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

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)

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.

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.)

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

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

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.

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.

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.

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.)

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

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.

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.).

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

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

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.)

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)

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

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.)

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

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)

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.

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)

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

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

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)

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.

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

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)

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

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.

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

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

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

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.)

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

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%

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.)

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

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

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

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...

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)

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)

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.

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)

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)

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.

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

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)

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.

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

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

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)

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.

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

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

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.

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.

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

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.

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

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.

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)

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

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.

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.

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

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

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)

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.)

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.)

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

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.

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.

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

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'.

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.)

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)

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

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.

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

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.

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.

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)

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

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

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

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

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

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

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

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)

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)

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

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

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

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/.

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)

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

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

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

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

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)

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

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

International Nuclear Information System (INIS)

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

1992-01-01

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

Isotopic 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

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)

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)

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

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

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)

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)

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)

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)

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)

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)

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

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)

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

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.)

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)

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.

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

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.

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.)

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)

[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.

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

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.

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.)

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

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

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)

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)

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

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

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)

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)

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.

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)

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)

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

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)

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)

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

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

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

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

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.

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

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.

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

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)

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

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.

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)

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

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

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

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.)

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%

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

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.)

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

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.

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.

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)

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.

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

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

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)

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.

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

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...

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.

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.

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

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.

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

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

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

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

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.

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

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)

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

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)

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

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.

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)

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

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)

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.)

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

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

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

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

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

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)

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

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.

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

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

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

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.

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

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

Study of oxalic acid effect on equilibrium and kinetics of isotopic exchange between penta- and hexavalent neptunium in nitric acid solutions

International Nuclear Information System (INIS)

Nikitenko, S.I.; Ionnikova, N.I.

1989-01-01

Spectrophotometry at 25 deg C and ionic force μ=1.0 mol/l (KNO 3 +HNO 3 ) was used to show that at HNO 3 concentration 0.1-1.0 mol/l H 2 C 2 O 4 introduction to nitric acid solutions of Np 5+ in the presence of nitrite-ion resulted in the shift of equilibrium between Np 5+ and Np 6+ to the side of Np 6+ accumulation. The presence of H 2 C 2 O 4 at HNO 3 concentration > 1.0 mol/l doesn't affect the equilibrium position. The values of nominal equilibrium constant at different HNO 3 and H 2 C 2 O 4 concentrations were calculated. It was found that isotope exchange ( 239 Np/ 237 Np) between Np 5+ and Np 6+ in oxalate solutions proceeded more slowly than in oxalate absence. Rate constants of isotope exchange calculated at 9 deg C, μ=1.0 mol/l (KNO 3 ), H 2 C 2 O 4 concentration 0.01 mol/l and pH=2.2 and 3.5 are equal to 0.49x10 3 and 0.67x10 2 l/mol·min respectively. Mechanism of isotope exchange including electron transport between Np 5+ and Np 6+ oxalate complexes is suggested

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...

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

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)

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.

Melatonin labeled with hydrogen isotopes

International Nuclear Information System (INIS)

Dmitrevskaya, L.I.; Smushkevich, Yu.I.; Kurkovskaya, L.N.; Ponomarenko, N.K.; Suvorov, N.N.

1989-01-01

A study has been made of isotope exchange between melatonin and deuterium (D 2 O) or tritium (HTO) oxide under different conditions. The ease of isotope exchange for the indole ring hydrogens of melatonin in an acidic medium decreases over the series H 4 > H 2 H 6 >> H 7 , enabling the authors to process a route for production of melatonin labeled with hydrogen isotopes at positions 4,6, and 2 of the indole ring. A method has been suggested for producing melatonin labeled with hydrogen isotopes at position 2 by desulfurization of 2-(2,4-dinitro-phenylsulfenyl)melatonin at Ni(Re) (D)

Melatonin labelled by hydrogen isotopes

International Nuclear Information System (INIS)

Dmitrevskaya, L.I.; Smushkevich, Yu.I.; Kurkovskaya, L.N.; Ponomarenko, N.K.; Suvorov, N.N.

1988-01-01

Isotope exchange of melatonin with deuterium (D 2 O) and tritium (HTO) oxides under different conditions is studied. Simplicity of isotope exchange of hydrogens of the indole ring of melatonin in the acidic medium decreases in series H 4 >H 2 >H 6 >>H 7 , that permits to suggest the way of melatonin preparation labelled by hydrogen isotopes in positions 4,6 and 2 of the indole ring. The way of melatonin preparation labelled by hydrogen isotopes in position 2 according to the reaction of desulfation 2-(2,4-dinitrophenylsulphenyl) melatonin at catalyst Ni(Re)(D) is suggested

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

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)

Multiple stable isotope fronts during non-isothermal fluid flow

Science.gov (United States)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may

Application of the isotopic index in isotope geochemical investigation

International Nuclear Information System (INIS)

Schuetze, H.

1982-06-01

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

The transport of oxygen isotopes in hydrothermal systems

International Nuclear Information System (INIS)

McKibbin, R.; Absar, A.; Blattner, P.

1986-01-01

As groundwater passes through porous rocks, exchange of oxygen between the fluid and the solid matrix causes a change in the oxygen isotope concentrations in both water and rock. If the rate at which the exchange takes place can be estimated (as a function of the isotope concentrations and temperature) then the time taken for a rock/water system to come to equilibrium with respect to isotope concentration might be calculated. In this paper, the equation for isotope transport is derived using conservation laws, and a simple equation to describe the rate of isotope exchange is proposed. These are combined with the equations for fluid flow in a porous medium, to produce a general set of equations describing isotope transport in a hydrothermal system. These equations are solved numerically, using typical parameters, for the one-dimensional case. Oxygen isotope data from the basement rocks underlying Kawerau geothermal field are modelled. The results indicate that the time taken for exchange of 18 O to present-day values is less than the postulated age of hydrothermal alteration in that field. This suggests that, although controlled by similar parameters, oxygen isotope exchange, in felsic rocks at least, is much faster than hydrothermal alteration. This conclusion is consistent with the petrographic observations from the Kawerau system as well as other geothermal fields

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

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.)

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

Energy Technology Data Exchange (ETDEWEB)

Wunderlich, Anja A.L.

2012-11-02

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.

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)

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)

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.)

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.

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

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)

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

Sm isotope composition and Sm/Eu ratio determination in an irradiated 153Eu sample by ion exchange chromatography-quadrupole inductively coupled plasma mass spectrometry combined with double spike isotope dilution technique

International Nuclear Information System (INIS)

Bourgeois, M.; Isnard, H.; Gourgiotis, A.; Stadelmann, G.; Gautier, C.; Mialle, S.; Nonell, A.; Chartier, F.

2011-01-01

Within the framework of the research undertaken by the French Atomic Energy Commission on transmutation of long-lived radionuclides, targets of highly enriched actinides and fission products were irradiated in the fast neutron reactor Phenix. Precise and accurate measurements of the isotopic and elemental composition of the enriched elements are therefore required. In order to obtain the uncertainties of several per mil and to reduce handling time and exposure to analyst on radioactive material, the on-line coupling of ion exchange chromatography with quadrupole inductively coupled plasma mass spectrometry has been associated with the technique of the double spike isotope dilution. We present in this paper the results obtained on an irradiated sample of Europium oxide powder (enriched at 99.13% in 153 Eu). After irradiation of around 5 mg of Eu 2 O 3 powder the theoretical calculations predict the formation of several micrograms of gadolinium and samarium isotopes. In relation to the very high activity of the sample after irradiation and the very low quantity of Sm formed, the on-line ion exchange chromatography separation of Gd, Sm and Eu before Sm isotope ratio measurements has been developed for the quantification of the 152 Sm/ 153 Eu ratio. These on-line measurements were associated with the double spike isotope dilution technique after calibration of a 147 Sm/ 151 Eu spike solution. The external reproducibility of Sm isotopic ratios was determined to be around 0.5% (2 σ) resulting in a final uncertainty on the 152 Sm/ 153 Eu ratio of around 1% (2 σ). These on-line measurements present therefore a robust and high-throughput alternative to the thermal-ionisation mass spectrometry technique used so far in combination with off-line chromatographic separation, particularly in nuclear applications where characterisation of high activity sample solutions is required. (authors)

Hydrogen/deuterium exchange in mass spectrometry.

Science.gov (United States)

Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

2018-03-30

The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

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.

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

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.

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

Boron isotopic enrichment by displacement chromatography

International Nuclear Information System (INIS)

Mohapatra, K.K.; Bose, Arun

2014-01-01

10 B enriched boron is used in applications requiring high volumetric neutron absorption (absorption cross section- 3837 barn for thermal and 1 barn for 1 MeV fast neutron). It is used in fast breeder reactor (as control rod material), in neutron counter, in Boron Neutron Capture Therapy etc. Owing to very small separation factor, boron isotopic enrichment is a complex process requiring large number of separation stages. Heavy Water Board has ventured in industrial scale production of 10 B enriched boron using Exchange Distillation Process as well as Ion Displacement Chromatography Process. Ion Displacement Chromatography process is used in Boron Enrichment Plant at HWP, Manuguru. It is based on isotopic exchange between borate ions (B(OH) 4 - ) on anion exchange resin and boric acid passing through resin. The isotopic exchange takes place due to difference in zero point energy of 10 B and 11 B

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)

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)

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)

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.

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.)

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)

Enrichment of 15N by ion exchange chromatography

International Nuclear Information System (INIS)

Ohwaki, Masao; Ohtsuka, Haruhisa; Nomura, Masao; Okamoto, Makoto; Fujii, Yasuhiko

1996-01-01

15 N isotope separation was studied using cation exchange resins which consist of functional groups: sulfonic acid, carboxylic acid and phenol at various concentration of the eluent LiOH. The isotope separation coefficients for these ion exchange resins were observed to be nearly equal, in spite of the large difference in ion exchange characteristics. The effect of flow rate on 15 N isotope separation was also studied, and the results indicate that the operation at high flow rate would be preferable for the industrial process of 15 N enrichment. Based on the preliminary investigations, a continuous operation using a series of ion exchange columns has been carried out in order to achieve high enrichment of 15 N. (author)

Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using 13C NMR hydrogen/deuterium isotope shifts

International Nuclear Information System (INIS)

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

1987-01-01

Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a 13 C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D 2 O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H 2 O solutions; in 1:1 H 2 O/D 2 O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with 13 C at the peptide carbonyls of alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results

Oxygen and U-Th isotopes and the timescales of hydrothermal exchange and melting in granitoid wall rocks at Mount Mazama, Crater Lake, Oregon

Science.gov (United States)

Ankney, Meagan E.; Bacon, Charles R.; Valley, John W.; Beard, Brian L.; Johnson, Clark M.

2017-01-01

We report new whole rock U-Th and in-situ oxygen isotope compositions for partially melted (0–50 vol% melt), low-δ18O Pleistocene granitoid blocks ejected during the ∼7.7 ka caldera-forming eruption of Mt. Mazama (Crater Lake, Oregon). The blocks are interpreted to represent wall rocks of the climactic magma chamber that, prior to eruption, experienced variable amounts of exchange with meteoric hydrothermal fluids and subsequent partial melting. U-Th and oxygen isotope results allow us to examine the timescales of hydrothermal circulation and partial melting, and provide an “outside in” perspective on the buildup to the climactic eruption of Mt. Mazama. Oxygen isotope compositions measured in the cores and rims of individual quartz (n = 126) and plagioclase (n = 91) crystals, and for transects across ten quartz crystals, document zonation in quartz (Δ18OCore-Rim ≤ 0.1–5.5‰), but show homogeneity in plagioclase (Δ18OCore-Rim ≤ ±0.8‰). We propose that oxygen isotope zonation in quartz records hydrothermal exchange followed by high-temperature exchange in response to partial melting caused by injection of basaltic to andesitic recharge magma into the deeper portions of the chamber. Results of modeling of oxygen diffusion in quartz indicates that hydrothermal exchange in quartz occurred over a period of ∼1000–63,000 years. Models also suggest that the onset of melting of the granitoids occurred a minimum of ∼10–200 years prior to the Mazama climactic eruption, an inference which is broadly consistent with results for magnetite homogenization and for Zr diffusion in melt previously reported by others.Uranium-thorium isotope compositions of most granitoid blocks are in 238U excess, and are in agreement with a 238U enriched array previously measured for volcanic rocks at Mt. Mazama. Uranium excess in the granitoids is likely due to enrichment via hydrothermal circulation, given their low δ18O values. The sample with the

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

Process and device for U isotope separation

International Nuclear Information System (INIS)

Aubert, Jacques; Carles, Maurice; Neige, Roger.

1976-01-01

The description is given of a process for enriching uranium with one of its isotopes by isotopic exchange in sub-cascades assembled to form a cascade, each sub-cascade having facilities for bringing into contact an aqueous phase charged with uranium of a lower valency with an organic phase charged with uranium of a higher valency, in conditions that restrict the transfer of upper valency uranium into the aqueous phase. Each sub-cascade has the following stages at least: isotopic exchange in a set of contact systems between the aqueous phase and the organic phase where the aqueous phase depletes and the organic phase becomes enriched with isotope 235; uranium extraction until depletion of the organic phase in a first extractor; reduction of the liquid phase uranium and acidification before this reduced aqueous phase passes into the isotopic exchange system then oxidation of the uranium of this aqueous phase coming from the system; extraction of the aqueous phase uranium until depletion in the second extractor by the organic phase [fr

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

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)

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

Study ω and φ photoproduction in the nucleon isotopic channels

International Nuclear Information System (INIS)

Zhao, Q.

2002-01-01

We present results for the photoproduction of ω and φ meson in the nucleon isotopic channels. A recently developed quark model with an effective Lagrangian is employed to account for the non-diffractive s- and u-channel processes; the diffractive feature arising from the natural parity exchange is accounted for by the t-channel pomeron exchange, while the unnatural parity exchange is accounted for by the t-channel pion exchange. In the ω production, the isotopic effects could provide more information concerning the search of 'missing resonances', while in the φ production, the isotopic effects could highlight non-diffractive resonance excitation mechanisms at large angles. (author)

Rapid deuterium exchange-in time for probing conformational change

International Nuclear Information System (INIS)

Dharmasiri, K.; Smith, D.L.

1995-01-01

Isotopic exchange of protein backbone amide hydrogens has been used extensively as a sensitive probe of protein structure. One of the salient features of hydrogen exchange is the vast range of exchange rates in one protein. Isotopic exchange methods have been used to study the structural features including protein folding and unfolding (1), functionally different forms of proteins (2), protein-protein complexation (3), and protein stability parameter. Many backbone amide protons that are surface accessible and are not involved in hydrogen bonding undergo rapid deuterium exchange. In order to study, fast exchanging amide protons, fast exchange-in times are necessary

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.)

Assessment of phyto-available cadmium in soils using isotopic methods

International Nuclear Information System (INIS)

Gerard, Emilie

2000-01-01

The quantification of phyto-available Cd in soils is necessary to determine the transfer risk of this toxic element to plants. Isotopic methods (isotopic exchange kinetics (IEK), isotopic dilution) were used to characterize the phyto-available Cd and, practically, to select chemical methods for determining available Cd to plants. Rye grass (Lolium perenne L.), lettuce (Lactuca saliva L.) and the Cd hyper-accumulator Thlaspi caerulescens J. Presl. and C. Presl. were selected as test plants because of their wide range of Cd uptake ability. The chosen soils had different pH and displayed a Cd-contamination gradient due the atmospheric deposition of industrial particles. In the acidic soil, plants had access to the same metal pool, the one that was isotopically exchangeable with Cd 2+ . This was also the case for rye grass on the calcareous Soils but there, lettuce and T. caerulescens accessed a bigger and non-isotopically exchangeable pool that accounted for 16 to 52 % of the plant available Cd. Most of the Cd was isotopically exchangeable in a short time in the acidic soil (87 % within 21 days). In the calcareous soils two pools were identified, one pool was isotopically exchangeable in a very short time, and the other one Was not exchangeable after 21 days (21 to 10 % of the total Cd). Actually, the quantities of labile cd in the industrial particles which had contaminated these soils were very small. IEK methods and the measurement of the isotopic composition of Cd 2+ in soil solutions allowed for the estimation of the phyto-available Cd in soils, but cannot he commonly used. Most of the chemical extractants studied such as CaCl 2 or DTP A are suitable to assess the phyto-available Cd. However, on calcareous soils, the choice of extractant needs to sometimes be modified in relation to the rate of Cd plant absorption. (author) [fr

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

Oxygen and hydrogen isotope fractionation during cellulose metabolism in Lemna gibba L

International Nuclear Information System (INIS)

Yakir, D.; DeNiro, M.J.

1990-01-01

Lemna gibba L. B3 was grown under heterotrophic, photoheterotrophic, and autotrophic conditions in water having a variety of hydrogen and oxygen isotopic compositions. The slopes of the linear regression lines between the isotopic composition of water and leaf cellulose indicated that under the three growth conditions about 40, 70, and 100% of oxygens and carbon-bound hydrogens of cellulose exchanged with those of water prior to cellulose formation. Using the equations of the linear relationships, we estimated the overall fractionation factors between water and the exchanged oxygen and carbon bound-hydrogen of cellulose. At least two very different isotope effects must determine the hydrogen isotopic composition of Lemna cellulose. One reflects the photosynthetic reduction of NADP, while the second reflects exchange reactions that occur subsequent to NADP reduction. Oxygen isotopic composition of cellulose apparently is determined by a single type of exchange reaction with water. Under different growth conditions, variations in metabolic fluxes affect the hydrogen isotopic composition of cellulose by influencing the extent to which the two isotope effects mentioned above are recorded. The oxygen isotopic composition of cellulose is not affected by such changes in growth conditions

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

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)

Ca isotopic fractionation patterns in forest ecosystems

Science.gov (United States)

Kurtz, A. C.; Takagi, K.

2012-12-01

Calcium stable isotope ratios are an emerging tracer of the biogeochemical cycle of Ca that are just beginning to see significant application to forest ecosystems. The primary source of isotopic fractionation in these systems is discrimination against light Ca during uptake by plant roots. Cycling of vegetation-fractionated Ca establishes isotopically distinct Ca pools within a forest ecosystem. In some systems, the shallow soil exchangeable Ca pool is isotopically heavy relative to Ca inputs. This has been explained by preferential removal of light Ca from the soil. In other systems, the soil exchange pool is isotopically light relative to inputs, which is explained by recycling of plant-fractionated light Ca back into soil. Thus vegetation uptake of light Ca has been called on to account for both isotopically heavy and light Ca in the shallow soil exchange pools. We interpret patterns in ecosystem δ44Ca with the aid of a simple box model of the forest Ca cycle. We suggest that the δ44Ca of exchangeable Ca in the shallow soil pool primarily reflects the relative magnitude of three key fluxes in a forest Ca cycle, 1) the flux of external Ca into the system via weathering or atmospheric deposition, 2) the uptake flux of Ca from soils into the vegetation pool, and 3) the return flux of Ca to shallow soils via remineralization of leaf litter. Two observations that emerge from our model may aid in the application of Ca isotopes to provide insight into the forest Ca cycle. First, regardless of the magnitude of both vegetation Ca uptake and isotopic fractionation, the δ44Ca of the soil exchange pool will equal the input δ44Ca unless the plant uptake and remineralization fluxes are out of balance. A second observation is that the degree to which the shallow soil exchange pool δ44Ca can differ from the input ratio is controlled by the relative rates of biological uptake and external Ca input. Significant differences between soil exchange and input δ44Ca are seen only

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

Isotope separation process

International Nuclear Information System (INIS)

Cabicar, J.; Stamberg, K.; Katzer, J.

1983-01-01

A process for separating isotopes by the method of controlled distribution is claimed. A first phase is either a solution of isotopic components and a ligand (from 10 - 6 M to a saturated solution), or a gaseous mixture of isotopic components, or a gaseous mixture of isotopic components and an inert gas. The isotopes are in the starting mixture in molar ratio from 1:10 5 to 1:10 - 5 . The second phase is a solid sorbent such as styrene-divinylbenzene ion exchangers, or bio-sorbents on the basis of mycelium of lower fungi and sorbents on the basis of cellulose, or an extraction agent such as tributyl phosphate and trioctyl amine, if need be, kept by a carrier such as teflon, silica gel and cellulose. The two-phase system exhibits non-linear equilibrium isotherm for sorption and/or desorption or for extraction and/or re-extraction. After bringing both phases into contact the rate of transport of isotopic components from one phase into another is not equal. Retardation of isotopic exchange takes place by complexation of isotopes with ligands such as cabonate, sulphate, citrate, chloride and ethylenediamine tetraacetate ions, or by using sorbents and extraction agents with chelating functional groups such as carboxyl and hyroxyl groups, groups on the basis of phosphorus, nitrogen and sulphur and/or by operating in darkness, or in the light having wave length between 2.5x10 2 and 10 9 nm. The contact time is between 10 - 2 and 10 6 s, temperature between 10 2 and 10 3 K, the number of stirrer revolutions between 10 - 2 and 10 4 revolutions per s, flow rate at column arrangement between 10 - 6 and 10 - 1 m/s and the size of particles of sorbent between 10 - 6 and 10 - 2 m

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)

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)

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

Homogeneous deuterium exchange using rhenium and platinum chloride catalysts

International Nuclear Information System (INIS)

Fawdry, R.M.

1979-01-01

Previous studies of homogeneous hydrogen isotope exchange are mostly confined to one catalyst, the tetrachloroplatinite salt. Recent reports have indicated that chloride salts of iridium and rhodium may also be homogeneous exchange catalysts similar to the tetrachloroplatinite, but with much lower activities. Exchange by these homogeneous catalysts is frequently accompanied by metal precipitation with the termination of homogeneous exchange, particularly in the case of alkane exchange. The studies presented in this thesis describe two different approaches to overcome this limitation of homogeneous hydrogen isotope exchange catalysts. The first approach was to improve the stability of an existing homogeneous catalyst and the second was to develop a new homogeneous exchange catalyst which is free of the instability limitation

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

A simple and reliable anion-exchange resin method for sulfate extraction and purification suitable for multiple O- and S-isotope measurements.

Science.gov (United States)

Le Gendre, Erwann; Martin, Erwan; Villemant, Benoit; Cartigny, Pierre; Assayag, Nelly

2017-01-15

The O- and S-isotope compositions of sulfates can be used as key tracers of the fate and sink of sulfate in both terrestrial and extra-terrestrial environments. However, their application remains limited in those geological systems where sulfate occurs in low concentrations. Here we present a simple and reliable method to extract, purify and concentrate sulfate from natural samples. The method allows us to take into account the separation of nitrate, which is known to be an issue in O-isotope analysis. The separation and concentration of sulfate from other anions in any aqueous solution are performed within a few hours via anion-exchange resin. The possible O- (δ 18 O and Δ 17 O) and S- (δ 34 S, Δ 33 S and Δ 36 S) isotope exchanges, fractionations and/or contaminations are for the first time monitored during the whole procedure using initial O- and S-mass-dependent and mass-independent sulfate solutions. After elution in HCl, pure sulfate is fully retrieved and precipitated into BaSO 4 , which is suitable for O- and S-isotopic measurements using established techniques. The analysis of retrieved barite presents no variation within 2σ uncertainties: ±0.5‰ and ±0.1‰ in O- (δ 18 O, Δ 17 O) and ±0.2‰, ±0.02‰ and ±0.09‰ in S- (δ 34 S, Δ 33 S and Δ 36 S) isotope ratios, respectively. This study shows that the resin method for sulfate extraction and purification, in addition to being cheap, simple and quick, is applicable for the measurements of all O- and S-isotopic ratios in sulfates (including the Δ 17 O, Δ 33 S and Δ 36 S values). Therefore, this method can be easily used for a high range of natural samples in which sulfate occurs in low concentration including aerosols, ice cores, sediments, volcanic deposits, (paleo)soils and rainwater, and thus it can be a key to our understanding of the sulfur cycle on Earth. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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)%

Process chemistry related to hydrogen isotopes

International Nuclear Information System (INIS)

Iwasaki, Matae; Ogata, Yukio

1991-01-01

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

Process and apparatus for the separtaion of isotopes

International Nuclear Information System (INIS)

Ma, I.J.

1983-01-01

A process is claimed for the separation of isotopes particularly uranium isotopes, characterized by the fact that this process is based on the charge exchange reaction (A + + B → A+B + ), with the atomic ions A + of one of the isotopes of an element being selectively excited and the atomic ions of the other isotope of the same element being allowed to remain in the ground state, and with the excited ions being neutralized by means of atoms or molecules (B) after the charge exchange reaction has been completed. For the selection of an atom or molecule B the first ionization potential thereof should be greater than the ionization potential of uranium. Laser radiation is used to excite the atoms

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)

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

Isotopic equilibria between sulphur solute species at high temperature

International Nuclear Information System (INIS)

Robinson, B.W.

1978-01-01

Sulphur solute species in ore solutions and geothermal discharges include HSO 4 - , SO 4 2- , H 2 S, and HS - , as well as the ion-paired species, NaHS 0 , NaHSO 4 - and Na 2 SO 4 0 . Observed sulphate-sulphide fractionation factors and the rates of attainment of isotopic equilibrium are likely to depend on the nature of the sulphur species actually taking part in these isotopic equilibria. Preliminary experiments in alkaline solution (pH 10.1 at 20 0 C) were carried out in a gold cell. No significant isotope fractionation was observed between the SO 4 2- and HS - in 29 days at 200 0 C, 63days at 300 0 C, or 90 days at 250 0 C. However, similar experiments at 350 0 C in sealed gold capsules at room temperature pH 8.5 showed slow exchange(t( 1 / 2 ) was calculated to be 510 days for the SO 4 2- -HS - exchange reaction using the theoretical fractionation of 20.2 0 / 00 ). The addition of NaCl appeared to have no affect on the exchange. However, pH strongly controls the reaction rate, and exchange probably involves H 2 S and the HSO 4 - ion. Additional preliminary experiments were conducted with a fivefold increase in the sulphur concentration; a decrease in t( 1 / 2 ) to 142 days resulted. Some inter-relationship between sulphur concentration and exchange rate thus exists. The important controlling parameters of isotope exchange (temperature, pH, and ΣS) can be seen to have influenced exchange in natural systems.(auth.)

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)

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)

Biology and air–sea gas exchange controls on the distribution of carbon isotope ratios (δ13C in the ocean

Directory of Open Access Journals (Sweden)

A. Schmittner

2013-09-01

Full Text Available Analysis of observations and sensitivity experiments with a new three-dimensional global model of stable carbon isotope cycling elucidate processes that control the distribution of δ13C of dissolved inorganic carbon (DIC in the contemporary and preindustrial ocean. Biological fractionation and the sinking of isotopically light δ13C organic matter from the surface into the interior ocean leads to low δ13CDIC values at depths and in high latitude surface waters and high values in the upper ocean at low latitudes with maxima in the subtropics. Air–sea gas exchange has two effects. First, it acts to reduce the spatial gradients created by biology. Second, the associated temperature-dependent fractionation tends to increase (decrease δ13CDIC values of colder (warmer water, which generates gradients that oppose those arising from biology. Our model results suggest that both effects are similarly important in influencing surface and interior δ13CDIC distributions. However, since air–sea gas exchange is slow in the modern ocean, the biological effect dominates spatial δ13CDIC gradients both in the interior and at the surface, in contrast to conclusions from some previous studies. Calcium carbonate cycling, pH dependency of fractionation during air–sea gas exchange, and kinetic fractionation have minor effects on δ13CDIC. Accumulation of isotopically light carbon from anthropogenic fossil fuel burning has decreased the spatial variability of surface and deep δ13CDIC since the industrial revolution in our model simulations. Analysis of a new synthesis of δ13CDIC measurements from years 1990 to 2005 is used to quantify preformed and remineralized contributions as well as the effects of biology and air–sea gas exchange. The model reproduces major features of the observed large-scale distribution of δ13CDIC as well as the individual contributions and effects. Residual misfits are documented and analyzed. Simulated surface and subsurface �

Hafnium at subduction zones: isotopic budget of input and output fluxes

International Nuclear Information System (INIS)

Marini, J.Ch.

2004-05-01

Subduction zones are the primary regions of mass exchanges between continental crust and mantle of Earth through sediment subduction toward the earth's mantle and by supply of mantellic magmas to volcanic arcs. We analyze these mass exchanges using Hafnium and Neodymium isotopes. At the Izu-Mariana subduction zone, subducting sediments have Hf and Nd isotopes equivalent to Pacific seawater. Altered oceanic crust has Hf and Nd isotopic compositions equivalent to the isotopic budget of unaltered Pacific oceanic crust. At Luzon and Java subduction zones, arc lavas present Hf isotopic ratios highly radiogenic in comparison to their Nd isotopic ratios. Such compositions of the Luzon and Java arc lavas are controlled by a contamination of their sources by the subducted oceanic sediments. (author)

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

International Nuclear Information System (INIS)

Dehez, F.

2002-01-01

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

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

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.

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

Catalytic process for tritium exchange reaction

International Nuclear Information System (INIS)

Hansoo Lee; Kang, H.S.; Paek, S.W.; Hongsuk Chung; Yang Geun Chung; Sook Kyung Lee

2001-01-01

The catalytic activities for a hydrogen isotope exchange were measured through the reaction of a vapor and gas mixture. The catalytic activity showed to be comparable with the published data. Since the gas velocity is relatively low, the deactivation was not found clearly during the 5-hour experiment. Hydrogen isotope transfer experiments were also conducted through the liquid phase catalytic exchange reaction column that consisted of a catalytic bed and a hydrophilic bed. The efficiencies of both the catalytic and hydrophilic beds were higher than 0.9, implying that the column performance was excellent. (author)

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

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.

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)

Radiotracer application for characterization of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC

International Nuclear Information System (INIS)

Singare, P.U.

2015-01-01

Radio isotopic tracer technique as one of the versatile nondestructive technique is employed to evaluate the performance of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC. The evaluation was made on the basis of ion-isotopic exchange reaction kinetics by using 131 I and 82 Br radioactive tracer isotopes. It was observed that for both the resins, the values of specific reaction rate (min -1 ), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) were calculated to be lower for bromide ion-isotopic exchange reaction than that for iodide ion-isotopic exchange reaction. It was observed that for iodide ion-isotopic exchange reaction under identical experimental conditions of 30.0 C, 1.000 g of ion exchange resins and 0.001 mol/L labeled iodide ion solution, the values of specific reaction rate (min -1 ), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K d were calculated as 0.377, 0.212, 0.080 and 15.5 respectively for Dowex SBR LC resin, which was higher than 0.215, 0.144, 0.031 and 14.1 respectively as that obtained for Tulsion A23 resins. Also at a constant temperature of 30.0 C, as the concentration of labeled iodide ion solution increases from 0.001 mol/L to 0.004 mol/L, the percentage of iodide ions exchanged increases from 84.75 % to 90.20 % for Dowex SBR LC resins which was higher than increases from 57.66 % to 62.38 % obtained for Tulsion A23 resins. The identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate superior performance of Dowex SBR LC over Tulsion A23 resins under identical experimental conditions.

Iodine isotopes and radiation safety

International Nuclear Information System (INIS)

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

1992-01-01

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

The reactivity of anion-exchange resins by applying OT-for-OH exchange reaction in the equilibrium state

International Nuclear Information System (INIS)

Kano, Naoki; Nihei, Makoto; Imaizumi, Hiroshi

1996-01-01

In order to reveal the behavior of hydroxyl group in isotope exchange reaction, OT-for-OH exchange reaction between each anion-exchange resin (OH - form) and tritiated water (abbreviated as HTO water below) was observed at 80degC under the equilibrium. Anion-exchange resins used were Amberlite IRA-400, IRA-410 (both strongly basic), and IRA-94S (weakly basic). It can be thought that an HTO molecule dissociates into H + +OT - (or T + +OH - ). The activity of each resin based on OT-for-OH exchange reaction was measured with a liquid scintillation counter. From the above-mentioned, the following five were found. Isotope exchange reaction as 'atomic group' occurred between the OH group in each anion-exchange resin and the OT group in HTO water. The reactivity of strongly basic anion-exchange resin is larger than that of weakly basic one. The ratio of the reactivity of these resins can roughly be expressed as follows: (IRA-410): (IRA-400): (IRA-94S)=42: 7: 1. The degree of OT-for-OH exchange reaction may be smaller than that of T-for-H exchange reaction. The method used and results obtained in this work may be helpful to obtain the data for the prevention of T-contamination, especially to obtain the data from certain atomic groups including T. (author)

Performance evaluation of anion exchange resins Purolite NRW-5050 and Duolite A-611 by application of radioisotopic techniques

International Nuclear Information System (INIS)

Singare, P.U.

2014-01-01

Radioanalytical techniques using 131 I and 82 Br as tracer isotopes were applied to study the kinetics of iodide and bromide ion-isotopic exchange reactions taking place between the external labeled ionic solution and the resin surface. The results indicate low values of specific reaction rate (min -1 ), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) for bromide ion-isotopic exchange reaction as compared to that obtained for iodide ion-isotopic exchange reaction. It was observed that for iodide ion-isotopic exchange reaction performed at 35.0 C, 1 000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution, the values of specific reaction rate (min -1 ), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K d were 0.340, 0.394, 0.134 and 20.2 respectively for Purolite NRW-5050 resin, which was higher than the respective values of 0.216, 0.290, 0.063 and 18.2 as that obtained by using Duolite A-611. The results of present investigation indicate that during the two ion-isotopic exchange reactions, for both the resins, there exists a strong positive linear correlation between amount of ions exchanged and concentration of ionic solution; and strong negative correlation between amount of ions exchanged and temperature of exchanging medium. From the results it appears that as compared to Duolite A-611 resins, Purolite NRW-5050 resins shows superior performance under identical experimental conditions.

Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

Science.gov (United States)

ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

2017-06-20

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short

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)

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

Energy Technology Data Exchange (ETDEWEB)

Arndt Schimmelmann; Maria Mastalerz

2010-03-30

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

Effects of arbuscular mycorrhizal fungi on gas exchange and stable isotope ratio of δ13C, δ15N of leymus chinensis plant

International Nuclear Information System (INIS)

Shi Weiqi; Wang Guoan; Li Xiaolin

2008-01-01

Leymus chinensis, one of dominant species in Inner Mongolia grassland, was selected to evaluate the effects of arbuscular mycorrhizal fungi (AMF) on plant gas change parameters and stable isotope ratio in pot culture. The plant was inoculated with two mycorrhizal fungi, Glomus intraradices and Glomus claroidum, and the uninoculated plant was used as the control check. On the 45th , 60th , 75th days after sowing, gas exchange parameters and stable isotope ratio were measured. The results showed that AM infection promoted phosphoms content, stomatal conductance and photosynthetic rate of Leymus chinensis, reduced host δ 15 N, however, it did not influence host intrinsic water using efficiency and δ 13 C. It was the growth time that significantly affected the gas exchange and stable isotope ratio of δ 13 C and δ 15 N. And the interaction of inoculation and growth time also influenced on the net photosynthetic rate, δ 13 C and δ 15 N of the host. Stomatal conductance and photosynthetic rate were always changed the same direction by arbuscular mycorrhizal fungi causing no significant difference between mycorrhizal and non-mycorrhizal plant. AMF absorbed nitrogen and accumulated δ 15 N, thus, it transformed less 15 N into the host, and as a result, the mycorrhizal plant had lower δ 15 N. Therefore, the results gave a new way and reference to know of the grass balance of carbon gain and water cost and the nitrogen cycle in grassland. (authors)

Geochemical isotope compartment model of the nitrogen cycle

International Nuclear Information System (INIS)

Weise, G.; Wetzel, K.; Stiehl, G.

1981-01-01

A model of the global cycle of nitrogen and its isotopes is described. It takes into account geochemical reservoirs (nitrogen in magmatic metamorphic, and sedimentary rocks and in the atmosphere) and the nitrogen exchange between magmatic rocks and the outer mantle, the transition of nitrogen exchange between sedimentary rocks and the atmosphere. With the aid of the mathematical formalisms of the compartment theory and on the basis of all available delta 11 N values assumptions regarding the isotope effects in forming these nitrogen fluxes data have been obtained on the degree of the nitrogen exchange between the earth crust and the outer mantle and on other nitrogen fluxes characterizing the global nitrogen cycle. (author)

Isotopic-spectral determination of hydrogen, nitrogen, oxygen and carbon in semiconductor materials

International Nuclear Information System (INIS)

Dudich, G.K.; Eremeev, V.A.; Li, V.N.; Nemets, V.M.

1981-01-01

Techniques of low-temperature isotopic-spectral determination of impurities of hydrogen, nitrogen, oxygen and carbon in semiconductor materials Bi, Ge, Pb tellurides are developed. The techniques include selection into special vessel with the known volume (exchanger) of sample analyzed, dosed introduction into exchanger of rare isotope of the element determined ( 2 H, 15 N, 18 O, 13 C) in the form of isotope-containing gas, balancing of the determined element isotopes in the system sample-isotope, containing gas, spectroscopic, determination of its isotope composition in gaseous phase of the system and calculation of the amount of the element determined in the sample. The lower boundaries of the amounts determined constitute 10 -7 , 10 -7 , 10 -6 and 10 -5 mass % respectively when sample of 20 g are used [ru

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

Science.gov (United States)

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

1989-01-01

The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and

Inferring foliar water uptake using stable isotopes of water.

Science.gov (United States)

Goldsmith, Gregory R; Lehmann, Marco M; Cernusak, Lucas A; Arend, Matthias; Siegwolf, Rolf T W

2017-08-01

A growing number of studies have described the direct absorption of water into leaves, a phenomenon known as foliar water uptake. The resultant increase in the amount of water in the leaf can be important for plant function. Exposing leaves to isotopically enriched or depleted water sources has become a common method for establishing whether or not a plant is capable of carrying out foliar water uptake. However, a careful inspection of our understanding of the fluxes of water isotopes between leaves and the atmosphere under high humidity conditions shows that there can clearly be isotopic exchange between the two pools even in the absence of a change in the mass of water in the leaf. We provide experimental evidence that while leaf water isotope ratios may change following exposure to a fog event using water with a depleted oxygen isotope ratio, leaf mass only changes when leaves are experiencing a water deficit that creates a driving gradient for the uptake of water by the leaf. Studies that rely on stable isotopes of water as a means of studying plant water use, particularly with respect to foliar water uptake, must consider the effects of these isotopic exchange processes.

Extraction separation of lithium isotopes with crown-ethers

International Nuclear Information System (INIS)

Tsivadze, A.Yu.; Demin, S.V.; Levkin, A.V.; Zhilov, V.I.; Nikol'skij, S.F.; Knyazev, D.A.

1990-01-01

By the method of extraction chromatography lithium isotope separation coefficients are measured during chemical isotope exchange between lithium aquocomplex and its complex in chloroform with crown-ethers: benzo-15-crown-5, 15crown-5, dicyclohexano-18-crown-6 and dibenzo-18-crown-6. Lithium perchlorate and trichloroacetate are the salts extracted. Values of 6 Li/ 7 Li isotope separation are 1.0032-1.020

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)

Natural radium and radon tracers to quantify water exchange and movement in reservoirs

Science.gov (United States)

Smith, Christopher G.; Baskaran, Mark

2011-01-01

Radon and radium isotopes are routinely used to quantify exchange rates between different hydrologic reservoirs. Since their recognition as oceanic tracers in the 1960s, both radon and radium have been used to examine processes such as air-sea exchange, deep oceanic mixing, benthic inputs, and many others. Recently, the application of radon-222 and the radium-quartet (223,224,226,228Ra) as coastal tracers has seen a revelation with the growing interest in coastal groundwater dynamics. The enrichment of these isotopes in benthic fluids including groundwater makes both radium and radon ideal tracers of coastal benthic processes (e.g. submarine groundwater discharge). In this chapter we review traditional and recent advances in the application of radon and radium isotopes to understand mixing and exchange between various hydrologic reservoirs, specifically: (1) atmosphere and ocean, (2) deep and shallow oceanic water masses, (3) coastal groundwater/benthic pore waters and surface ocean, and (4) aquifer-lakes. While the isotopes themselves and their distribution in the environment provide qualitative information about the exchange processes, it is mixing/exchange and transport models for these isotopes that provide specific quantitative information about these processes. Brief introductions of these models and mixing parameters are provided for both historical and more recent studies.

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

Biogeochemistry of the stable hydrogen isotopes

International Nuclear Information System (INIS)

Estep, M.F.; Hoering, T.C.

1980-01-01

The fractionation of H isotopes between the water in the growth medium and the organically bonded H from microalgae cultured under conditions, where light intensity and wavelength, temperature, nutrient availability, and the H isotope ratio of the water were controlled, is reproducible and light dependent. All studies were based either on the H isotope ratios of the total organic H or on the lipids, where most of the H is firmly bonded to C. H bonded into other macromolecules, proteins, carbohydrates and nucleic acids, does not exchange with water, when algae are incubated in water enriched with deuterium. Only after the destruction of quaternary H bonds are labile hydrogens in macromolecules free to exchange with water. By growing algae (18 strains), including blue-green algae, green algae and diatoms, in continuous light, the isotope fractionations in photosynthesis were reproducibly -93 to -178 per thousand, depending on the organism tested. This fractionation was not temperature dependent. Microalgae grown in total darkness with an organic substrate did not show the isotope fractionation seen in cells grown in light. In both light- and dark-grown algae, however, additional depletion of deuterium (-30 to -60 per thousand) in cellular organic matter occurs during the metabolism of carbohydrates to form lipids. Plants from several natural populations also fractionated isotopes during photosynthesis by an average of -90 to -110 per thousand. In addition, the organically bonded H in nonsaponifiable lipids was further fractionated by -80 per thousand from that in saponifiable lipids, isolated from two geographically distinct populations of marsh plants. This difference between H isotope ratios of these two groups of lipids provides an endogenous isotopic marker. (author)

Biogeochemistry of the stable hydrogen isotopes

Energy Technology Data Exchange (ETDEWEB)

Estep, M F; Hoering, T C [Carnegie Institution of Washington, DC (USA)

1980-08-01

The fractionation of H isotopes between the water in the growth medium and the organically bonded H from microalgae cultured under conditions, where light intensity and wavelength, temperature, nutrient availability, and the H isotope ratio of the water were controlled, is reproducible and light dependent. All studies were based either on the H isotope ratios of the total organic H or on the lipids, where most of the H is firmly bonded to C. H bonded into other macromolecules, proteins, carbohydrates and nucleic acids, does not exchange with water, when algae are incubated in water enriched with deuterium. Only after the destruction of quaternary H bonds are labile hydrogens in macromolecules free to exchange with water. By growing algae (18 strains), including blue-green algae, green algae and diatoms, in continuous light, the isotope fractionations in photosynthesis were reproducibly -93 to -178 per thousand, depending on the organism tested. This fractionation was not temperature dependent. Microalgae grown in total darkness with an organic substrate did not show the isotope fractionation seen in cells grown in light. In both light- and dark-grown algae, however, additional depletion of deuterium (-30 to -60 per thousand) in cellular organic matter occurs during the metabolism of carbohydrates to form lipids. Plants from several natural populations also fractionated isotopes during photosynthesis by an average of -90 to -110 per thousand. In addition, the organically bonded H in nonsaponifiable lipids was further fractionated by -80 per thousand from that in saponifiable lipids, isolated from two geographically distinct populations of marsh plants. This difference between H isotope ratios of these two groups of lipids provides an endogenous isotopic marker.

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

Science.gov (United States)

Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

2017-05-17

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

The lack of potassium-isotopic fractionation in Bishunpur chondrules

Science.gov (United States)

Alexander, C.M. O'D.; Grossman, J.N.; Wang, Jingyuan; Zanda, B.; Bourot-Denise, M.; Hewins, R.H.

2000-01-01

In a search for evidence of evaporation during chondrule formation, the mesostases of 11 Bishunpur chondrules and melt inclusions in olivine phenocrysts in 7 of them have been analyzed for their alkali element abundances and K-isotopic compositions. Except for six points, all areas of the chondrules that were analyzed had δ41K compositions that were normal within error (typically ±3%, 2s̀). The six “anomalous” points are probably all artifacts. Experiments have shown that free evaporation of K leads to large 41K enrichments in the evaporation residues, consistent with Rayleigh fractionation. Under Rayleigh conditions, a 3% enrichment in δ41K is produced by ∼12% loss of K. The range of L-chondrite-normalized K/Al ratios (a measure of the K-elemental fractionation) in the areas analyzed vary by almost three orders of magnitude. If all chondrules started out with L-chondrite-like K abundances and the K loss occurred via Rayleigh fractionation, the most K-depleted chondrules would have had compositions of up to δ41K ≅ 200%. Clearly, K fractionation did not occur by evaporation under Rayleigh conditions. Yet experiments and modeling indicate that K should have been lost during chondrule formation under currently accepted formation conditions (peak temperature, cooling rate, etc.). Invoking precursors with variable alkali abundances to produce the range of K/Al fractionation in chondrules does not explain the K-isotopic data because any K that was present should still have experienced sufficient loss during melting for there to have been a measurable isotopic fractionation. If K loss and isotopic fractionation was inevitable during chondrule formation, the absence of K-isotopic fractionation in Bishunpur chondrules requires that they exchanged K with an isotopically normal reservoir during or after formation. There is evidence for alkali exchange between chondrules and rim-matrix in all unequilibrated ordinary chondrites. However, melt inclusions can have

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.

Exchange of deuterium with hydrogen of zeolite catalyst surface

International Nuclear Information System (INIS)

Minachev, Kh.M.; Dmitriev, R.V.; Penchev, V.; Kanazirev, V.; Minchev, Kh.; Kasimov, Ch.K.; Bylgarska Akademiya na Naukite, Sofia. Inst. za Obshta i Organichna Khimiya; AN Azerbajdzhanskoj SSR, Baku. Inst. Neftekhimicheskikh Protsessov)

1981-01-01

Isotope heteromolecular exchange of hydrogen on the reduced nickel-containing zeolites takes places at the temperatures above 100 deg and it is controlled by activated hydrogen transfer from metal particles on the substrate surface. High-temperature redox treatment of nickel-containing zeolites results in the formation of large nickel crystallites on zeolite external faces. The rest part of nickel remains in zeolite pores and conditions a high promoting effect in the exchange reaction. Catalytic activity of reduced zeolites NiCaNaY in toluene disproportionation increases considerably only in the cases when nickel is introduced into zeolite by means of ion exchange. Close spatial location of nickel particles and OH groups promotes the procedure of both isotope exchange and disproportionation of toluene [ru

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

Isotopic fractionation of tritium in biological systems.

Science.gov (United States)

Le Goff, Pierre; Fromm, Michel; Vichot, Laurent; Badot, Pierre-Marie; Guétat, Philippe

2014-04-01

Isotopic fractionation of tritium is a highly relevant issue in radiation protection and requires certain radioecological considerations. Sound evaluation of this factor is indeed necessary to determine whether environmental compartments are enriched/depleted in tritium or if tritium is, on the contrary, isotopically well-distributed in a given system. The ubiquity of tritium and the standard analytical methods used to assay it may induce biases in both the measurement and the signification that is accorded to the so-called fractionation: based on an exhaustive review of the literature, we show how, sometimes large deviations may appear. It is shown that when comparing the non-exchangeable fraction of organically bound tritium (neOBT) to another fraction of tritium (e.g. tritiated water) the preparation of samples and the measurement of neOBT reported frequently led to underestimation of the ratio of tritium to hydrogen (T/H) in the non-exchangeable compartment by a factor of 5% to 50%. In the present study, corrections are proposed for most of the biological matrices studied so far. Nevertheless, the values of isotopic fractionation reported in the literature remain difficult to compare with each other, especially since the physical quantities and units often vary between authors. Some improvements are proposed to better define what should encompass the concepts of exchangeable and non-exchangeable fractions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Novel PEFC Application for Deuterium Isotope Separation

Directory of Open Access Journals (Sweden)

Hisayoshi Matsushima

2017-03-01

Full Text Available The use of a polymer electrolyte fuel cell (PEFC with a Nafion membrane for isotopic separation of deuterium (D was investigated. Mass analysis at the cathode side indicated that D diffused through the membrane and participated in an isotope exchange reaction. The exchange of D with protium (H in H2O was facilitated by a Pt catalyst. The anodic data showed that the separation efficiency was dependent on the D concentration in the source gas, whereby the water produced during the operation of the PEFC was more enriched in D as the D concentration of the source gas was increased.

On the basic substances used in the separation process by isotope exchange H2S - H2O, at two temperatures, in view of producing heavy water

International Nuclear Information System (INIS)

Popescu, V.

1977-01-01

In view of producing heavy water, the influence of the deuterium proportion in the basic substances, on the efficiency of the isotope exchange process H 2 S - H 2 O for two temperatures was studied. Heavy water is extracted from ordinary water and concentrated from 0.014 per cent to 5-15 per cent D 2 O by isotope bithermal exchange with the hydrogen sulphite. Theoretical and experimental research was carried out in laboratories and then applied on a pilot plant by designing and testing a drying equipment for hydrogen sulphite. The maximum H 2 S concentration rose to 99.84 per cent. The purity of the hydrogen sulphite resulting from the pilot plant, as well as the optimization of the installation for producing H 2 S depending on the deuterium distribution, make sure that the two methods for the preparation of sodium sulphite and hydrogen sulphite can be applied in industry. (author)

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)

Mutual complementation between water chemistry and isotope techniques

International Nuclear Information System (INIS)

Matthess, G.

1976-01-01

In the water chemistry and isotope methods which applied together enable more extensive statements to be made than each on its own, the following regions of cooperation are brought out: 1) Isotopes as conservative indicators a) microbial decomposition of organic substances in the anaerobic and aerobic region; b) precipitation and coprecipitation; c) mechanical filtration, adsorption and coprecipitation; d) gas exchange; e) dilution by infiltration; 2) geochemical observations as additional basis for isotope investigations; 3) the investigation of the water content substances as additional help to isotope hydrology. (HK/LH) [de

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

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)

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)

Pion double charge exchange

International Nuclear Information System (INIS)

Cooper, M.D.

1978-01-01

The pion double charge exchange data on the oxygen isotopes is reviewed and new data on 9 Be, 12 C, 24 Mg, and 28 Si are presented. Where theoretical calculations exist, they are compared to the data. 9 references

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%

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

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

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)

The Strontium Isotope Record of Zavkhan Terrane Carbonates: Strontium Isotope Stability Through the Ediacaran-Cambrian Transition

OpenAIRE

Petach, Tanya N.

2015-01-01

First order trends in the strontium isotopic (87Sr/86Sr) composition of seawater are controlled by radiogenic inputs from the continent and non-radiogenic inputs from exchange at mid-ocean ridges. Carbonates precipitated in seawater preserve trace amounts of strontium that record this isotope ratio and therefore record the relative importance of mid-ocean ridge and weathering chemical inputs to sea water composition. It has been proposed that environmental changes during the Ediacaran-Cambria...

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.)

Hydrogen exchange

DEFF Research Database (Denmark)

Jensen, Pernille Foged; Rand, Kasper Dyrberg

2016-01-01

Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

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

Fishing for isotopes in the Brookhaven Lab Isotope Producer (BLIP) cooling water

Energy Technology Data Exchange (ETDEWEB)

Fitzsimmons, Jonathan [Brookhaven National Lab. (BNL), Upton, NY (United States). Collider Accelerator Dept.

2016-04-29

Be-7 has been used in environmental studies; the isotope is produced during BLIP irradiations and accumulates in the 320 gallons of cooling water. Be-7 has a 53.24 day half-life, so the optimal production/purification time is at the end of the BLIP run season. To purify Be-7 fifteen to twenty gallons of BLIP cooling water are removed and pumped through ion exchange columns that retain Be-7. This labor intensive approach captures ~15 mCi of Be-7, but the solution requires further purification. The method can lead to increased radiation exposure to staff. The ideal way to capture isotopes from large volumes is to reach in to the solution and selectively pull out the desired isotope. It is a lot like fishing.

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)

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

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

Utilization of stable isotopes for characterizing an underground gas generator; Utilisation des isotopes stables pour caracteriser un gazogene souterrain

Energy Technology Data Exchange (ETDEWEB)

Pirard, J P; Antenucci, D; Renard, X [Liege Univ. (Belgium); Letolle, R [Paris-6 Univ., 75 (France)

1994-12-31

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O{sub 2}, H{sub 2}O) and in the effluent (CO{sub 2}, CO, H{sub 2}, H{sub 2}O, CH{sub 4}, O{sub 2}, heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs.

Sulfur-induced offsets in MC-ICP-MS silicon-isotope measurements

NARCIS (Netherlands)

van den Boorn, S.; Vroon, P.Z.; van Bergen, M.J.

2009-01-01

Sample preparation methods for MC-ICP-MS silicon-isotope measurements often involve a cation-exchange purification step. A previous study has argued that this would suffice for geological materials, as the occasional enrichment of anionic species would not compromise silicon-isotope analysis. Here

Sulphur-induced offsets in MC-ICP-MS silicon-isotope measurements

NARCIS (Netherlands)

van den Boorn, S.; Vroon, P.Z.; van Bergen, M.J.

2010-01-01

Sample preparation methods for MC-ICP-MS silicon-isotope measurements often involve a cation-exchange purification step. A previous study has argued that this would suffice for geological materials, as the occasional enrichment of anionic species would not compromise silicon-isotope analysis. Here

Amalgam-chromatographic separation of magnesium isotopes

International Nuclear Information System (INIS)

Klinskij, G.D.; Levkin, A.V.; Ivanov, S.A.

1990-01-01

Separation of magnesium isotopes within Mg(Hg)-MgI 2 system (in dimethylformamide) is conducted under amalgam-chromatographic conditions. Separation maximal degree, that is (1.09), for 24 Mg and 26 Mg and separation coefficient (α = 1.0089±0.006) are determined. Light isotopes are found to concentrate in the amalgam. Technique of thermal conversion of flows within amalgam-dimethylformamide system is suggested on the basis of reversible reaction of Ca-Mg element exchange

Carbon isotopes in mollusk shell carbonates

Science.gov (United States)

McConnaughey, Ted A.; Gillikin, David Paul

2008-10-01

Mollusk shells contain many isotopic clues about calcification physiology and environmental conditions at the time of shell formation. In this review, we use both published and unpublished data to discuss carbon isotopes in both bivalve and gastropod shell carbonates. Land snails construct their shells mainly from respired CO2, and shell δ13C reflects the local mix of C3 and C4 plants consumed. Shell δ13C is typically >10‰ heavier than diet, probably because respiratory gas exchange discards CO2, and retains the isotopically heavier HCO3 -. Respired CO2 contributes less to the shells of aquatic mollusks, because CO2/O2 ratios are usually higher in water than in air, leading to more replacement of respired CO2 by environmental CO2. Fluid exchange with the environment also brings additional dissolved inorganic carbon (DIC) into the calcification site. Shell δ13C is typically a few ‰ lower than ambient DIC, and often decreases with age. Shell δ13C retains clues about processes such as ecosystem metabolism and estuarine mixing. Ca2+ ATPase-based models of calcification physiology developed for corals and algae likely apply to mollusks, too, but lower pH and carbonic anhydrase at the calcification site probably suppress kinetic isotope effects. Carbon isotopes in biogenic carbonates are clearly complex, but cautious interpretation can provide a wealth of information, especially after vital effects are better understood.

The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

Science.gov (United States)

Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

2014-05-01

Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

Transendothelial lipoprotein exchange and microalbuminuria

DEFF Research Database (Denmark)

Jensen, Jan Skov; Feldt-Rasmussen, Bo; Jensen, Kurt Svarre

2004-01-01

OBJECTIVE: Microalbuminuria associates with increased risk of atherosclerosis in individuals without diabetes. We hypothesized that transendothelial lipoprotein exchange is elevated among such individuals, possibly explaining increased intimal lipoprotein accumulation and thus atherosclerosis....... METHODS: Using an in vivo isotope technique, transendothelial exchange of low density lipoprotein (LDL) was measured in 77 non-diabetic individuals. Autologous 131-iodinated LDL was reinjected intravenously, and the 1-h fractional escape rate was calculated as index of transendothelial exchange. RESULTS......: There was no difference in transendothelial LDL exchange between subjects with microalbuminuria versus normoalbuminuria (mean (95% confidence interval) 3.8%/h (3.3-4.3%/h) versus 4.2%/h (3.7-4.7%/h); P=0.33). In contrast, there was a positive correlation between transendothelial LDL exchange and (logarithmically...

Transition of the Isotopic Composition of Leaf Water to the Isotopic Steady State in Soybean and Corn

Science.gov (United States)

Kim, K.; Lee, X.; Welp, L. R.

2007-12-01

The isotope composition of leaf water (δL) plays an important role in the isotopic water and carbon fluxes between terrestrial plants and the atmosphere. The objective of this study is to improve our understanding of environmental and biological controls on the transition of δL to steady state through laboratory experiments. Plants (soybean, Glycine max; corn, Zea mays) were grown hydroponically with water of a known isotopic content in a greenhouse. On the day of the experiment, they were first moved to ambient environment in full sunlight for at least 6 hr and then into a dark container inside the lab for up to 48 hr in which water vapor isotope ratios, temperature, and humidity were controlled. This arrangement created a step change in the forcing on the plant isotopic exchange. Leaves were sampled prior to the transfer to the dark container and 6 more times every 4 - 12 hr over the experiment. In the first set of experiments, humidity inside the container was saturated to mimic dew events in field conditions. In the second set, humidity was controlled at approximately 95%. Water from the leaf samples was extracted by a vacuum line and was analyzed for both δD and δ18O. The dataset will allow us to evaluate leaf water isotopic theories by exploring the transitions of δL in response to the step change. Specifically, we are interested in whether the stomatal opening is an effective pathway for gaseous exchange in total darkness and how the transitional behaviors of δL differ between the C3 and C4 photosynthesis pathways.

An experimental study on the effect of carbonic anhydrase on the oxygen isotope exchange kinetics and equilibrium in the carbonic acid system

Science.gov (United States)

Uchikawa, J.; Zeebe, R. E.

2011-12-01

Stable oxygen isotopes of marine biogenic carbonates are often depleted in 18O relative to the values expected for thermodynamic equilibrium with ambient seawater. One possibility is that 18O-depletion in carbonates is kinetically controlled. The kinetic isotope effect associated with the hydration of CO2 results in 18O-depleted HCO3-. If the HCO3- is utilized before re-establishing equilibrium with ambient water under rapid calcification, the 18O-depletion will be recorded in carbonates. But one caveat in this kinetic model is the fact that many marine calcifiers posses carbonic anhydrase, a zinc-bearing enzyme that catalyzes the CO2 hydration reaction. It is expected that this enzyme accelerates 18O-equilibration in the carbonic acid system by facilitating direct oxygen isotope exchange between HCO3- and H2O via CO2 hydration. Clearly this argues against the conceptual framework of the kinetic model. Yet the critical variable here is the effectiveness of the carbonic anhydrase, which is likely to depend on its concentration and the carbonate chemistry of the aqueous medium. It is also hitherto unknown whether the presence of carbonic anhydrase alters the equilibrium oxygen isotope fractionations between dissolved carbonate species and water. We performed a series of quantitative inorganic carbonate precipitation experiments to examine the changes in the oxygen isotope equilibration time as a function of carbonic anhydrase concentrations. We conducted experiments at pH 8.3 and 8.9. These pH values are similar to the average surface ocean pH and the elevated pH levels observed within calcification microenvironments of certain corals and planktonic foraminifera. A summary of our new experimental results will be presented.

Process and device for stage by stage enrichment of deuterium and/or tritium in a material suitable for isotope exchange of deuterium and tritium with hydrogen

International Nuclear Information System (INIS)

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

1983-01-01

Water containing deuterium and/or tritium is first introduced into a carrier gas flow and reduced for the stage by stage enrichment of deuterium and/or tritium. A hydrogen partial pressure of a maximum of 100 millibar is set in the carrier gas flow. The carrier gas flow is taken along the primary side of an exchange wall suitable for the permeation of hydrogen, and a further carrier gas flow flows on its secondary side, which contains water or hydrogen. Reaction products formed after isotope exchange of deuterium and/or tritium with hydrogen are removed by the secondary carrier gas flow. (orig./HP) [de

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.

Relationships between tree height and carbon isotope discrimination

Science.gov (United States)

Nate G. McDowell; Barbara J. Bond; Lee T. Dickman; Michael G. Ryan; David Whitehead

2011-01-01

Understanding how tree size impacts leaf- and crown-level gas exchange is essential to predicting forest yields and carbon and water budgets. The stable carbon isotope ratio of organic matter has been used to examine the relationship of gas exchange to tree size for a host of species because it carries a temporally integrated signature of foliar photosynthesis and...

Lithium isotope separation factors of some two-phase equilibrium systems

International Nuclear Information System (INIS)

Palko, A.A.; Drury, J.S.; Begun, G.M.

1976-01-01

Isotope separation factors of seventeen two-phase equilibrium systems for lithium isotope enrichment have been determined. In all cases, lithium amalgam was used as one of the lithium-containing phases and was equilibrated with an aqueous or organic phase containing a lithium compound. In all systems examined, isotopic exchange was found to be extremely rapid, and 6 Li was concentrated in the amalgam phase. The isotopic separation factor for the LiOH(aqueous) vs Li(amalgam) system has been studied as a function of temperature from -2 to 80 degreeC. The values obtained have been compared with the ''electrolysis'' and exchange separation factors given in the literature. The two-phase systems, LiCl(ethylenediamine) vs Li(amalgam) and LiCl(propylenediamine) vs Li(amalgam), have been studied, and the isotopic separation factors have been determined as functions of the temperature. The factors for the two systems have been found to be substantially the same (within limits of the errors involved) over the temperature range studied (0 to 100 degreeC) as those for the aqueous system. The isotopic separation factors for the seventeen systems have been tabulated, and correlations have been drawn that show the salt and solvent effects upon the values obtained

Catalyst for hydrogen-amine D exchange

International Nuclear Information System (INIS)

Holtslander, W.J.; Johnson, R.E.

1976-01-01

A process is claimed for deuterium isotopic enrichment (suitable for use in heavy water production) by amine-hydrogen exchange in which the exchange catalyst comprises a mixture of alkyl amides of two metals selected from the group consisting of the alkali metals. Catalyst mixtures comprising at least one of the alkali amides of lithium and potassium are preferred. At least one of the following benefits are obtained: decreased hydride formation, decreased thermal decomposition of alkyl amide, increased catalyst solubility in the amine phase, and increased exchange efficiency. 11 claims

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

Direct lead isotope analysis in Hg-rich sulfides by LA-MC-ICP-MS with a gas exchange device and matrix-matched calibration

Energy Technology Data Exchange (ETDEWEB)

Zhang, Wen [State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan, 430074 (China); Hu, Zhaochu, E-mail: zchu@vip.sina.com [State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan, 430074 (China); Günther, Detlef, E-mail: guenther@inorg.chem.ethz.ch [ETH Zurich, Laboratory for Inorganic Chemistry, CH-8093, Zurich (Switzerland); Liu, Yongsheng; Ling, Wenli; Zong, Keqing; Chen, Haihong; Gao, Shan [State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan, 430074 (China)

2016-12-15

In situ Pb isotope data of sulfide samples measured by LA-MC-ICP-MS provide valuable geochemical information for studies of the origin and evolution of ore deposits. However, the severe isobaric interference of {sup 204}Hg on {sup 204}Pb and the lack of matrix-matched sulfide reference materials limit the precision of Pb isotopic analyses for Hg-rich sulfides. In this study, we observe that Hg forms vapor and can be completely removed from sample aerosol particles produced by laser ablation using a gas exchange device. Additionally, this device does not influence the signal intensities of Pb isotopes. The within-run precision, the external reproducibility and the analytical accuracy are significantly improved for the Hg-rich sulfide samples using this mercury-vapor-removing device. Matrix effects are observed when using silicate glass reference materials as the external standards to assess the relationship of mass fractionation factors between Tl and Pb in sulfide samples, resulting in a maximum deviation of ∼0.20% for {sup 20x}Pb/{sup 204}Pb. Matrix-matched reference materials are therefore required for the highly precise and accurate Pb isotope analyses of sulfide samples. We investigated two sulfide samples, MASS-1 (the Unites States Geological Survey reference materials) and Sph-HYLM (a natural sphalerite), as potential candidates. Repeated analyses of the two proposed sulfide reference materials by LA-MC-ICP-MS yield good external reproducibility of <0.04% (RSD, k = 2) for {sup 20x}Pb/{sup 206}Pb and <0.06% (RSD, k = 2) for {sup 20x}Pb/{sup 204}Pb with the exception of {sup 20x}Pb/{sup 204}Pb in MASS-1, which provided an external reproducibility of 0.24% (RSD, k = 2). Because the concentration of Pb in MASS-1 (76 μg g{sup −1}) is ∼5.2 times lower than that in Sph-HYLM (394 ± 264 μg g{sup −1}). The in situ analytical results of MASS-1 and Sph-HYLM are consistent with the values obtained by solution MC-ICP-MS, demonstrating the reliability

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

International Nuclear Information System (INIS)

Bogdan, Mircea

2001-01-01

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

Isotope effects: definitions and consequences for pharmacologic studies

International Nuclear Information System (INIS)

Van Langenhove, A.

1986-01-01

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

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

Inorganic anion exchangers for the treatment of radioactive wastes

International Nuclear Information System (INIS)

Dyer, A.; Jamil, M.A.

1987-07-01

Inorganic anion exchangers are evaluated for Tc, I and S isotope removal from aqueous nuclear waste streams. Chemical, thermal, and radiation stabilities were examined. Selected exchangers were examined in detail for their selectivities, kinetics and mechanism of the sorption process (especially in NO 3 - , OH - and BO 3 - environments). Cement encapsulation and leaching experiments were made on the exchangers showing most promise for 'radwaste' treatment. (author)

Proceedings of the Conference on Isotopic and Molecular Processes

International Nuclear Information System (INIS)

Pamula, A.

1999-01-01

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

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

Isotopes in Weed Research. Proceedings of the Symposium on the Use of Isotopes in Weed Research

Energy Technology Data Exchange (ETDEWEB)

NONE

1966-05-15

The Symposium on the Use of Isotopes in Weed Research was convened jointly by the Food and Agriculture Organization of the United Nations and the International Atomic Energy Agency, and was held in Vienna at the Headquarters of IAEA from 25 to 29 October 1965. It was attended by 67 participants representing 18 countries. The Symposium provided an occasion for the exchange of information on recent advances in the subject. Additionally it gave an opportunity for investigators who had not used isotopes in their research to assess the potentialities and applications of this technique. Isotopes have already been extensively used in weed research, particularly for studying the comparative absorption of herbicides by different plant species and the movement and distribution of the herbicide within the plant. Radioisotopes have proved of particular value in these studies through the ability of autoradiographic techniques to detect even the trace amounts involved. The mode of action of herbicides has also been quite widely studied through the use of isotopes. It is probably a general rule that the practical selective herbicidal nature of a chemical compound is usually known some time before the actual metabolic mode of action is traced. Nevertheless the mode of action is of great importance, as its study may lead to the development of other herbicides; isotope techniques may be expected to play an increasing role here. Weed control is a continuing world agriculture problem of serious dimensions and there is constant effort both to develop and utilize herbicides. As part of the general widespread concern over the residual effects of chemicals applied to crop plants, the study of herbicide residues in plants and soil, and the detoxification of herbicides, has become essential. For these studies isotopic techniques can be usefully used to identify degradation products and trace the ultimate fate of the herbicide. Such studies are of growing importance. Features of the

Isotopes in Weed Research. Proceedings of the Symposium on the Use of Isotopes in Weed Research

International Nuclear Information System (INIS)

1966-01-01

The Symposium on the Use of Isotopes in Weed Research was convened jointly by the Food and Agriculture Organization of the United Nations and the International Atomic Energy Agency, and was held in Vienna at the Headquarters of IAEA from 25 to 29 October 1965. It was attended by 67 participants representing 18 countries. The Symposium provided an occasion for the exchange of information on recent advances in the subject. Additionally it gave an opportunity for investigators who had not used isotopes in their research to assess the potentialities and applications of this technique. Isotopes have already been extensively used in weed research, particularly for studying the comparative absorption of herbicides by different plant species and the movement and distribution of the herbicide within the plant. Radioisotopes have proved of particular value in these studies through the ability of autoradiographic techniques to detect even the trace amounts involved. The mode of action of herbicides has also been quite widely studied through the use of isotopes. It is probably a general rule that the practical selective herbicidal nature of a chemical compound is usually known some time before the actual metabolic mode of action is traced. Nevertheless the mode of action is of great importance, as its study may lead to the development of other herbicides; isotope techniques may be expected to play an increasing role here. Weed control is a continuing world agriculture problem of serious dimensions and there is constant effort both to develop and utilize herbicides. As part of the general widespread concern over the residual effects of chemicals applied to crop plants, the study of herbicide residues in plants and soil, and the detoxification of herbicides, has become essential. For these studies isotopic techniques can be usefully used to identify degradation products and trace the ultimate fate of the herbicide. Such studies are of growing importance. Features of the

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)

Robust optical carbon dioxide isotope analyzer, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — Isotopic analysis of carbon dioxide is an important tool for characterization of the exchange and transformation of carbon between the biosphere and the atmosphere....

Hydrogen Isotopes in Amino Acids and Soils Offer New Potential to Study Complex Processes

Science.gov (United States)

Fogel, M. L.; Newsome, S. D.; Williams, E. K.; Bradley, C. J.; Griffin, P.; Nakamoto, B. J.

2016-12-01

Hydrogen isotopes have been analyzed extensively in the earth and biogeosciences to trace water through various environmental systems. The majority of the measurements have been made on water in rocks and minerals (inorganic) or non-exchangeable H in lipids (organic), important biomarkers that represent a small fraction of the organic molecules synthesized by living organisms. Our lab has been investigating hydrogen isotopes in amino acids and complex soil organic matter, which have traditionally been thought to be too complex to interpret owing to complications from potentially exchangeable hydrogen. For the amino acids, we show how hydrogen in amino acids originates from two sources, food and water, and demonstrate that hydrogen isotopes can be routed directly between organisms. Amino acid hydrogen isotopes may unravel cycling in extremophiles in order to discover novel biochemical pathways central to the organism. For soil organic matter, recent approaches to understanding the origin of soil organic matter are pointing towards root exudates along with microbial biomass as the source, rather than aboveground leaf litter. Having an isotope tracer in very complex, potentially exchangeable organic matter can be handled with careful experimentation. Although no new instrumentation is being used per se, extension of classes of organic matter to isotope measurements has potential to open up new doors for understanding organic matter cycling on earth and in planetary materials.

Simultaneous determination of platinum group elements and rhenium in rock samples using isotope dilution inductively coupled plasma mass spectrometry after cation exchange separation followed by solvent extraction

International Nuclear Information System (INIS)

Shinotsuka, Kazunori; Suzuki, Katsuhiko

2007-01-01

A simple and precise determination method for platinum group elements (PGEs) and Re in rock samples was developed using isotope dilution coupled with inductively coupled plasma mass spectrometry (ID-ICP-MS). Cation exchange separation was employed for simplicity, because it is applicable to group separation and simultaneous isotopic measurement in contrast with the widely used anion exchange separation which entails separate elution. However, its application to ID-ICP-MS has been limited due to spectral interferences from impurities retained in the PGE fraction even after ion chromatography. To overcome this limitation, solvent extraction using N-benzoyl-N-phenylhydroxylamine (BPHA) in chloroform was successfully applied for further purification. After the examination of optimum experimental parameters in cation exchange separation and solvent extraction using synthetic PGE solution, the established procedure was applied to the determination of PGEs and Re in some geochemical reference materials. The obtained results agreed well with the literature data determined using the different digestion methods (NiS fire assay and the use of a high-pressure asher) within the analytical uncertainties of each other. Significant difference in reproducibility between Ru, Ir, Pt and Os group, and Pd and Re group was observed in the results for BHVO-2 and JA-2. By considering the error factors affecting analytical reproducibility, we concluded that the difference is ascribed to the sample heterogeneity of minor minerals enriched in Ru, Ir, Pt and Os

Application of the bidimensional ion-exchange chromatography for the laboratory preparation of different 15N enrichments and depletions

International Nuclear Information System (INIS)

Farjo, K.

1989-01-01

The ion-exchange application of the bidimensional solid/liquid technique for the preparation of different 15 N-abundances utilizing the isotope exchange system NH 4 + /NH 3 · aq is reported and the application of the technique for the separation of nitrogen isotopes is briefly discussed. (author)

Titanium Isotopes Provide Clues to Lunar Origin

Science.gov (United States)

Taylor, G. J.

2012-05-01

The idea that the Moon formed as the result of the giant impact of a Mars-sized impactor with the still-growing Earth explains two central facts about the Earth-Moon system: its total angular momentum (Earth's spin and the Moon's orbital motion), and the sizes of the metallic cores of the Earth (large) and Moon (tiny). This gives cosmochemists some confidence in the hypothesis, but they would greatly appreciate additional compositional tests. One undisputed point is the identical abundance of the three oxygen isotopes in Earth and Moon. Junjun Zhang and colleagues at the University of Chicago (USA) and the University of Bern (Switzerland) have added another isotopic system to the cosmochemical testing tool kit, titanium isotopes. They find that the ratio of titanium-50 to titanium-47 is identical in Earth and Moon to within four parts per million. In contrast, other solar system materials, such as carbonaceous chondrites, vary by considerably more than this-- up to 150 times as much. The identical oxygen and titanium isotopic compositions in Earth and Moon are surprising in light of what we think we know about planet formation and formation of the Moon after a giant impact. The variations in oxygen and titanium isotopes among meteorite types suggest that it is unlikely that the Moon-forming giant impactor would have had the same isotopic composition as the Earth. Simulations show that the Moon ends up constructed mostly (40-75%) from the impactor materials. Thus, the Moon ought to have different isotopic composition than does Earth. The isotopes might have exchanged in the complicated, messy proto-lunar disk (as has been suggested for oxygen isotopes), making them the same. However, Zhang and colleagues suggest that this exchange is unlikely for a refractory element like titanium. Could the impact simulations be greatly overestimating the contributions from the impactor? Was the mixing of building-block materials throughout the inner solar system much less than

Ageing and structural effects on the sorption characteristics of Cd2+ by clinoptilolite and Y-type zeolite studied using isotope exchange technique

International Nuclear Information System (INIS)

Ahmed, I.A.M.; Young, S.D.; Crout, N.M.J.

2010-01-01

This research investigates the long-term kinetics of Cd 2+ sorption and desorption by calcium-exchanged clinoptilolite (CaCpt) and Y-type (CaY) zeolite using isotopic exchange with 109 Cd while maintaining pH at circumneutral values. The effects of Si/Al ratio and crystal structure of these zeolitic materials on intracrystalline transport of Cd are discussed. A first-order kinetic model was developed to describe the progressive transfer of Cd 2+ to a less reactive form within the zeolite structure, following initial sorption and subsequent desorption of Cd subject to different initial contact times. The kinetic model differentiates between two forms of sorbed Cd 2+ designated 'labile' and 'non-labile' in which the labile form is in immediate equilibrium with the free Cd 2+ ion activity in solution. A model combining diffusion and first-order kinetics for cation exchange was also employed to determine Cd 2+ diffusivity and intracrystalline exchange rates in CaY and CaCpt. The efficiency of Permeable Reactive Barriers (PRBs) containing zeolitic materials in protecting water systems against lateral flow of metal-contaminated leachate was simulated for three contrasting zeolites. The slow transfer of Cd between labile and non-labile forms was particularly important in moderating high concentration pulses of Cd traversing the PRB. In addition, the reversibility of Cd fixation effectively restored the sorption capability of the zeolite through slow leakage to drainage water.

Analytical techniques for determination of framework oxygen isotope ratio of wairakite

International Nuclear Information System (INIS)

Noto, Masami; Kusakabe, Minoru; Uchida, Tetsuo.

1990-01-01

Dehydration techniques were developed for the analysis of isotopic ratios of framework oxygen of wairakite, one of calcium zeolites often encountered in geothermal systems. Channel water in wairakite were separated from aluminosilicate framework by dehydration in vacuum at 300 deg, 400 deg, 450 deg, 500 deg, 550 deg, 650 deg, 750 deg, 850 deg, and 950 degC, and by stepwise heating at temperatures from 300 deg to 700 degC. The oxygen isotopic analyses of the separated channel water and the residual aluminosilicate framework of wairakite indicated that dehydration at temperatures higher than 400 degC is accompanied by isotopic exchang between the framework oxygen and dehydrating water vapor. The isotopic exchange during the high temperature dehydration makes the δ 18 O of framework oxygen lower and that of channel water higher than those obtained by dehydration at 300 degC. These results are consistent with dehydration behavior of wairakite under vacuum that the maximum rate of dehydration of channel water is attained at about 400 degC. Consequently it is recommended to dehydrate wairakite at a temperature as low as possible in order to avoid the effect of the isotopic exchange. Time required to attain complete dehydration becomes longer with lowering the temperature of dehydration. To compromise these conflicting effects, the optimum conditions of dehydration have been found that most of the channel water is dehydrated at 300 degC for 24 hours, followed by stepwise heating for additional 17 hours up to 700 degC. We obtained a better than ± 0.1 reproducibility for the framework oxygen isotopic determinations with this technique. (author)

Separation of uranium and plutonium isotopes for measurement by multi collector inductively coupled plasma mass spectroscopy

International Nuclear Information System (INIS)

Martinelli, R.E.; Hamilton, T.F.; Kehl, S.R.; Williams, R.W.

2009-01-01

Uranium (U) and plutonium (Pu) isotopes in coral soils, contaminated by nuclear weapons testing in the northern Marshall Islands, were isolated by ion-exchange chromatography and analyzed by mass spectrometry. The soil samples were spiked with 233 U and 242 Pu tracers, dissolved in minerals acids, and U and Pu isotopes isolated and purified on commercially available ion-exchange columns. The ion-exchange technique employed a TEVA R column coupled to a UTEVA R column. U and Pu isotope fractions were then further isolated using separate elution schemes, and the purified fractions containing U and Pu isotopes analyzed sequentially using multi-collector inductively coupled plasma mass spectrometer (MCICP-MS). High precision measurements of 234 U/ 235 U, 238 U/ 235 U, 236 U/ 235 U, and 240 Pu/ 239 Pu in soil samples were attained using the described methodology and instrumentation, and provide a basis for conducting more detailed assessments of the behavior and transfer of uranium and plutonium in the environment. (author)

Isotopically labelled pyrimidines and purines

International Nuclear Information System (INIS)

Balaban, A.T.; Bally, I.

1987-01-01

Among the three diazines, pyrimidine is by far the most important one because its derivatives uracil, thymine and cytosine are constituents of the ubiquitous deoxynucleic acids (DNA) and ribonucleic acids (RNA). Other derivatives of pyrimidine without condensed rings include barbiturates, alloxan, orotic acid and thiamine or vitamin B 1 . From the polycyclic derivatives of pyrimidine such as pteridine, alloxazine, and purine, the latter, through its derivatives adenine and guanine complete the list of bases which occur in DNA and RNA: in addition, other purine derivatives such as hypoxanthine, xanthine, theobromine, theophylline, caffeine and uric acid are important natural products with biological activity. The paper presents methods for preparing isotopically labeled pyrimidines as well as purine derivatives. For convenience, the authors describe separately carbon-labeled with radioisotopes 11 C (T 1/2 = 20.3 min) and 14 C (T 1/2 = 5736 years) or the stable isotope 13 C (natural abundance 1.1%) and then hydrogen-labeled systems with the radioisotope 3 H ≡ T (T 1/2 = 12.346 years) or with the stable isotope 2 H ≡ D (natural abundance 0.015%). We do not separate stable from radioactive isotopes because the synthetic methods are identical for the same element; however, the introduction of hydrogen isotopes into organic molecules is often performed by reactions such as isotope exchange which cannot take place in the case of carbon isotopes

Utilization of stable isotopes for characterizing an underground gas generator

International Nuclear Information System (INIS)

Pirard, J.P.; Antenucci, D.; Renard, X.; Letolle, R.

1994-01-01

The principles of isotopic exchange and isotope ratio result interpretation are first reviewed; then, in the framework of an underground coal gasification project in Belgium, experiments and modelling of the underground gas generator have been carried out: isotopic abundances of carbon, hydrogen and oxygen have been measured in the gasifying agent (O 2 , H 2 O) and in the effluent (CO 2 , CO, H 2 , H 2 O, CH 4 , O 2 , heavy oils and various organic and mineral substances). Gasification kinetics and temperatures have been evaluated and isotope application to thermometry is discussed. 1 fig., 9 refs

A Hydrogen Exchange Method Using Tritium and Sephadex: Its Application to Ribonuclease*

Science.gov (United States)

Englander, S. Walter

2012-01-01

A new method for measuring the hydrogen exchange of macromolecules in solution is described. The method uses tritium to trace the movement of hydrogen, and utilizes Sephadex columns to effect, in about 2 minutes, a separation between tritiated macromolecule and tritiated solvent great enough to allow the measurement of bound tritium. High sensitivity and freedom from artifact is demonstrated and the possible value of the technique for investigation of other kinds of colloid-small molecule interaction is indicated. Competition experiments involving tritium, hydrogen, and deuterium indicate the absence of any equilibrium isotope effect in the ribonuclease-hydrogen isotope system, though a secondary kinetic isotope effect is apparent when ribonuclease is largely deuterated. Ribonuclease shows four clearly distinguishable kinetic classes of exchangeable hydrogens. Evidence is marshaled to suggest the independently measurable classes II, III, and IV (in order of decreasing rate of exchange) to represent “random-chain” peptides, peptides involved in α-helix, and otherwise shielded side-chain and peptide hydrogens, respectively. PMID:14075117

Method for separation and enrichment of isotopes

International Nuclear Information System (INIS)

Kakihana, H.; Miyamatsu, T.

1977-01-01

Boron or uranium isotopes can be chemically separated and enriched with high speed and with high separating efficiency by using weakly basic anion exchange fibers having a diameter of not more than 100 μ, an aspect ratio of at least 5 and an exchange capacity of at least 2 meq/g-dry fiber, which are packed in a column at a specific volume of 2.0 to 20.0 ml/g-dry fiber

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

Stable Fe isotope fractionation during anaerobic microbial dissimilatory iron reduction at low pH

Science.gov (United States)

Chanda, P.; Amenabar, M. J.; Boyd, E. S.; Beard, B. L.; Johnson, C.

2017-12-01

In low-temperature anaerobic environments microbial dissimilatory iron reduction (DIR) plays an important role in Fe cycling. At neutral pH, sorption of aqueous Fe(II) (Fe(II)aq, produced by DIR) catalyzes isotopic exchange between Fe(II) and solid Fe(III), producing 56Fe/54Fe fractionations on the order of 3‰ during DIR[1,2,3]. At low pH, however, the absence of sorbed Fe(II) produces only limited abiologic isotopic exchange[4]. Here we investigated the scope of isotopic exchange between Fe(II)aq and ferric (hydr)oxides (ferrihydrite and goethite) and the associated stable Fe isotope fractionation during DIR by Acidianus strain DS80 at pH 3.0 and 80°C[5]. Over 19 days, 13% reduction of both minerals via microbial DIR was observed. The δ56Fe values of the fluid varied from -2.31 to -1.63‰ (ferrihydrite) and -0.45 to 0.02‰ (goethite). Partial leaching of bulk solid from each reactor with dilute HCl showed no sorption of Fe(II), and the surface layers of the solids were composed of Fe(III) with high δ56Fe values (ferrihydrite: 0.20 to 0.48‰ and goethite: 1.20 to 1.30‰). These results contrast with the lack of Fe isotope exchange in abiologic low-pH systems and indicate a key role for biology in catalyzing Fe isotope exchange between Fe(II)aq and Fe(III) solids, despite the absence of sorbed Fe(II). The estimated fractionation factor (ΔFeFe(III) -Fe(II)aq 2.6‰) from leaching of ferrihydrite is similar to the abiologic equilibrium fractionation factor ( 3.0‰)[3]. The fractionation factor (ΔFeFe(III) -Fe(II)aq 2.0‰) for goethite is higher than the abiologic fractionation factor ( 1.05‰)[2], but is consistent with the previously proposed "distorted surface layer" of goethite produced during the exchange with Fe(II)aq at neutral pH[1]. This study indicates that significant variations in Fe isotope compositions may be produced in low-pH environments where biological cycling of Fe occurs, in contrast to the expected lack of isotopic fractionation in

Phosphorus isotopic evaluation of a Red Ferralitic soil under various fertilization systems

International Nuclear Information System (INIS)

Rodríguez Guzmán, Ricardo M.

2017-01-01

Soil samples from a red ferralitic soil from the 'Juan Tomas Roig' Experimental Station, belonging to Ciego de Avila University were analyzed under two crop rotations and four phosphoric fertilization systems. The objective was to evaluate, through the 32 P isotopic dilution, phosphor (P) static parameters in a soil that has received P fertilizer through two placement methods (banding and broadcasting) for several years. A radiochemical laboratory method using a free-carrier solution as a tracer based on isotopic exchange between solid phase and soil solution phosphate ions was used. Soil samples were analyzed at the CEA Department laboratories, in Francia. Quantity (), as isotopic exchangeable P at one minute, intensity (Cp), as P concentration in soil solution, and capacity, as (/Cp), factors were determined. 32 P isotopic evaluation indicated that the soil needs high banding P application to reach adequate and Cp values for crop nutrition. A cumulative P effect in the soil through banding fertilization after three crop rotation cycles was obtained, which allows to increase plant P availability. The capacity factor was very high in all soil samples, indicating that soil maintains a P reserve that is difficult to exchange with the phosphor present in the soil solution. (author)

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

International Nuclear Information System (INIS)

Ishida, Takanobu.

1987-01-01

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

Solution of operational problems utilization of an EX-IRT-2000 heat exchanger

International Nuclear Information System (INIS)

Razak, Abdu

1986-01-01

The Bandung TRIGA Mark II Reactor has been successfully operated for 21 years, especially in low power operation or as neutron sources for various experiments. Most of the operating time, approximately 80% of routine operation, was dedicated for radio-isotope production. During routine operation for radio-isotope production, the reactor could not be operated at full power. The reactor was operated at 60% of the maximum power (1 MWth) due to the inability of the original heat exchanger to operate properly. The reason is that slack deposition was built-up on the secondary side of the heat exchanger. Therefore, it reduced the coefficient of heat transfer considerably. To solve the problems, a set of heat exchanger including the pump was installed In parallel with the original unit. The heat exchanger was an IRT-2000 Reactor Heat exchanger which was collected from the abandoned IRT-2000 Project. The heat exchanger has capacity of 1.25 MW. The new heat exchanger could reduced the outlet temperature of the primary coolant Into 42 deg. C. While the original-heat exchanger at the worst condition and at 600 kW of power reach outlet temperature 49 deg. C. The IRT Heat Exchanger is a counter flow heat exchanger. (author)

Solution of operational problems utilization of an EX-IRT-2000 heat exchanger

Energy Technology Data Exchange (ETDEWEB)

Razak, Abdu [Research Centre for Nuclear Techniques, National Atomic Energy Agency (Indonesia)

1986-07-01

The Bandung TRIGA Mark II Reactor has been successfully operated for 21 years, especially in low power operation or as neutron sources for various experiments. Most of the operating time, approximately 80% of routine operation, was dedicated for radio-isotope production. During routine operation for radio-isotope production, the reactor could not be operated at full power. The reactor was operated at 60% of the maximum power (1 MWth) due to the inability of the original heat exchanger to operate properly. The reason is that slack deposition was built-up on the secondary side of the heat exchanger. Therefore, it reduced the coefficient of heat transfer considerably. To solve the problems, a set of heat exchanger including the pump was installed In parallel with the original unit. The heat exchanger was an IRT-2000 Reactor Heat exchanger which was collected from the abandoned IRT-2000 Project. The heat exchanger has capacity of 1.25 MW. The new heat exchanger could reduced the outlet temperature of the primary coolant Into 42 deg. C. While the original-heat exchanger at the worst condition and at 600 kW of power reach outlet temperature 49 deg. C. The IRT Heat Exchanger is a counter flow heat exchanger. (author)

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)

Classical and quasi-classical trajectory calculations of isotope exchange and ozone formation proceeding through O+O2 collision complexes

Science.gov (United States)

Baker, Thomas A.; Gellene, Gregory I.

2002-10-01

The isotope exchange reaction, and the three-body ozone formation rate proceeding through an ozone complex, have been studied by classical and quasi-classical trajectory techniques. The exchange rate studies indicate that the rate of this reaction is dominantly sensitive to the O+O2 entrance channel characteristics of the potential energy surface. A detailed consideration of the dynamics of the intermediate ozone complex reveals three important classes. In one class, the complex adopts an ozonelike geometry, largely undergoing asymmetric stretchinglike motion until it dissociates. In a second class, the oxygen atom and molecule never visit the ozonelike geometry but rather remain separated by relatively large distances trapped near the angular momentum barrier in the entrance channel of a pseudo-effective potential. These complexes, which cannot undergo exchange, are, nevertheless, found to contribute significantly to ozone formation at high density of the third body suggesting that the association of the high-density effective formation rate constant with twice the exchange rate may not be valid. The third class can be considered a hybrid of the first two, spending some time as an ozonelike complex and some time as a large atom-diatomic complex. This third class provides a mechanism for rearranging atom locations in the complex (e.g., end and middle position swapping) and, consequently, would not be well accounted for by statistical treatments of the ozone complex based on a single ozonelike reference geometry. In general, the survival time distributions of the complexes are found to be nonexponential. However, when the detailed survival time distributions are coupled with a Lennard-Jones collision model for the stabilization step, the experimental ozone formation rate can be adequately modeled over a broad range of temperature and density.

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

Science.gov (United States)

Bullen, Thomas D.; Chadwick, Oliver A.

2016-01-01

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons ( 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in

The use of isotopes in soil fertility and soil chemistry

International Nuclear Information System (INIS)

Neptune, A.M.L.; Muraoka, T.

1978-01-01

The concept of radioactive and enriched stable isotopes is reminded. The main topics studied with isotopes which are pointed out are the following: the isotopic exchange and its application; the E and L values; the determination of CEC; the fixing capacity of some ions by the soil particles; the measurement of the A value; the efficiency of fertilizers utilization, the interaction between nutrients, their movements through the soil, the residual effect of the fertilizers and, finally, the root system and soil organic matter. (author) [pt

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

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...

A general procedure for isotopic (deuterium) labelling of non-steroidal antiinflammatory 2-arylpropionic acids

International Nuclear Information System (INIS)

Castell, J.V.; Martinez, L.A.; Universidad Politecnica de Valencia; Miranda, M.A.; Tarrega, Pilar

1994-01-01

Alkaline treatment of nonsteroidal antiinflammatory 2-arylpropionic acids in deuterium oxide led in all cases to isotopic exchange of the proton located at the α-position of the side chain. Monodeuteration was observed in the case of carprofen, ibuprofen, ketoprofen, fenoprofen, flurbiprofen and naproxen. Additional exchange of one or two protons of the heterocyclic ring occurred in indoprofen, suprofen and tiaprofenic acid. The isotopic labelling survived under the conditions required to perform in vitro photoallergic studies (photolysis in non-deuterated aqueous media). (Author)

A general procedure for isotopic (deuterium) labelling of non-steroidal antiinflammatory 2-arylpropionic acids

Energy Technology Data Exchange (ETDEWEB)

Castell, J.V. (Valencia Univ. Hospital (Spain). Centro de Investigacion); Martinez, L.A. (Valencia Univ. Hospital (Spain). Centro de Investigacion Universidad Politecnica de Valencia (Spain). Dept. de Quimica); Miranda, M.A.; Tarrega, Pilar (Universidad Politecnica de Valencia (Spain). Dept. de Quimica)

1994-01-01

Alkaline treatment of nonsteroidal antiinflammatory 2-arylpropionic acids in deuterium oxide led in all cases to isotopic exchange of the proton located at the [alpha]-position of the side chain. Monodeuteration was observed in the case of carprofen, ibuprofen, ketoprofen, fenoprofen, flurbiprofen and naproxen. Additional exchange of one or two protons of the heterocyclic ring occurred in indoprofen, suprofen and tiaprofenic acid. The isotopic labelling survived under the conditions required to perform in vitro photoallergic studies (photolysis in non-deuterated aqueous media). (Author).

On the migration of uranium isotopes in sandstone aquifers

International Nuclear Information System (INIS)

Froehlich, K.; Gellermann, R.

1982-01-01

Measurements of natural 238 U and 234 U activity in groundwater of sandstone aquifers have been used to study the migration of these uranium isotopes. Regarding the uranium exchange between liquid phase and rock surface during migration, two different models were applied for evaluating the experimental results. Values of corresponding parameters (retardation factor K, removal rate R) reflecting different behaviour concerning this exchange were determined. For example, the values obtained for 238 U in a Triassic sandstone aquifer of the GDR are K = 8.6 x 10 6 and R = 1.3 x 10 -3 a -1 , respectively. It was found that, under the conditions of the sandstone aquifer concerned, the removal rate model is better suited for calculating uranium-isotope migration in groundwater. (author)

Acquisition system of analysis and control data for the catalytic isotopic exchange module of the cryogenic pilot plant with mathematical modeling

International Nuclear Information System (INIS)

Retevoi, Carmen Maria; Cristescu, Ioana; Bornea, Anisia; Cristescu, Ion

2000-01-01

The main problem of the isotope exchange is the catalytic action of the reaction. In order to increase the economic efficiency it is suggested using the hydrophobic catalysts. The 'virtual instrument' which we design is made for monitoring the constant temperature of column, analysis and power supply commands for electrical heat exchangers. With the most popular signal conditioning product line, SCXI 1100 and DAQ hardware AT-MIO-16-XE-10 from National Instruments, we perform the multi-channel acquisition at DAQ boards rates. We chose signal conditioning owing to the following advantages: electrically isolation, transducer interfacing, signal amplification, filtering and high-speed channel multiplexing. The mathematical modeling allows us the equilibrium graphical representation of operating curve for system with equation H 2 O+HD -> HDO+H 2 . With Mc. Cobe-Thicle diagram there are determined the numbers of theoretical taller for different configurations of hydrophilic package / catalyst bed. Also, it is easy to monitor the operating parameter variation (L/G-liquid/gas, temperature, etc.) and feeding concentration on gaseous and liquid phase for separation performances. (authors)

Optical spectroscopy versus mass spectrometry: The race for fieldable isotopic analysis

International Nuclear Information System (INIS)

Barshick, C.M.; Young, J.P.; Shaw, R.W.

1995-01-01

Several techniques have been developed to provide on-site isotopic analyses, including decay-counting and mass spectrometry, as well as methods that rely on the accessibility of optical transitions for isotopic selectivity (e.g., laser-induced fluorescence and optogalvanic spectroscopy). The authors have been investigating both mass spectrometry and optogalvanic spectroscopy for several years. Although others have considered these techniques for isotopic analysis, the authors have focussed on the use of a dc glow discharge for atomization and ionization, and a demountable discharge cell for rapid sample exchange. The authors' goal is a fieldable instrument that provides useful uranium isotope ratio information

Heterogeneously catalyzed deuterium separation processes: Hydrogen-water exchange studies at elevated temperatures and pressures

International Nuclear Information System (INIS)

Halliday, J.D.; Rolston, J.H.; Au, J.C.; Den Hartog, J.; Tremblay, R.R.

1985-01-01

New processes for the separation of hydrogen isotopes are required to produce heavy water for CANDU nuclear reactors and to extract tritium formed in the moderator during reactor operation. Wetproofed platinum catalysts capable of promoting rapid exchange of isotopes between countercurrent flows of hydrogen and liquid water in packed columns have been developed at CRNL over the past 15 years. These catalysts provide a catalystic surface for the gas phase exchange reaction H/sub 2/O/sub (v)/ + HD/sub (g)/ ↔ HDO/sub (v)/ + H/sub 2(g)/ as well as a large liquid surface for the liquid phase isotope transfer reaction HDO/sub (v)/ + H/sub 2/O/sub (iota)/↔HDO/sub (iota)/+H/sub 2/O/sub (v)/. Any economic stand-alone heavy water separation process, based on bithermal hydrogen-water exchange over wetproofed platinum catalysts, requires rapid overall exchange of isotopes between two phases at two temperatures. Catalysts developed for cold tower operation at 25-60 0 C are now being tested in a laboratory scale stainless steel trickle bed reactor for performance and stability at simulated hot tower conditions, 150 0 C and 2.0 MPa pressure. Catalytically active layers containing platinum supported on carbon or crystalline silica and wetproofed with Teflon have been prepared on ceramic spheres and stainless steel screening and tested in both random and ordered bed columns

The production of stable isotopes in Spain

Energy Technology Data Exchange (ETDEWEB)

Urgel, M; Iglesias, J; Casas, J; Saviron, J M; Quintanilla, M

1965-07-01

The activities developed in the field of the production of stable isotopes by means of ion-exchange chromatography and thermal diffusion techniques are reported. The first method was used to study the separation of the nitrogen and boron isotopes, whereby the separation factor was determined by the break through method. Values ranging from 1,028 to 1,022 were obtained for the separation factor of nitrogen by using ammonium hydroxide solutions while the corresponding values as obtained for boron amounted to 1,035-1,027 using boric acid solutions. Using ammonium chloride or acetate and sodium borate, respectively, resulted in the obtention of values for the separation factor approaching unity. The isotopic separation has been carried out according to the method of development by displacement. The separation of the isotopes of the noble gases, oxygen, nitrogen and carbon has been accomplished resorting to the method of thermal diffusion. (Author) 16 refs.

Synthesis, spectroscopy, and hydrogen/deuterium exchange in high-spin iron(II) hydride complexes.

Science.gov (United States)

Dugan, Thomas R; Bill, Eckhard; MacLeod, K Cory; Brennessel, William W; Holland, Patrick L

2014-03-03

Very few hydride complexes are known in which the metals have a high-spin electronic configuration. We describe the characterization of several high-spin iron(II) hydride/deuteride isotopologues and their exchange reactions with one another and with H2/D2. Though the hydride/deuteride signal is not observable in NMR spectra, the choice of isotope has an influence on the chemical shifts of distant protons in the dimers through the paramagnetic isotope effect on chemical shift. This provides the first way to monitor the exchange of H and D in the bridging positions of these hydride complexes. The rate of exchange depends on the size of the supporting ligand, and this is consistent with the idea that H2/D2 exchange into the hydrides occurs through the dimeric complexes rather than through a transient monomer. The understanding of H/D exchange mechanisms in these high-spin iron hydride complexes may be relevant to postulated nitrogenase mechanisms.

Hydrogen/Denterium exchange during n.butane conversion on H-ZSM-5

NARCIS (Netherlands)

Narbeshuber, T.; Narbeshuber, Thomas F.; Stockenhuber, Michael; Brait, Axel; Brait, A.; Seshan, Kulathuiyer; Lercher, J.A.

1996-01-01

Steady-state isotope tracer studies and isotope transient response experiments ofn-butane conversion on H-ZSM-5 (Si/Al = 35) were carried out between 673 and 823 K. Among the three main reactions, the rate of H/D-exchange is at least one order of magnitude higher compared to the rates of cracking or

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

Comparison of hydrogen isotope exchange reactions between HTO vapor and the sodium salts of o-, m-, and p-aminobenzoic acid

International Nuclear Information System (INIS)

Okada, Minoru; Imaizumi, Hiroshi; Itoh, Tomoko

1991-01-01

Hydrogen isotope exchange reaction between HTO vapor and one of the sodium salts of o-, m-, and p-aminobenzoic acid (solid) was observed at 50 ∼ 80 degC. The acidity (acidity based on kinetic logic) for the materials at each temperature has been obtained with the A''-McKay plots based on the respective data obtained. The followings have been clarified by comparing these acidities (and the acidities obtained previously). 1) The acidity of aromatic amines can be expressed in terms of the acidity based on kinetic logic. 2) The reactivity of aromatic amine is strongly affected by both I-effect and R-effect. 3) It can be deduced that aromatic amines are more reactive than aliphatic amines. (author)

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.

A solvent extraction technique for the isotopic measurement of dissolved copper in seawater

Energy Technology Data Exchange (ETDEWEB)

Thompson, Claire M., E-mail: claire.thompson@anu.edu.au; Ellwood, Michael J., E-mail: michael.ellwood@anu.edu.au; Wille, Martin, E-mail: martin.wille@uni-tuebingen.de

2013-05-02

Graphical abstract: -- Highlights: •A new sample preparation method for seawater copper isotopic analysis (δ{sup 65}Cu). •Solvent-extraction was used to pre-concentrate metals from seawater samples. •Anion-exchange was used to purify copper from the metal-rich extract. •δ{sup 65}Cu was measured in the north Tasman Sea. •Seawater δ{sup 65}Cu may be linked to marine biological activity. -- Abstract: Stable copper (Cu) isotope geochemistry provides a new perspective for investigating and understanding Cu speciation and biogeochemical Cu cycling in seawater. In this work, sample preparation for isotopic analysis employed solvent-extraction with amino pyrollidine dithiocarbamate/diethyl dithiocarbamate (APDC/DDC), coupled with a nitric acid back-extraction, to concentrate Cu from seawater. This was followed by Cu-purification using anion-exchange. This straightforward technique is high yielding and fractionation free for Cu and allows precise measurement of the seawater Cu isotopic composition using multi-collector inductively coupled plasma mass-spectrometry. A deep-sea profile measured in the oligotrophic north Tasman Sea shows fractionation in the Cu isotopic signature in the photic zone but is relatively homogenised at depth. A minima in the Cu isotopic profile correlates with the chlorophyll a maximum at the site. These results indicate that a range of processes are likely to fractionate stable Cu isotopes in seawater.

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

Methyl-coenzyme M reductase from methanogenic archaea: isotope effects on label exchange and ethane formation with the homologous substrate ethyl-coenzyme M.

Science.gov (United States)

Scheller, Silvan; Goenrich, Meike; Thauer, Rudolf K; Jaun, Bernhard

2013-10-09

Ethyl-coenzyme M (CH3CH2-S-CH2CH2-SO3(-), Et-S-CoM) serves as a homologous substrate for the enzyme methyl-coenzyme M reductase (MCR) resulting in the product ethane instead of methane. The catalytic reaction proceeds via an intermediate that already contains all six C-H bonds of the product. Because product release occurs after a second, rate-limiting step, many cycles of intermediate formation and reconversion to substrate occur before a substantial amount of ethane is released. In deuterated buffer, the intermediate becomes labeled, and C-H activation in the back reaction rapidly leads to labeled Et-S-CoM, which enables intermediate formation to be detected. Here, we present a comprehensive analysis of this pre-equilibrium. (2)H- and (13)C-labeled isotopologues of Et-S-CoM were used as the substrates, and the time course of each isotopologue was followed by NMR spectroscopy. A kinetic simulation including kinetic isotope effects allowed determination of the primary and α- and β-secondary isotope effects for intermediate formation and for the C-H/C-D bond activation in the ethane-containing intermediate. The values obtained are in accordance with those found for the native substrate Me-S-CoM (see preceding publication, Scheller, S.; Goenrich, M.; Thauer, R. K.; Jaun, B. J. Am. Chem. Soc. 2013, 135, DOI: 10.1021/ja406485z) and thus imply the same catalytic mechanism for both substrates. The experiment by Floss and co-workers, demonstrating a net inversion of configuration to chiral ethane with CH3CDT-S-CoM as the substrate, is compatible with the observed rapid isotope exchange if the isotope effects measured here are taken into account.

Isotopic composition of chemical elements in natural cycles