained for other uranium compounds (Uranium tetrafluoride, UF 4 ; uranium oxide, UO 2 and U 3 O 8 ; Yellow cake) by establishing a characteristic signature for each one. Through the assays the uranium compounds were classify by origin groups, as far as they are from different manufactured process and/ or origin. It was also possible to show the importance of a nuclear forensic database during an investigation of a nuclear forensic event. (author)

  6. Isotopic analysis of plutonium by computer controlled mass spectrometry

    International Nuclear Information System (INIS)

    1974-01-01

    Isotopic analysis of plutonium chemically purified by ion exchange is achieved using a thermal ionization mass spectrometer. Data acquisition from and control of the instrument is done automatically with a dedicated system computer in real time with subsequent automatic data reduction and reporting. Separation of isotopes is achieved by varying the ion accelerating high voltage with accurate computer control

  7. Lead isotope analyses of standard rock samples

    International Nuclear Information System (INIS)

    Koide, Yoshiyuki; Nakamura, Eizo

    1990-01-01

    New results on lead isotope compositions of standard rock samples and their analytical procedures are reported. Bromide form anion exchange chromatography technique was adopted for the chemical separation lead from rock samples. The lead contamination during whole analytical procedure was low enough to determine lead isotope composition of common natural rocks. Silica-gel activator method was applied for emission of lead ions in the mass spectrometer. Using the data reduction of 'unfractionated ratios', we obtained good reproducibility, precision and accuracy on lead isotope compositions of NBS SRM. Here we present new reliable lead isotope compositions of GSJ standard rock samples and USGS standard rock, BCR-1. (author)

  8. The measurement of the chemically mobile fraction of lead in soil using isotopic dilution analysis

    International Nuclear Information System (INIS)

    Kirchhoff, J.; Brand, J.; Schuettelkopf, H.

    1992-12-01

    The chemically available fraction of lead in eight soils measured by isotopic dilution analysis using 212 Pb ranged from 7 to 16% of the total content of lead in soil. The soluble fractions achieved values up to 63% of the total content in 1 M NH 4 NO 3 , 1 M MgCl 2 and 0.05 M DTPA solutions. Increasing the contact time between water and soil, the water-soil ratio from 1:1 to 5:1 and increasing the temperature of the soil-water suspension raised the chemically available fraction in soil. Comparing various soil parameters and the mobile fraction of lead, only pH shows a significant correlation. The amphoteric character of lead causes a minimum of mobility about pH 6; pH-values below are responsible for the higher mobility of lead as Pb 2+ , at pH-values above 6 soluble hydroxy and humic acid complexes are formed. (orig.) [de

  9. A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O.

    Science.gov (United States)

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

    2005-11-10

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

  10. Metal and hydrogen catalysis in isotopic hydrogen exchange in some biologically important heterocyclic compounds

    International Nuclear Information System (INIS)

    Buncel, E.; Joly, H.A.; Jones, J.R.; Onyido, I.

    1989-01-01

    This study reports on the catalytic roles of metal and hydrogen ions in tritium exchange in some heterocyclic substrates which occur as residues in many biologically important molecules. We have found that detritiation of 1-methyl[2- 3 H]imidazole is inhibited by a number of metal ions. As well, inhibition of exchange rates was noted with Ag(I) and Cu(II) for [2- 3 H]thiazole and 1-methyl[8- 3 H]inosine, with Ag(I) for [2- 3 H]benzothiazole, and with Cu(II) for 1-methyl[8- 3 H]guanosine. A complete mechanistic description, which includes the various metal ion-coordinated species generated under the experimental conditions, is presented. The results demonstrate the reactivity order: protonated >> metal-coordinated >> neutral substrates. The differential catalytic effects of metal and hydrogen ions in these processes are discussed in terms of the extent of charge developed on the ligating heteroatom in the reaction intermediate. (author). 13 refs.; 1 fig

  11. Investigation of Chemical and Physical Changes to Bioapatite During Fossilization Using Trace Element Geochemistry, Infrared Spectroscopy and Stable Isotopes

    Science.gov (United States)

    Suarez, C. A.; Kohn, M. J.

    2013-12-01

    Bioapatite in the form of vertebrate bone can be used for a wide variety of paleo-proxies, from determination of ancient diet to the isotopic composition of meteoric water. Bioapatite alteration during diagenesis is a constant barrier to the use of fossil bone as a paleo-proxy. To elucidate the physical and chemical alteration of bone apatite during fossilization, we analyzed an assortment of fossil bones of different ages for trace elements, using LA-ICP-MS, stable isotopes, and reflected IR spectroscopy. One set of fossil bones from the Pleistocene of Idaho show a diffusion recrystallization profile, however, rare earth element (REE) profiles indicate diffusion adsorption. This suggests that REE diffusion is controlled by changing (namely decreasing) boundary conditions (i.e. decreasing concentration of REE in surrounding pore fluids). Reflected IR analysis along this concentration profile reveal that areas high in U have lost type A carbonate from the crystal structure in addition to water and organics. Stable isotopic analysis of carbon and oxygen will determine what, if any, change in the isotopic composition of the carbonate component of apatite has occurred do to the diffusion and recrystallization process. Analysis of much older bone from the Cretaceous of China reveal shallow REE and U concentration profiles and very uniform reflected IR spectra with a significant loss of type A carbonate throughout the entire bone cortex. Analysis of stable isotopes through the bone cortex will be compared to the stable isotopes collected from the Pleistocene of Idaho.

  12. [Chemical Exchange Saturation Transfer Imaging of Creatine Metabolites: a 3.0 T MRI Pilot].

    Science.gov (United States)

    Guo, Ying-kun; Li, Zhen-lin; Rong, Yu; Xia, Chun-chao; Zhang, Li-zhi; Peng, Wan-ling; Liu, Xi; Xu, Hua-yan; Zhang, Ti-jiang; Zuo, Pan-li; Schmitt, Benjamin

    2016-03-01

    To determine the feasibility of using chemical exchange saturation transfer (CEST) imaging to measure creatine (Cr) metabolites with 3.0 T MR. Phantoms containing different concentrations of Cr under various pH conditions were studied with CEST sequence on 3.0 T MR imaging. CEST effect and Z spectra were analyzed. Cr exhibited significant CEST effect (± 1.8 ppm, F = 99.08, P 3.0 T MR imaging, and positive correlation was found between the signal intensity and concentration of Cr (r = 0.963, P 3.0 T MR imaging. Creatine concentrations and pH influence CEST effect.

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

    Science.gov (United States)

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

    2011-01-01

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

  14. Chemical and Isotopes study of pollutants transport through unsaturated zone in Damascus oasis (Syria)

    International Nuclear Information System (INIS)

    Abou Zakhem, B.; Hafez, R.

    2011-08-01

    The primary objectives of this study were to determine the hydrochemical and isotopic characteristics of groundwater and to study vertical transport processes for trace elements through the unsaturated zone, from the surface water into the groundwater system. A third objective is to identifying the importance of the unsaturated zone in protecting groundwater from contamination. Distribution of trace elements, including Cu, Pb, Cr, Cd, Zn and As in the soil with depth were studied. Mineralogy was investigated using X-Ray diffraction techniques and granulometry in three drilled soil profile (KA, KB and KS) in Damascus Oasis, which indicated that the soil consists mainly of calcite, a mineral that has the ability to bind some of the trace elements. Measurement of nitrate concentrations in groundwater permitted an investigation of the urban, industrial and agricultural pollution in the Oasis, in particular, in the eastern part of Damascus city and in the north of Oasis where the irrigation by treated wastewater is applied. Depending on the chemical characteristics of the studied trace elements and soil conditions, these elements have high concentrations in the upper part of the soil (20-30 cm depth), due to absorption by clay minerals and organic matter. These high concentrations represent pollution by leather industries (tannery) in the area. The trace element concentrations decrease towards the east in parallel with river flow direction. The lower part of profiles show low trace element concentrations, below the international permitted limit. The low concentrations of trace elements in groundwater which are also below the international limit, indicates no pollution is presented. The isotopic composition of shallow groundwater indicates the underground recharge, originated from the Anti-Lebanon Mountain, is more significant than the direct recharge through unsaturated zone. It is concluded the unsaturated zone and the decrease of groundwater levels have played an

  15. Metal Chemical and Isotope Characterisation in the Upper Loire River Basin, France

    Science.gov (United States)

    Widory, D.; Nigris, R.; Morard, A.; Gassama, N.; Poirier, A.; Bourrain, X.

    2016-12-01

    The Water Framework Directive (WFD) elaborated by the European Commission regulates water resources in the EC based on five years management plans. A new management plan that started in 2016 imposes strict water quality criteria to its member states, including good status thresholds for metallic contaminants. The Loire River, the most important river in France, flows through areas with lithologies naturally containing high metal concentrations in the upper part of its basin. Understanding these metal fluxes into the river is thus a prerequisite to understand their potential impact on the quality of its water in regards to the criteria defined by the WFD. The Massif Central, a residue of the Hercynian chain, is composed of granitic and volcanic rocks. Both its upstream position in the Loire basin and its numerous metal mineralizations made this region a good candidate for characterizing the natural metal geochemical background of its surface waters. To fulfill this objective we focused on the Pb, Cd and Zn chemical and isotope characteristics of selected non-anthropized small watersheds. The investigated small watersheds were selected for supposedly draining a single lithology and undergoing (as far as possible) negligible to no anthropogenic pressure. Results showed that although the high metal potential of the upper part of the Loire River basin has been highly exploited by humans for centuries, metal concentrations during the hydrological cycle are still under the guidelines defined by the WFD. Isotope compositions/ratios are strongly related to the corresponding lithologies along the rivers and help precisely define the local geochemical background that can then be used to identify and quantify any anthropogenic inputs downstream.

  16. Quantitative chemical exchange saturation transfer (qCEST) MRI--RF spillover effect-corrected omega plot for simultaneous determination of labile proton fraction ratio and exchange rate.

    Science.gov (United States)

    Sun, Phillip Zhe; Wang, Yu; Dai, ZhuoZhi; Xiao, Gang; Wu, Renhua

    2014-01-01

    Chemical exchange saturation transfer (CEST) MRI is sensitive to dilute proteins and peptides as well as microenvironmental properties. However, the complexity of the CEST MRI effect, which varies with the labile proton content, exchange rate and experimental conditions, underscores the need for developing quantitative CEST (qCEST) analysis. Towards this goal, it has been shown that omega plot is capable of quantifying paramagnetic CEST MRI. However, the use of the omega plot is somewhat limited for diamagnetic CEST (DIACEST) MRI because it is more susceptible to direct radio frequency (RF) saturation (spillover) owing to the relatively small chemical shift. Recently, it has been found that, for dilute DIACEST agents that undergo slow to intermediate chemical exchange, the spillover effect varies little with the labile proton ratio and exchange rate. Therefore, we postulated that the omega plot analysis can be improved if RF spillover effect could be estimated and taken into account. Specifically, simulation showed that both labile proton ratio and exchange rate derived using the spillover effect-corrected omega plot were in good agreement with simulated values. In addition, the modified omega plot was confirmed experimentally, and we showed that the derived labile proton ratio increased linearly with creatine concentration (p plot for quantitative analysis of DIACEST MRI. Copyright © 2014 John Wiley & Sons, Ltd.

  17. Optimization of the operational parameters in isotopic exchange installations. ROMAG PROD plant production of heavy water for the nuclear power plant

    International Nuclear Information System (INIS)

    Pop, A.

    2002-01-01

    The ROMAG PROD heavy water plant at Drobeta Turnu Severin together with SN Nuclearelectrica Company and Nuclear Fuel Plant at Pitesti are the most important pillars the National Nuclear Program is based on. The plant became operational on 17th July 1988, was later modernized and now reached in the field a leading position known world wide. There are described the modifications adopted to the two stages of the isotopic exchange installation besides some refurbishment measures of general character. The increase of discharge flow rate in cool columns vs hot columns resulted in a rise of technological regime stability and the feeding rate. Also in the first stage the stripping vapor injection in the hot columns was modified to avoid vacuum excursion in the columns. In the second stage two isotopic exchange trays were replaced with dry trays to obtain drop separation at the cool column top. All the trays from the isotopic exchange section of the cool column were replaced by trays from the hot column. The thermal exchange zone in the cool column was modified by introducing trays with number of holes. The gas flow rate of the stage two compressor was adapted to the design requirements. By these changes of the parameters in the original design were substantially improved, the operation became easier, more secure and safer for the environment while the production of the heavy water doubled between 1995 and 2001 reaching a value of 163 t/y in 2001

  18. Solvent effects on the kinetics of the chlorine isotopic exchange reaction between chloride ion and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorchloridothioate

    International Nuclear Information System (INIS)

    Mikolajczyk, M.; Slebocka-Tilk, H.; Reimschussel, W.

    1982-01-01

    The effect of solvent on the kinetics of the chlorine isotopic exchange reaction between 36 Cl- ions and O,O-diphenyl phosphorochloridate or O,O-diphenyl phosphorochloridothioate has been investigated in nitromethane, acetonitrile, propylene carbonate, benzonitrile, nitrobenzene, and hexamethyl-phosphoric triamide. The rate constants decrease with increasing electrophilicity of the solvent. A good correlation between the logarithm of the rate constants and acceptor number (AN) of the solvent was obtained with identical slopes for reactions with phosphoryl and thiophosporyl compounds. The slopes for the dependence of ΔH or TΔS vs. AN for chlorine isotopic exchange in (PHO) 2 pace are opposite those for the exchange reaction in (PHO) 2 PSCl, so a constant ratio of k/sub p=O//k/sub p=s/ is observed, resulting from compensation of ΔH by ΔS. The effect of solvent on the initial state (from solubility measurements) and the transition state of the reaction between (PhO) 2 PSCl and the Cl- ion was evaluated. Changes of solvation of (PHO) 2 PSCE have practically no effect on the kinetics of the reactions. Changes of solvation of the chloride ion and of the transition state primarily influence the rate constants and activation parameters of the investigated isotopic-exchange reaction

  19. Quantitative chemical exchange saturation transfer with hyperpolarized nuclei (qHyper-CEST): sensing xenon-host exchange dynamics and binding affinities by NMR.

    Science.gov (United States)

    Kunth, M; Witte, C; Schröder, L

    2014-11-21

    The reversible binding of xenon to host molecules has found numerous applications in nuclear magnetic resonance studies. Quantitative characterization of the Xe exchange dynamics is important to understand and optimize the physico-chemical behavior of such Xe hosts, but is often challenging to achieve at low host concentrations. We have investigated a sensitive quantification technique based on chemical exchange saturation transfer with hyperpolarized nuclei, qHyper-CEST. Using simulated signals we demonstrated that qHyper-CEST yielded accurate and precise results and was robust in the presence of large amounts of noise (10%). This is of particular importance for samples with completely unknown exchange rates. Using these findings we experimentally determined the following exchange parameters for the Xe host cryptophane-A monoacid in dimethyl sulfoxide in one type of experiment: the ratio of bound and free Xe, the Xe exchange rate, the resonance frequencies of free and bound Xe, the Xe host occupancy, and the Xe binding constant. Taken together, qHyper-CEST facilitates sensitive quantification of the Xe exchange dynamics and binding to hydrophobic cavities and has the potential to analyze many different host systems or binding sites. This makes qHyper-CEST an indispensable tool for the efficient design of highly specific biosensors.

  20. Effect of hydrostatic and chemical pressure on the exchange interaction in magnetic borocarbide superconductors

    Science.gov (United States)

    Michor, H.; El-Hagary, M.; Naber, L.; Bauer, E.; Hilscher, G.

    2000-03-01

    The investigation of pair-breaking effects in magnetic rare-earth nickel borocarbide superconductors reveals a considerable increase of the magnetic exchange integral Jsf by hydrostatic as well as chemical pressure. In both, Jsf is governed by the R-C distance (or lattice constant a) and is described quantitatively by a simple phenomenological model. Thereby, just two parameters Jsf0=31 meV and ΔJsf/Δa=165 meV/Å explain well the influence of chemical pressure upon the initial depression rates of Tc in solid solutions R'1-xRxNi2B2C with R=Gd, Tb, Dy, Ho and R'=Y and Lu.