WorldWideScience

Sample records for oxygen isotope exchange

  1. 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

  2. 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

  3. Isotope anomalies in oxygen isotope exchange equilibrium systems

    International Nuclear Information System (INIS)

    Kotaka, M.

    1997-01-01

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

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

    Science.gov (United States)

    Kaneko, Masanori; Poulson, Simon R

    2012-04-17

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

  5. 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.

  6. 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.

  7. 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

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

    International Nuclear Information System (INIS)

    Chiba, H.; Sakai, H.

    1985-01-01

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

  9. 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.

  10. 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.

  11. 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

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

    International Nuclear Information System (INIS)

    Gerster, Richard

    1971-01-01

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

  13. 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

  14. 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.

  15. 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.

  16. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    Science.gov (United States)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  17. 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.

  18. Isotopically exchangeable phosphorus

    International Nuclear Information System (INIS)

    Barbaro, N.O.

    1984-01-01

    A critique revision of isotope dilution is presented. The concepts and use of exchangeable phosphorus, the phosphate adsorption, the kinetics of isotopic exchange and the equilibrium time in soils are discussed. (M.A.C.) [pt

  19. 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

  20. 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.

  1. 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.

  2. Oxygen isotope exchange kinetics between coexistent minerals and water in the Ertaibei granite pluton, northern Xinjiang

    Institute of Scientific and Technical Information of China (English)

    刘伟; 李志安; 赵志忠

    1996-01-01

    Coexistent minerals quartz, feldspar and biotite vary widely in δ18O value and display remarkable 18O/16O disequilibrium relations in the Ertaibei granite pluton, northern Xinjiang. The 18O/16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic water are evaluated by the mass balance consideration. The results show that the 18O/16O exchange reaction is not necessarily accompanied by what geologists describe as petrological and mineralogiesl alteration effects, indicating that the exchange reaction occurs at a comparatively high temperature during subsolidus cooling of magmas. Exchange mechanism is mainly controlled by diffusion. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Ertaibei pluton lived for 0.8-3 Ma, with a fluid flow rate of 3 × 10-14 mol · s-1 and water/rock (W/R) ratio of 0.79 - 3.08. Flow path and initial heterogeneity of the exotic metamorphic fluid are modelled with the δ1

  3. Spontaneous Oxygen Isotope Exchange between Carbon Dioxide and Oxygen-Containing Minerals: Do the Minerals "breathe" CO2?

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Bouša, Milan; Zukal, Arnošt; Knížek, Antonín; Kubelík, Petr; Rojík, P.; Nováková, Jana; Ferus, Martin

    2016-01-01

    Roč. 120, č. 1 (2016), s. 508-516 ISSN 1932-7447 R&D Projects: GA MŠk LD14115; GA MŠk(CZ) LD13060; GA ČR(CZ) GA14-12010S Grant - others:COST(XE) CM1104 Institutional support: RVO:61388955 Keywords : Absorption spectroscopy * Infrared spectrometers * Oxygen Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.536, year: 2016

  4. 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

  5. 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.

  6. 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

  7. 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

  8. Oxygen isotopic anomalies in Allende inclusion HAL

    International Nuclear Information System (INIS)

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

    1980-01-01

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

  9. Uranium isotope separation using styrene cation exchangers

    International Nuclear Information System (INIS)

    Kahovec, J.

    1980-01-01

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

  10. 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

  11. 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)

  12. Stable carbon and oxygen isotope ratios of annual rings of pinus radiata provide an integrative record of canopy gas exchange

    International Nuclear Information System (INIS)

    Barbour, M.M.; Farquhar, G.D.

    2000-01-01

    Full text: Seasonal variation in δ 13 C and δ 18 O of cellulose from annual rings of Pinus radiata growing at each of three sites in New Zealand was measured. The three sites differed in annual water balance, temperature, and vapour pressure deficit, and these differences were reflected in cellulose δ 13 C and δ 18 O. Specific events such as drought or heavy rain were recorded as peaks and troughs in enrichment. A canopy-level combined photosynthesis and conductance model was linked to a model of soil water content and δ 18 O of xylem water to allow daily prediction of δ 13 C and δ 18 O of cellulose. A photosynthesis-weighted average of δ 13 C and δ 18 O was calculated for each sampling period. Each sample represented between 3 and 30 days, depending on stem growth rate. The timing and amplitude of changes in δ 13 C were predicted accurately by the model, while general seasonal patterns and event related peaks in δ 18 O enrichment were well predicted. These results suggest that stable isotope ratios of cellulose from annual rings reflect the canopy response to interactions between site-specific and seasonal variation in climatic conditions and soil water availability

  13. Isotope exchange reactions in hydrogen mixtures

    International Nuclear Information System (INIS)

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

    1990-12-01

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

  14. Separation of uranium isotopes by accelerated isotope exchange reactions

    International Nuclear Information System (INIS)

    Seko, M.; Miyake, T.; Inada, K.; Ochi, K.; Sakamoto, T.

    1977-01-01

    A novel catalyst for isotope exchange reaction between uranium(IV) and uranium(VI) compounds enables acceleration of the reaction rate as much as 3000 times to make industrial separation of uranium isotopes economically possible

  15. Oxygen isotope ratios of the Icelandic crust

    International Nuclear Information System (INIS)

    Hattori, K.; Muehlenbachs, K.

    1982-01-01

    Oxygen isotope ratios of hydrothermally altered basalts from depth of up to approx.3 km are reported from three localities in Iceland: International Research Drilling Project (IRDP) core at Reydarfjordur, eastern Iceland (Tertiary age); drill cuttings from Reykjavik (Plio-Pleistocene age); and Halocene drill cuttings from the active Krafla central volcano. Whole rock samples from these three localities have delta 18 O values averaging +3.9 +- 1.3, +2.4 +- 1.1, and -7.7 +- 2.4%, respectively. The observed values in the deeper samples from Krafla are as low as the values for any rocks previously reported. There seems to be a slight negative gradient in delta 18 O with depth at the former two localities and a more pronounced one at Krafla. Oxygen isotope fractionations between epidote and quartz and those between calcite and fluid suggests that the basalts were altered at temperatures of 300 0 --400 0 C. Low deltaD and delta 18 O of epidote and low delta 34 S of anhydrite indicate that the altering fluids in all three areas originated as meteoric waters and have undergone varied 'oxygen shifts'. Differences in the 18 O shift of the fluids are attributed to differences in hydrothermal systems; low water/rock ratios ( 5) at Krafla. The convective hydrothermal activity, which is probably driven by silicic magma beneath the central volcanoes, has caused strong subsolidus depletion of 18 O in the rocks. The primary-magnetic delta 18 O value of the rocks in the Tertiary IRDP core was about +3.9%, which is lower than that obtained for fresh basalt from other places. Such exceptionally low delta 18 O magmas are common in Iceland and may occur as the result of oxygen isotope exchange with or assimilation of altered rocks that form a thick sequence beneath the island due to isostatic subsidence

  16. Stable oxygen isotope and flux partitioning demonstrates understory of an oak savanna contributes up to half of ecosystem carbon and water exchange

    Directory of Open Access Journals (Sweden)

    Maren eDubbert

    2014-10-01

    Full Text Available Semi-arid ecosystems contribute about 40% to global net primary production (GPP even though water is a major factor limiting carbon uptake. Evapotranspiration (ET accounts for up to 95% of the water loss and in addition, vegetation can also mitigate drought effects by altering soil water distribution. Hence, partitioning of carbon and water fluxes between the soil and vegetation components is crucial to gain mechanistic understanding of vegetation effects on carbon and water cycling. However, the possible impact of herbaceous vegetation in savanna type ecosystems is often overlooked. Therefore, we aimed at quantifying understory vegetation effects on the water balance and productivity of a Mediterranean oak savanna. ET and net ecosystem CO2 exchange (NEE were partitioned based on flux and stable oxygen isotope measurements and also rain infiltration was estimated.The understory vegetation contributed importantly to total ecosystem ET and GPP with a maximum of 43% and 51%, respectively. It reached water-use efficiencies (WUE; ratio of carbon gain by water loss similar to cork-oak trees. The understory vegetation inhibited soil evaporation (E and, although E was large during wet periods, it did not diminish WUE during water-limited times. The understory strongly increased soil water infiltration, specifically following major rain events. At the same time, the understory itself was vulnerable to drought, which led to an earlier senescence of the understory growing under trees as compared to open areas, due to competition for water. Thus, beneficial understory effects are dominant and contribute to the resilience of this ecosystem. At the same time the vulnerability of the understory to drought suggests that future climate change scenarios for the Mediterranean basin threaten understory development. This in turn will very likely diminish beneficial understory effects like infiltration and ground water recharge and therefore ecosystem resilience to

  17. 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.

  18. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

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

    1979-12-01

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

  19. 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

  20. Normalization of oxygen and hydrogen isotope data

    Science.gov (United States)

    Coplen, T.B.

    1988-01-01

    To resolve confusion due to expression of isotopic data from different laboratories on non-corresponding scales, oxygen isotope analyses of all substances can be expressed relative to VSMOW or VPDB (Vienna Peedee belemnite) on scales normalized such that the ??18O of SLAP is -55.5% relative to VSMOW. H3+ contribution in hydrogen isotope ratio analysis can be easily determined using two gaseous reference samples that differ greatly in deuterium content. ?? 1988.

  1. Scavenging of oxygen vacancies at modulation-doped oxide interfaces: Evidence from oxygen isotope tracing

    DEFF Research Database (Denmark)

    Chen, Yunzhong; Döbeli, M.; Pomjakushina, E.

    2017-01-01

    , the mechanisms underlying the extreme mobility enhancement remain elusive. Herein, we used 18O isotope exchanged SrTi18O3 as substrates to create 2DEG at room temperature with and without the LSMO buffer layer. By mapping the oxygen profile across the interface between STO18 and disordered LaAlO3 or yttria...

  2. Isotope exchange reaction on solid breeder materials

    International Nuclear Information System (INIS)

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

    2000-01-01

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

  3. Oxygen isotopic fractionation during bacterial sulfate reduction

    Science.gov (United States)

    Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.

    2006-12-01

    Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

  4. Stable Oxygen-18 and Deuterium Isotopes

    DEFF Research Database (Denmark)

    Müller, Sascha

    The application of stable Oxygen-18 (18O) and Deuterium (2H) isotopes, as a tracer for fluxes between different compartments of the water cycle was subject of the present PhD-thesis. During a three year period, temporal data from a wide range of water cycle constituents was collected from...... the Skjern River catchment, Denmark. The presented applications focused on studying the isotopic 'input signal' to the hydrosphere in the form of precipitation, the isotopic 'output signal' with its related dynamic processes at a coastal saltwater-freshwater interface (groundwater isotopes) and the temporal...... development within a given lowland headwater catchment (stream water isotopes). Based on our investigations on the precipitation isotopic composition a local meteoric water line (LMWL) was constructed and expressed as: δ2H=7.4 δ18O + 5.36‰. Moreover, we showed that under maritime temperature climate influence...

  5. 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.

  6. Major events in Neogene oxygen isotopic records

    International Nuclear Information System (INIS)

    Kennett, J.P.; Hodell, D.A.

    1986-01-01

    Changes in oxygen isotopic ratios of foraminiferal calcite during the cainozoic have been one of the primary tools for investigating the history of Arctic and Antarctic glaciation, although interpretations of the oxygen isotopic record differ markedly. The ambiguity in interpretation results mainly from the partitioning of temperature from ice volume effects in delta 18 O changes. Oxygen isotopic records for the Cainozoic show an increase in delta 18 O values towards the present, reflecting gradual cooling and increased glaciation of the Earth's climate since the late Cretaceous. A variety of core material from the South Atlantic and South-west Pacific oceans are investigated. This composite data represents one of the most complete available with which to evaluate the evolution of glaciation during the Neogene. Expansion of ice shelves in Antarctica undoubtedly accompanied the increased glaciation of the northern hemisphere, since eustatic sea-level lowering would positively reinforce ice growth on Antarctica

  7. Tritium isotopic exchange in air detritiation dryers

    International Nuclear Information System (INIS)

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

    1989-02-01

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

  8. 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

  9. 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)

  10. Oxygen isotope fractionation in uranium oxides

    International Nuclear Information System (INIS)

    Zheng Yongfei

    1995-01-01

    Thermodynamic oxygen isotope factors for uranium oxides have been calculated by means of the modified increment method. The sequence of 18 O-enrichment in the uranium oxides with respect to the common rock-forming minerals is predicted as follows: spinel 3 < illite. Two sets of self-consistent fractionation factors between the uranium oxides and water and between the uranium oxides and the other minerals have been obtained for 0∼1200 degree C. The theoretical results are applicable to the isotopic geothermometry of uranium ores when pairing with other gangue minerals in hydrothermal uranium deposits

  11. Contribution to the study of isotopic exchange of oxygen between nickel oxide and the gases arising from the oxidation reaction of carbon monoxide; Contribution a l'etude de l'echange isotopique de l'oxygene entre l'oxyde de nickel et les gaz de la reaction d'oxydation de l'oxyde de carbone

    Energy Technology Data Exchange (ETDEWEB)

    Bailly, J C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-12-01

    The 3 isotopic reactions of oxygen: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, and C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O between CO, CO{sub 2}, O{sub 2} and NiO are studied using a mass spectrometer. The isotopic gaseous mixtures are prepared from oxygen-18 enriched water. A first order kinetic law has been found for these reactions in the gaseous phase, and the activation energies have been determined. Only CO and CO{sub 2} exchange oxygen, at room temperature, but only with part of the oxide surface. Gaseous O{sub 2} reacts with the whole surface at 250 C, the slow step of the exchange process, in the gaseous phase, being certainly the mobility of oxygen ions on the surface of NiO. (author) [French] Les 3 reactions d'echange isotopique de l'oxygene: C{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O + Ni{sup 18}O, {sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} {sup 16}O{sub 2} + Ni{sup 18}O, et C{sup 16}O{sup 18}O + Ni{sup 16}O {r_reversible} C{sup 16}O{sub 2} + Ni{sup 18}O entre l'oxyde de carbone, l'oxygene gazeux, le gaz carbonique et l'oxyde de nickel sont etudiees par spectrometrie de masse. Les melanges isotopiques gazeux sont prepares a partir d'une eau enrichie en isotope 18 de l'oxygene. Une loi cinetique du premier ordre a ete trouvee pour les trois reactions d'echange en phase gazeuse, et des energies d'activation de ces reactions ont ete determinees. Seuls CO et CO{sub 2} echangent l'oxygene, des la temperature ambiante, mais avec une fraction seulement de la surface de l'oxyde. O{sub 2} gazeux reagit avec toute la surface du solide a 250 C, l'etape lente du processus d'echange en phase gazeuse etant vraisemblablement liee a la mobilite des ions oxygene superficiels de NiO. (auteur)

  12. Fractionation of oxygen isotopes between mammalian bone-phosphate and environmental drinking water

    International Nuclear Information System (INIS)

    Luz, B.; Kolodny, V.; Horowitz, M.

    1984-01-01

    The delta 18 O of mammalian bone-phosphate varies linearly with delta 18 O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of delta 18 O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relative to its energy expenditure is sensitive to isotopic ratio changes in environmental water. (author)

  13. 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.

  14. 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)

  15. Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

    NARCIS (Netherlands)

    Mrozek, D. J.; Van Der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.

    2015-01-01

    This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from atmospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses

  16. OXYGEN ISOTOPIC COMPOSITIONS OF SOLAR CORUNDUM GRAINS

    International Nuclear Information System (INIS)

    Makide, Kentaro; Nagashima, Kazuhide; Huss, Gary R.; Krot, Alexander N.

    2009-01-01

    Oxygen is one of the major rock-forming elements in the solar system and the third most abundant element of the Sun. Oxygen isotopic composition of the Sun, however, is not known due to a poor resolution of astronomical spectroscopic measurements. Several Δ 17 O values have been proposed for the composition of the Sun based on (1) the oxygen isotopic measurements of the solar wind implanted into metallic particles in lunar soil ( 2 O 3 ) is thermodynamically the first condensate from a cooling gas of solar composition. Corundum-bearing CAIs, however, are exceptionally rare, suggesting either continuous reaction of the corundum condensates with a cooling nebular gas and their replacement by hibonite (CaAl 12 O 19 ) or their destruction by melting together with less refractory condensates during formation of igneous CAIs. In contrast to the corundum-bearing CAIs, isolated micrometer-sized corundum grains are common in the acid-resistant residues from unmetamorphosed chondrites. These grains could have avoided multistage reprocessing during CAI formation and, therefore, can potentially provide constraints on the initial oxygen isotopic composition of the solar nebula, and, hence, of the Sun. Here we report oxygen isotopic compositions of ∼60 micrometer-sized corundum grains in the acid-resistant residues from unequilibrated ordinary chondrites (Semarkona (LL3.0), Bishunpur (LL3.1), Roosevelt County 075 (H3.2)) and unmetamorphosed carbonaceous chondrites (Orgueil (CI1), Murray (CM2), and Alan Hills A77307 (CO3.0)) measured with a Cameca ims-1280 ion microprobe. All corundum grains, except two, are 16 O-rich (Δ 17 O = -22.7 per mille ± 8.5 per mille, 2σ), and compositionally similar to the mineralogically pristine CAIs from the CR carbonaceous chondrites (-23.3 per mille ± 1.9 per mille, 2σ), and solar wind returned by the Genesis spacecraft (-27 per mille ± 6 per mille, 2σ). One corundum grain is highly 17 O-enriched (δ 17 O ∼ +60 per mille, δ 18 O

  17. The effect of carbonic anhydrase on the kinetics and equilibrium of the oxygen isotope exchange in the CO2-H2O system: Implications for δ18O vital effects in biogenic carbonates

    Science.gov (United States)

    Uchikawa, Joji; Zeebe, Richard E.

    2012-10-01

    Interpretations of the primary paleoceanographic information recorded in stable oxygen isotope values (δ18O) of biogenic CaCO3 can be obscured by disequilibrium effects. CaCO3 is often depleted in 18O relative to the δ18O values expected for precipitation in thermodynamic equilibrium with ambient seawater as a result of vital effects. Vital effects in δ18O have been explained in terms of the influence of fluid pH on the overall δ18O of the sum of dissolved inorganic carbon (DIC) species (often referred to as "pH model") and in terms of 18O depletion as a result of the kinetic effects associated with CO2 hydration (CO2 + H2O ↔ H2CO3 ↔ HCO3- + H+) and CO2 hydroxylation (CO2 + OH- ↔ HCO3-) in the calcification sites (so-called "kinetic model"). This study addresses the potential role of an enzyme, carbonic anhydrase (CA), that catalyzes inter-conversion of CO2 and HCO3- in relation to the underlying mechanism of vital effects. We performed quantitative inorganic carbonate precipitation experiments in order to examine the changes in 18O equilibration rate as a function of CA concentration. Experiments were performed at pH 8.3 and 8.9. These pH values are comparable to the average surface ocean pH and elevated pH levels observed in the calcification sites of some coral and foraminiferal species, respectively. The rate of uncatalyzed 18O exchange in the CO2-H2O system is governed by the pH-dependent DIC speciation and the kinetic rate constant for CO2 hydration and hydroxylation, which can be summarized by a simple mathematical expression. The results from control experiments (no CA addition) are in agreement with this expression. The results from control experiments also suggest that the most recently published kinetic rate constant for CO2 hydroxylation has been overestimated. When CA is present, the 18O equilibration process is greatly enhanced at both pH levels due to the catalysis of CO2 hydration by the enzyme. For example, the time required for 18O

  18. 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

  19. 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)

  20. 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

  1. Oxygen isotopic abundances in calcium- aluminum-rich inclusions from ordinary chondrites: implications for nebular heterogeneity.

    Science.gov (United States)

    McKeegan, K D; Leshin, L A; Russell, S S; MacPherson, G J

    1998-04-17

    The oxygen isotopic compositions of two calcium-aluminum-rich inclusions (CAIs) from the unequilibrated ordinary chondrite meteorites Quinyambie and Semarkona are enriched in 16O by an amount similar to that in CAIs from carbonaceous chondrites. This may indicate that most CAIs formed in a restricted region of the solar nebula and were then unevenly distributed throughout the various chondrite accretion regions. The Semarkona CAI is isotopically homogeneous and contains highly 16O-enriched melilite, supporting the hypothesis that all CAI minerals were originally 16O-rich, but that in most carbonaceous chondrite inclusions some minerals exchanged oxygen isotopes with an external reservoir following crystallization.

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

    International Nuclear Information System (INIS)

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

    1975-01-01

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

  3. Fractionation of oxygen and hydrogen isotopes at the hydrate gas forming in the sea sediments

    International Nuclear Information System (INIS)

    Pashkina, V.I.; Esikov, A.D.

    1990-01-01

    The paper gives data on isotope composition of interstitial and near-bottom waters sampled in a region of gas-hydrate formation in the Sea of Okhotsk. The studies show that heavy isotopes of oxygen and hydrogen is used in gas-hydrate formation, with the result that isotope composition of its constitution water constitutes δ 18 O=+1.99per mille, δD=+23per mille relatively to SMOW. Formation of autogenic carbonates leads to isotope exchange with interstitial water wich, in turn, changes its primary isotope composition in the direction of increasing of O-18 content. The near-bottom waters are isotope-light relatively to the SMOW standard and to the mean isotope composition of interstitial water in the studied region of gas-hydrate spreading. (orig.) [de

  4. Preparation and use of nitrogen (2) oxide of special purity for production of oxygen and nitrogen isotopes

    International Nuclear Information System (INIS)

    Polevoj, A.S.

    1989-01-01

    Problems related with production of oxygen and nitrogen isotopes by means of low-temperature rectification of nitrogen (2) oxide are analyzed. Special attention, in particular, is payed to the techniques of synthesis and high purification of initial NO, utilization of waste flows formed during isotope separation. Ways to affect the initial isotope composition of nitrogen oxide and the rate of its homogeneous-isotope exchange, which provide for possibility of simultaneous production of oxygen and nitrogen isotopes by means of NO rectification, are considered. Description of a new technique for high purification of nitrogen oxide, prepared at decomposition of nitric acid by sulfurous anhydride, suggested by the author is presented

  5. Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

    Science.gov (United States)

    Cao, Xiaobin; Liu, Yun

    2011-12-01

    With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for

  6. 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

  7. Evaporation Induced Oxygen Isotope Fractionation in Impact Ejecta

    Science.gov (United States)

    Macris, C. A.; Young, E. D.; Kohl, I. E.; zur Loye, T. E.

    2017-12-01

    Tektites are natural glasses formed as quenched impact melt ejecta. Because they experienced extreme heating while entrained in a hot impact vapor plume, tektites allow insight into the nature of these ephemeral events, which play a critical role in planetary accretion and evolution. During tektite formation, the chemical and isotopic composition of parent materials may be modified by (1) vapor/liquid fractionation at high T in the plume, (2) incorporation of meteoric water at the target site, (3) isotope exchange with atmospheric oxygen (if present), or some combination of the three. Trends from O isotope studies reveal a dichotomy: some tektite δ18O values are 4.0-4.5‰ lower than their protoliths (Luft et al. 1987; Taylor & Epstein 1962), opposite in direction to a vaporization induced fractionation; increases in δ18O with decreasing SiO2 in tektites (Taylor & Epstein 1969) is consistent with vapor fractionation. Using an aerodynamic levitation laser furnace (e.g. Macris et al. 2016), we can experimentally determine the contributions of processes (1), (2) and (3) above to tektite compositions. We conducted a series of evaporation experiments to test process (1) using powdered tektite fused into 2 mm spheres and heated to 2423-2473 K for 50-90 s while levitated in Ar in the furnace. Mass losses were from 23 to 26%, reflecting evaporation of Si and O from the melt. The starting tektite had a δ18O value of 10.06‰ (±0.01 2se) and the residues ranged from 13.136‰ (±0.006) for the least evaporated residue to 14.30‰ (±0.02) for the most evaporated (measured by laser fluorination). The increase in δ18O with increasing mass loss is consistent with Rayleigh fractionation during evaporation, supporting the idea that O isotopes are fractionated due to vaporization at high T in an impact plume. Because atmospheric O2 and water each have distinctive Δ17O values, we should be able to use departures from our measured three-isotope fractionation law to evaluate

  8. Study of isotopic exchange reactions of azidothymidine with tritium

    International Nuclear Information System (INIS)

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

    2003-01-01

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

  9. Fractionation of lithium isotopes in cation-exchange chromatography

    International Nuclear Information System (INIS)

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

    1991-01-01

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

  10. Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

    Science.gov (United States)

    Knoeller, K.; Vogt, C.; Hoth, N.

    2009-12-01

    Bacterial reduction of dissolved sulfate (BSR) is a key process determining the natural attenuation in many contaminated aquifers. For example, in groundwater bodies affected by acid mine drainage (AMD) BSR reduces the contaminant load by producing alkalinity and facilitating a sustainable fixation of sulfur in the sediment. In aquifers contaminated with petroleum hydrocarbons sulfate may act as a terminal electron acceptor for the anaerobic oxidation of the organic contaminants to carbon dioxide and water. Due to the isotope selectivity of sulfate reducing bacteria, BSR shows the most pronounced isotope fractionation within the sulfur cycle. While sulfur displays a straightforward kinetic enrichment in the residual sulfate described by the enrichment factor epsilon (ɛ), the mechanism of oxygen isotope fractionation is still being discussed controversially. Nevertheless, it is agreed on that oxygen isotope exchange between ambient water and residual sulfate occurs during BSR in natural environments. With respect to this potential isotope exchange, the fractionation parameter theta (θ) is introduced instead of the kinetic enrichment factor epsilon (ɛ). The dual isotope system considering both sulfate-sulfur and sulfate-oxygen isotope fractionation and the respective fractionation parameters ɛ and θ provides an excellent tool for the recognition and quantification of BSR. Beyond that, the dual isotope approach may help identify and estimate interfering sulfur transformations such as re-oxidation and disproportionation processes which is especially vital for the understanding of the overall natural attenuation potential of the investigated aquifers. We present two examples from different field studies showing the benefits of applying the combination of sulfur and oxygen isotopes in dissolved sulfate to reveal the details of the sulfur cycle. The first case study is concerned with the evaluation of the potential for BSR in an AMD-affected aquifer close to an

  11. 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)

  12. 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

  13. Quantitative aspects of oxygen and carbon dioxide exchange ...

    African Journals Online (AJOL)

    Quantitative aspects of oxygen and carbon dioxide exchange through the ... ceratophthalmus (Crustacea: Decapoda) during rest and exercise in water and ... intersects zero time on the x-axis, indicating rapid gas exchange at the lung surface.

  14. Kinetics of isotopic exchanges by using radioactive indicators

    International Nuclear Information System (INIS)

    May, S.

    1958-12-01

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

  15. Near Surface CO2 Triple Oxygen Isotope Composition

    Directory of Open Access Journals (Sweden)

    Sasadhar Mahata

    2016-02-01

    Full Text Available The isotopic composition of carbon dioxide in the atmosphere is a powerful tool for constraining its sources and sinks. In particular, the 17O oxygen anomaly [Δ17O = 1000 × ln(1 + δ17O/1000 - 0.516 × 1000 × ln(1 + δ18O/1000], with a value > 0.5‰ produced in the middle atmosphere, provides an ideal tool for probing the exchange of carbon dioxide between the biosphere/hydrosphere and atmosphere. The biosphere/hydrosphere and anthropogenic emissions give values ≤ 0.3‰. Therefore, any anomaly in near surface CO2 would reflect the balance between stratospheric input and exchange with the aforementioned surface sources. We have analyzed Δ17O values of CO2 separated from air samples collected in Taipei, Taiwan, located in the western Pacific region. The obtained mean anomaly is 0.42 ± 0.14‰ (1-σ standard deviation, in good agreement with model prediction and a published decadal record. Apart from typically used δ13C and δ18O values, the Δ17O value could provide an additional tracer for constraining the carbon cycle.

  16. 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.)

  17. 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)

  18. 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

  19. 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

  20. 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

  1. Hydrogen and oxygen isotope ratios of geothermal waters in the southern hachimantai area

    International Nuclear Information System (INIS)

    Matsubaya, Osamu; Etchu, Hiroshi; Takenaka, Teruo; Yoshida, Yutaka.

    1985-01-01

    Geothermal waters from the Matsukawa and Kakkonda Geothermal Plants, wells at Amihari-Motoyu, and Nyuto and Tazawako areas were isotopically studied. The geothermal waters from Mutsukawa, Kakkonda and Amihari-Motoyu have hydrogen isotope ratios similar to the local meteoric waters, while have higher oxygen isotope ratios than the local meteoric waters. This relationship of hydrogen and oxygen isotope ratios, that is called ''oxygen shift'', means that these geothermal waters are meteoric waters undergone the oxygen isotope exchange with rocks at high temperature of underground. The exygen shifts are 2 -- 3 per mil in Matsukawa and Kakkonda, and 7 per mil in Amihari-Motoyu. This difference may be important to understand the processe of water-rock interaction in this area. The geothermal waters at Nyuto and Tazawako areas also show 2 -- 3 per mil oxygen shift. The steam from the Tazawako-cho well and the hot spring water form the Tsurunoyu are estimated to be vapor and liquid phases separated form a single geothermal water of NaCl type, though the hot water from the Tsurunoyu is diluted with shallow meteoric water. (author)

  2. Temperature evolution and the oxygen isotope composition of Phanerozoic oceans from carbonate clumped isotope thermometry

    Science.gov (United States)

    Henkes, Gregory A.; Passey, Benjamin H.; Grossman, Ethan L.; Shenton, Brock J.; Yancey, Thomas E.; Pérez-Huerta, Alberto

    2018-05-01

    Surface temperature is among the most important parameters describing planetary climate and habitability, and yet there remains considerable debate about the temperature evolution of the Earth's oceans during the Phanerozoic Eon (541 million years ago to present), the time during which complex metazoan life radiated on Earth. Here we critically assess the emerging record of Phanerozoic ocean temperatures based on carbonate clumped isotope thermometry of fossil brachiopod and mollusk shells, and we present new data that fill important gaps in the Late Paleozoic record. We evaluate and reject the hypothesis that solid-state reordering of 13C-18O bonds has destroyed the primary clumped isotope temperature signal of most fossils during sedimentary burial at elevated temperatures. The resulting Phanerozoic record, which shows a general coupling between tropical seawater temperatures and atmospheric carbon dioxide (CO2) levels since the Paleozoic, indicates that tropical temperatures during the icehouse climate of the Carboniferous period were broadly similar to present (∼25-30 °C), and suggests that benthic metazoans were able to thrive at temperatures of 35-40 °C during intervals of the early and possibly the latest Paleozoic when CO2 levels were likely 5-10× higher than present-day values. Equally important, there is no resolvable trend in seawater oxygen isotope ratios (δ18 O) over the past ∼500 million years, indicating that the average temperature of oxygen exchange between seawater and the oceanic crust has been high (∼270 °C) since at least the early Paleozoic, which points to mid-ocean ridges as the dominant locus of water-rock interaction over the past half-billion years.

  3. 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)

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

    Science.gov (United States)

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

    2016-02-01

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

  5. A latitudinal study of oxygen isotopes within horsehair

    Science.gov (United States)

    Thompson, E.; Bronk Ramsey, C.; McConnell, J. R.

    2016-12-01

    This study aims to explore the hypothesis that 'if oxygen isotope ratios deplete with decreasing temperature then a study of oxygen isotope ratios within horsehair from Oxfordshire to Iceland will show a latitudinal depletion gradient'. By looking at oxygen isotope values at different geographical positions, we can track the relationship with latitude and with different regional climate features. This will provide a firmer understanding of how to compare climate records from different locations. Additionally, a comparison of the horse breeds from this study to those analysed within previous studies will create an even better understanding of the intra-species variation within the δ18O values of horsehair. A total of 24 horses were sampled on the 7th March from Thordale Stud in Shetland, the Icelandic Food And Veterinary Authority in Iceland, the Exmoor Pony Centre in Exmoor and the Pigeon House Equestrian Centre in Oxfordshire. By starting the sampling process from the most recent growth at the follicle, the sampling date becomes a chronological marker, temporally fixing the first sample within a sequential set of data points extending for one year or longer, depending on the length of each individual hair. The samples were analysed for oxygen isotope values using an IRMS coupled within a Sercon HTEA. Preliminary results show a latitudinal gradient is evident on comparison between the locations, consistent with the findings of Darling and Talbot's study of fresh water isotopes in the British Isles (2003). These results support the hypothesis, showing that a study of oxygen isotope ratios within horse hair from Oxfordshire to Iceland showing a latitudinal depletion gradient, consistent with a depletion of oxygen isotope ratios due to decreasing temperatures. Darling, W. and Talbot, J. (2003). The O and H stable isotope composition of freshwaters in the British Isles. 1. Rainfall. Hydrol. Earth System Science, 7(2), pp.163-181.

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

    International Nuclear Information System (INIS)

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

    1993-01-01

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

  7. 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

  8. Calcium isotope fractionation in ion-exchange chromatography

    International Nuclear Information System (INIS)

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

    1978-01-01

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

  9. 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

  10. 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

  11. 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

  12. OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

    Energy Technology Data Exchange (ETDEWEB)

    Byrn, Marianne; Calvin, Melvin

    1965-12-01

    Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

  13. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    OpenAIRE

    Hannah B Vander Zanden; David X Soto; Gabriel J Bowen; Keith A Hobson; Keith A Hobson

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicat...

  14. Expanding the Isotopic Toolbox: Applications of Hydrogen and Oxygen Stable Isotope Ratios to Food Web Studies

    OpenAIRE

    Vander Zanden, Hannah B.; Soto, David X.; Bowen, Gabriel J.; Hobson, Keith A.

    2016-01-01

    The measurement of stable carbon (δ13C) and nitrogen (δ15N) isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H) and oxygen (δ18O) isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applicatio...

  15. Carbon and Oxygen isotopic composition in paleoenvironmental determination

    International Nuclear Information System (INIS)

    Silva, J.R.M. da.

    1978-01-01

    This work reports that the carbon and oxygen isotopic composition separate the mollusks from marine environment of the mollusks from continental environment in two groups isotopically different, making the biological control outdone by environment control, in the isotopic fragmentation mechanisms. The patterns from the continental environment are more rich in O 16 than the patterns from marine environments. The C 12 is also more frequent in the mollusks from continental environments. The carbon isotopic composition in paterns from continental environments is situated betwen - 10.31 and - 4,05% and the oxygen isotopic composition is situated between - 6,95 and - 2,41%. To the marine environment patterns the carbon isotopic composition is between - 2,08 and + 2,65% and the oxigen isotopic composition is between - 2,08 and + 0,45%. Was also analysed fossil marine mollusks shells and their isotopic composition permit the formulation of hypothesis about the environment which they lived. (C.D.G.) [pt

  16. 99 Tc NMR determination of the oxygen isotope content in 18 O-enriched water.

    Science.gov (United States)

    Tarasov, Valerii P; Kirakosyan, Gayana А; German, Konstantin E

    2018-03-01

    99 Tc NMR has been suggested as an original method of evaluating the content of oxygen isotopes in oxygen-18-enriched water, a precursor for the production of radioisotope fluorine-18 used in positron emission tomography. To this end, solutions of NH 4 TcO 4 or NaTcO 4 (up to 0.28 mol/L) with natural abundance of oxygen isotopes in virgin or recycled 18 O-enriched water have been studied by 99 Tc NMR. The method is based on 16 O/ 17 O/ 18 O intrinsic isotope effects in the 99 Tc NMR chemical shifts, and the statistical distribution of oxygen isotopes in the coordination sphere of TcO 4 - and makes it possible to quantify the composition of enriched water by measuring the relative intensities of the 99 Tc NMR signals of the Tc 16 O 4-n 18 O n - isotopologues. Because the oxygen exchange between TcO 4 - and enriched water in neutral and alkaline solutions is characterized by slow kinetics, gaseous HCl was bubbled through a solution for a few seconds to achieve the equilibrium distribution of oxygen isotopes in the Tc coordination sphere without distortion of the oxygen composition of the water. Pertechnetate ion was selected as a probe due to its high stability in solutions and the significant 99 Tc NMR shift induced by a single 16 O→ 18 O substitution (-0.43 ± 0.01 ppm) in TcO 4 - and spin coupling constant 1 J( 99 Tc- 17 O) (131.46 Hz) favourable for the observation of individual signals of Tc 16 O 4-n 18 O n - isotopologues. Copyright © 2017 John Wiley & Sons, Ltd.

  17. 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.)

  18. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  19. 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

  20. 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.

  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)

  2. Isotopically exchangeable Al in coastal lowland acid sulfate soils

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  3. 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

  4. 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

  5. Sources of Holocene variability of oxygen isotopes in paleoclimate archives

    Directory of Open Access Journals (Sweden)

    A. N. LeGrande

    2009-08-01

    Full Text Available Variability in water isotopes has been captured in numerous archives and used to infer past climate changes. Here we examine water isotope variability over the course of the Holocene using the water-isotope enabled, coupled atmosphere-ocean general circulation model, GISS ModelE-R. Eight Holocene time slices, ~1000 years apart are simulated and driven by estimated changes in orbital configuration, greenhouse gases, and ice sheet extent. We find that simulated water isotope archives match well with those seen in ice cores, ocean sediment cores, and speleothems. The climate changes associated with the water isotope changes, however, are more complex than simple modern spatial slope interpretations might suggest. In particular, water isotope variability in Asian speleothems is linked to alterations in landward water vapor transport, not local precipitation, and ice sheet changes over North America lead to the masking of temperature signals in Summit, Greenland. Salinity-seawater isotope variability is complicated by inter-ocean basin exchanges of water vapor. Water isotopes do reflect variability in the hydrology, but are better interpreted in terms of regional hydrological cycle changes rather than as indicators of local climate.

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

    Science.gov (United States)

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

    2004-04-01

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

  7. Exploring Neutron-Rich Oxygen Isotopes with MoNA

    International Nuclear Information System (INIS)

    Frank, N.; Gade, A.; Peters, W. A.; Thoennessen, M.; Baumann, T.; Bazin, D.; Lecouey, J.-L.; Scheit, H.; Schiller, A.; Brown, J.; DeYoung, P. A.; Finck, J. E.; Hinnefeld, J.; Howes, R.; Luther, B.

    2007-01-01

    The Modular Neutron Array (MoNA) was used in conjunction with a large-gap dipole magnet (Sweeper) to measure neutron-unbound states in oxygen isotopes close to the neutron dripline. While no excited states were observed in 24 O, a resonance at 45(2) keV above the neutron separation energy was observed in 23 O

  8. Carbon and oxygen isotope compositions of the carbonate facies

    Indian Academy of Sciences (India)

    The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleopro- terozoic to the Neoproterozoic period.Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies.However,the ...

  9. Nitrogen and Oxygen Isotopic Studies of the Marine Nitrogen Cycle.

    Science.gov (United States)

    Casciotti, Karen L

    2016-01-01

    The marine nitrogen cycle is a complex web of microbially mediated reactions that control the inventory, distribution, and speciation of nitrogen in the marine environment. Because nitrogen is a major nutrient that is required by all life, its availability can control biological productivity and ecosystem structure in both surface and deep-ocean communities. Stable isotopes of nitrogen and oxygen in nitrate and nitrite have provided new insights into the rates and distributions of marine nitrogen cycle processes, especially when analyzed in combination with numerical simulations of ocean circulation and biogeochemistry. This review highlights the insights gained from dual-isotope studies applied at regional to global scales and their incorporation into oceanic biogeochemical models. These studies represent significant new advances in the use of isotopic measurements to understand the modern nitrogen cycle, with implications for the study of past ocean productivity, oxygenation, and nutrient status.

  10. 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.

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

    International Nuclear Information System (INIS)

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

    2006-01-01

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

  12. Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

    Science.gov (United States)

    Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

    2018-03-01

    Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

  13. Oxygen isotope analysis of plant water without extraction procedure

    International Nuclear Information System (INIS)

    Gan, K.S.; Wong, S.C.; Farquhar, G.D.; Yong, J.W.H.

    2001-01-01

    Isotopic analyses of plant water (mainly xylem, phloem and leaf water) are gaming importance as the isotopic signals reflect plant-environment interactions, affect the oxygen isotopic composition of atmospheric O 2 and CO 2 and are eventually incorporated into plant organic matter. Conventionally, such isotopic measurements require a time-consuming process of isolating the plant water by azeotropic distillation or vacuum extraction, which would not complement the speed of isotope analysis provided by continuous-flow IRMS (Isotope-Ratio Mass Spectrometry), especially when large data sets are needed for statistical calculations in biological studies. Further, a substantial amount of plant material is needed for water extraction and leaf samples would invariably include unenriched water from the fine veins. To measure sub-microlitre amount of leaf mesophyll water, a new approach is undertaken where a small disc of fresh leaf is cut using a specially designed leaf punch, and pyrolysed directly in an IRMS. By comparing with results from pyrolysis of the dry matter of the same leaf, the 18 O content of leaf water can be determined without extraction from fresh leaves. This method is validated using a range of cellulose-water mixtures to simulate the constituents of fresh leaf. Cotton leaf water δ 18 O obtained from both methods of fresh leaf pyrolysis and azeotropic distillation will be compared. The pyrolysis technique provides a robust approach to measure the isotopic content of water or any volatile present in a homogeneous solution or solid hydrous substance

  14. 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.

  15. 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.

  16. 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

  17. 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

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

    Science.gov (United States)

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

    2016-08-01

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

  19. 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%

  20. Oxygen isotopic ratio of the diatom siliceous valves: development of a new method in quantitative paleoclimatology

    International Nuclear Information System (INIS)

    Labeyrie, Laurent.

    1979-07-01

    This paper describes a new method allowing the measurement of the 18 O/ 16 O ratio of the biogenic silica oxygen, which takes into account the effects due to the organic matter and hydration water associated with this type of silica. By isotopic exchange with enriched water, we have been able to fix a treatment which eliminate all contamination and memory effects. This has permitted us to study the temperature dependance of the hydrated silica-water oxygen isotopic fractionation. As application, we present a study of the variations of the delta 18 O of fossil diatoms valves along an Equatorial Pacific sediment core covering the last 20.000 years. The results demonstrate the usefulness of the delta 18 O of the diatom silica for paleoclimatic investigations [fr

  1. Oxygen isotopes in garnet and accessory minerals to constrain fluids in subducted crust

    Science.gov (United States)

    Rubatto, Daniela; Gauthiez-Putallaz, Laure; Regis, Daniele; Rosa Scicchitano, Maria; Vho, Alice; Williams, Morgan

    2017-04-01

    Fluids are considered a fundamental agent for chemical exchanges between different rock types in the subduction system. Constraints on the sources and pathways of subduction fluids thus provide crucial information to reconstruct subduction processes. Garnet and U-Pb accessory minerals constitute some of the most robust and ubiquitous minerals in subducted crust and can preserve multiple growth zones that track the metamorphic evolution of the sample they are hosted in. Microbeam investigation of the chemical (major and trace elements) and isotopic composition (oxygen and U-Pb) of garnet and accessory minerals is used to track significant fluid-rock interaction at different stages of the subduction system. This approach requires consideration of the diffusivity of oxygen isotopes particularly in garnet, which has been investigated experimentally. The nature of the protolith and ocean floor alteration is preserved in relict accessory phases within eclogites that have been fully modified at HP conditions (e.g. Monviso and Dora Maira units in the Western Alps). Minerals in the lawsonite-blueschists of the Tavsanli zone in Turkey record pervasive fluid exchange between mafic and sedimentary blocks at the early stage of subduction. High pressure shear zones and lithological boundaries show evidence of intense fluid metasomatism at depth along discontinuities in Monviso and Corsica. In the UHP oceanic crust of the Zermatt-Saas Zone, garnet oxygen isotopes and tourmaline boron isotopes indicate multistage fluid infiltration during prograde metamorphism. Localized exchanges of aqueous fluids are also observed in the subducted continental crust of the Sesia-Lanzo Zone. In most cases analyses of distinct mineral zones enable identification of multiple pulses of fluids during the rock evolution.

  2. 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

  3. How the oxygen isotope ratio of rain water influences the isotope ratio of chicken eggshell carbonate

    Science.gov (United States)

    Price, Gregory; Grimes, Stephen

    2015-04-01

    The stable oxygen isotope ratio of chicken eggshell carbonate was analysed from chicken eggs laid under free range, and organic farming regimes from across the UK. The eggshell carbonate oxygen isotope data shows a clear depletion in delta18O distribution from the southwest to the northeast. Although consistently offset by around 1 permil, the same isotopic distribution as that seen in eggshell carbonate is observed in the delta18O ratio of rainfall and groundwater from across the UK. This distribution is related to the Rayleigh distillation of rainfall driven by westerly winds across the UK landmass. The clear relationship observed between eggshell delta18O values and that of rainwater presumably reflects the nature of free range chickens which must be drinking locally derived rainwater and supplementing their diet and water intake with locally derived food. These results suggest that the oxygen isotope value of chicken eggshells can be used as a forensic tool to identify the locality that free range and organic eggs were laid within the UK. Furthermore, if suitable material is preserved in the archaeological and geological record then such a relationship can potentially be used to establish the oxygen isotope value of rainwater from which ancient and / or ancestral birds lived.

  4. Oxygen isotopic signature of CO2 from combustion processes

    Directory of Open Access Journals (Sweden)

    W. A. Brand

    2011-02-01

    Full Text Available For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (13C and 18O abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the δ18O signature of CO2 from combustion processes, which are widely present both naturally (wild fires, and human induced (fossil fuel combustion, biomass burning in the carbon cycle. All these combustion processes use atmospheric oxygen, of which the isotopic signature is assumed to be constant with time throughout the whole atmosphere. The combustion is generally presumed to take place at high temperatures, thus minimizing isotopic fractionation. Therefore it is generally supposed that the 18O signature of the produced CO2 is equal to that of the atmospheric oxygen. This study, however, reveals that the situation is much more complicated and that important fractionation effects do occur. From laboratory studies fractionation effects on the order of up to 26%permil; became obvious in the derived CO2 from combustion of different kinds of material, a clear differentiation of about 7‰ was also found in car exhausts which were sampled directly under ambient atmospheric conditions. We investigated a wide range of materials (both different raw materials and similar materials with different inherent 18O signature, sample geometries (e.g. texture and surface-volume ratios and combustion circumstances. We found that the main factor influencing the specific isotopic signatures of the combustion-derived CO2 and of the concomitantly released oxygen-containing side products, is the case-specific rate of combustion. This points firmly into the direction of (diffusive transport of oxygen to the reaction zone as the cause of the isotope fractionation. The original total 18O signature of the material appeared to have little influence, however, a contribution of specific bio

  5. 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

  6. 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

  7. Oxygen Isotopes in Chondritic Interplanetary Dust: Parent-Bodies and Nebular Oxygen Reservoirs

    International Nuclear Information System (INIS)

    Aleon, J; McKeegan, K D; Leshin, L

    2006-01-01

    Planetary objects have preserved various amounts of oxygen issued from isotopically different oxygen reservoirs reflecting their origin and physico-chemical history. An 16 O-rich component is preserved in refractory inclusions (CAIs) whereas meteorites matrices are enriched in an 16 O-poor component. The origin of these components is still unclear. The most recent models are based on isotope selective photodissociation of CO in a 16 O-rich nebula/presolr cloud resulting in a 16 O-poor gas in the outer part of the nebula. However because most meteorite components are thought to be formed in the inner 3AU of the solar nebula, the precise isotopic composition of outer solar system components is yet unknown. In that respect, the oxygen isotopic composition of cometary dust is a key to understand the origin of the solar system. The Stardust mission will bring back to the Earth dust samples from comet Wild2, a short period comet from the Jupiter family. A precise determination of the oxygen isotope composition of Wild2 dust grains is essential to decipher the oxygen reservoirs of the outer solar system. However, Stardust samples may be extremely fragmented upon impact in the collector. In addition, interplanetary dust particles (IDPs) collected in the stratosphere are likely to contain comet samples. Therefore, they started to investigate the oxygen isotopic composition of a suite of chondritic interplanetary dust particles that includes IDPs of potential cometary origin using a refined procedure to increase the lateral resolution for the analysis of Stardust grains or IDP subcomponents down to ∼ 3 (micro)m. High precision data for 4 IDPs were previously reported, here they have measured 6 additional IDPs

  8. 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)

  9. 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.).

  10. 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)

  11. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    Science.gov (United States)

    Boshers, D.; Granger, J.; Bohlke, J. K.

    2016-12-01

    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  12. 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

  13. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    International Nuclear Information System (INIS)

    Vickridge, I.C.; Ganem, J.-J.; Battistig, G.; Szilagyi, E.

    2000-01-01

    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in 18 O. Measurement of the 18 O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in 18 O(p,α) 15 N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in 16 O 2 , is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar

  14. Oxygen isotopic tracing study of the dry thermal oxidation of 6H SiC

    Energy Technology Data Exchange (ETDEWEB)

    Vickridge, I.C. E-mail: vickridge@gps.jussieu.fr; Ganem, J.-J.; Battistig, G.; Szilagyi, E

    2000-03-01

    The (0 0 0 1) and (0 0 0 1-bar) faces of 6H SiC have been oxidised sequentially at 1100 deg. C and 100 mbar in ultra-dry oxygen of natural isotopic concentration and in ultra-dry oxygen highly enriched in {sup 18}O. Measurement of the {sup 18}O isotopic concentration profiles by nuclear resonance profiling with the narrow resonance at 151 keV in {sup 18}O(p,{alpha}){sup 15}N shows that on the carbon-terminated face (0 0 0 1-bar) the oxidation mechanism is rather similar to that observed on Si(1 0 0), but that on the silicon-terminated face (0 0 0 1) the surface isotopic exchange and oxide formation are superposed. The surface exchange observed during a third dry oxidation, in {sup 16}O{sub 2}, is very similar in magnitude and spatial extent on Si(1 0 0), and the two 6H SiC faces, suggesting that at least near the surface the nature and composition of the three oxides are very similar.

  15. Origin of the brines near WIPP from the drill holes ERDA-6 and WIPP-12 based on stable isotope concentrations of hydrogen and oxygen

    International Nuclear Information System (INIS)

    Spiegler, P.; Updegraff, D.

    1983-03-01

    Pathways which might alter the isotopic compositions of deuterium and oxygen-18 meteoric water, seawaters, and in hydration waters in gypsum to the isotopic compositions of brines encountered at ERDA-6 and WIPP-12 are discussed. Present geologic conditions do not favor the alteration of the isotopic compositions of waters that exist near the WIPP site to those of the brines by these pathways. It is concluded that the brines encountered at ERDA-6 and WIPP-12 are probably derived from ancient ocean waters that have been isotopically enriched in oxygen-18 by exchange interaction with rock. The dehydration of gypsum as a process of origin of these brines cannot be ruled out

  16. 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)

  17. 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

  18. Oxygen isotope variations in phosphate of biogenic apatites. Pt.1

    International Nuclear Information System (INIS)

    Kolodny, Y.; Luz, B.; Navon, O.

    1983-01-01

    The major advantage of the oxygen in phosphate isotope paleothermometry is that it is a system which records temperatures with great sensitivity while bone (and teeth) building organisms are alive, and the record is nearly perfectly preserved after death. Fish from seven water bodies of different temperatures (3-23 0 C) and different delta 18 O (values - 16 to + 3) of the water were analysed. The delta 18 O values of the analysed PO 4 vary from 6 to 25. The system passed the following tests: (a) the temperature deduced from isotopic analyses of the sequence of fish from Lake Baikal are in good agreement with the temperatures measured in the thermally stratified lake; (b) the isotopic composition of fish bone phosphate is not influenced by the isotopic composition of the phosphate which is fed to the fish, but only by temperature and water composition. Isotopic analysis of fossil fish in combination with analysis of mammal bones should be a useful tool in deciphering continental paleoclimates. (orig.)

  19. Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

    Science.gov (United States)

    Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

    2018-06-01

    Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

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

    Science.gov (United States)

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

    2013-12-01

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

  1. Reactive oxygen species production and discontinuous gas exchange in insects

    OpenAIRE

    Boardman, Leigh; Terblanche, John S.; Hetz, Stefan K.; Marais, Elrike; Chown, Steven L.

    2011-01-01

    While biochemical mechanisms are typically used by animals to reduce oxidative damage, insects are suspected to employ a higher organizational level, discontinuous gas exchange mechanism to do so. Using a combination of real-time, flow-through respirometry and live-cell fluorescence microscopy, we show that spiracular control associated with the discontinuous gas exchange cycle (DGC) in Samia cynthia pupae is related to reactive oxygen species (ROS). Hyperoxia fails to increase mean ROS produ...

  2. 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)

  3. Assessing the identifiability in isotope exchange depth profiling measurements

    DEFF Research Database (Denmark)

    Ciucci, Francesco; Panagakos, Grigorios; Chen, Chi

    2014-01-01

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

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

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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

  10. 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)

  11. 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.)

  12. 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.

  13. Oxygen isotope fractionation in the CaCO3-DIC-H2O system

    Science.gov (United States)

    Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

    2017-10-01

    The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading

  14. 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...

  15. Oxygen isotope geochemistry of The Geysers reservoir rocks, California

    Energy Technology Data Exchange (ETDEWEB)

    Gunderson, Richard P.; Moore, Joseph N.

    1994-01-20

    Whole-rock oxygen isotopic compositions of Late Mesozoic graywacke, the dominant host rock at The Geysers, record evidence of a large liquid-dominated hydrothermal system that extended beyond the limits of the present steam reservoir. The graywackes show vertical and lateral isotopic variations that resulted from gradients in temperature, permeability, and fluid composition during this early liquid-dominated system. All of these effects are interpreted to have resulted from the emplacement of the granitic "felsite" intrusion 1-2 million years ago. The {delta}{sup 18}O values of the graywacke are strongly zoned around a northwest-southeast trending low located near the center of and similar in shape to the present steam system. Vertical isotopic gradients show a close relationship to the felsite intrusion. The {delta}{sup 18}O values of the graywacke decrease from approximately 15 per mil near the surface to 4-7 per mil 300 to 600 m above the intrusive contact. The {delta}{sup 18}O values then increase downward to 8-10 per mil at the felsite contact, thereafter remaining nearly constant within the intrusion itself. The large downward decrease in {delta}{sup 18}O values are interpreted to be controlled by variations in temperature during the intrusive event, ranging from 150{degree}C near the surface to about 425{degree}C near the intrusive contact. The upswing in {delta}{sup 18}O values near the intrusive contact appears to have been caused by lower rock permeability and/or heavier fluid isotopic composition there. Lateral variations in the isotopic distributions suggests that the effects of temperature were further modified by variations in rock permeability and/or fluid-isotopic composition. Time-integrated water:rock ratios are thought to have been highest within the central isotopic low where the greatest isotopic depletions are observed. We suggest that this region of the field was an area of high permeability within the main upflow zone of the liquid

  16. Triple oxygen isotope systematics of structurally bonded water in gypsum

    Science.gov (United States)

    Herwartz, Daniel; Surma, Jakub; Voigt, Claudia; Assonov, Sergey; Staubwasser, Michael

    2017-07-01

    The triple oxygen isotopic composition of gypsum mother water (gmw) is recorded in structurally bonded water in gypsum (gsbw). Respective fractionation factors have been determined experimentally for 18O/16O and 17O/16O. By taking previous experiments into account we suggest using 18αgsbw-gmw = 1.0037; 17αgsbw-gmw = 1.00195 and θgsbw-gmw = 0.5285 as fractionation factors in triple oxygen isotope space. Recent gypsum was sampled from a series of 10 ponds located in the Salar de Llamara in the Atacama Desert, Chile. Total dissolved solids (TDS) in these ponds show a gradual increase from 23 g/l to 182 g/l that is accompanied by an increase in pond water 18O/16O. Gsbw falls on a parallel curve to the ambient water from the saline ponds. The offset is mainly due to the equilibrium fractionation between gsbw and gmw. However, gsbw represents a time integrated signal biased towards times of strong evaporation, hence the estimated gmw comprises elevated 18O/16O compositions when compared to pond water samples taken on site. Gypsum precipitation is associated with algae mats in the ponds with lower salinity. No evidence for respective vital effects on the triple oxygen isotopic composition of gypsum hydration water is observed, nor are such effects expected. In principle, the array of δ18Ogsbw vs. 17Oexcess can be used to: (1) provide information on the degree of evaporation during gypsum formation; (2) estimate pristine meteoric water compositions; and (3) estimate local relative humidity which is the controlling parameter of the slope of the array for simple hydrological situations. In our case study, local mining activities may have decreased deep groundwater recharge, causing a recent change of the local hydrology.

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

    International Nuclear Information System (INIS)

    Obanawa, Heiichiro; Takeda, Kunihiko; Seko, Maomi

    1991-01-01

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

  18. Oxygen and carbon isotopic compositions of gases respired by humans

    International Nuclear Information System (INIS)

    Epstein, S.; Zeiri, L.

    1988-01-01

    Oxygen-isotope fractionation associated with respiration in human individuals at rest is linearly related to the fraction of the O 2 utilized in the respiration process. The slope of this relationship is affected by a history of smoking, by vigorous exercise, and by the N 2 /O 2 ratio of the inhaled gas. For patients who suffer anemia-related diseases, the slope of this relationship is directly proportional to their level of hemoglobin. These results introduce a new approach for studying the mechanisms of O 2 consumption in human respiration and how they are affected by related diseases

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

    Science.gov (United States)

    Keedakkadan, Habeeb Rahman; Abe, Osamu

    2015-04-30

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

  20. 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.

  1. Oxygen isotopic analyses of individual planktic foraminifera species: Implications for seasonality in the western Arabian Sea

    Digital Repository Service at National Institute of Oceanography (India)

    Naidu, P.D.; Niitsuma, N.; Naik, S.S.

    The variation of stable isotopes between individual shells of planktic foraminifera of a given species and size may provide short-term seasonal insight on Paleoceanography. In this context, oxygen isotope analyses of individual Globigerinoides...

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  3. 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

  4. The Oxygen Isotopic Composition of Phosphate: A Tracer for Phosphate Sources and Cycling

    Energy Technology Data Exchange (ETDEWEB)

    Mclaughlin, K. [Southern California Coastal Water Research Project, Costa Mesa, University of California, CA (United States); Young, M. B.; Paytan, A.; Kendall, C. [U.S. Geological Survey, University of California, CA (United States)

    2013-05-15

    Phosphorus (P) is a limiting macro-nutrient for primary productivity and anthropogenic P-loading to aquatic ecosystems is one of the leading causes of eutrophication in many ecosystems throughout the world. Because P has only one stable isotope, traditional isotope techniques are not possible for tracing sources and cycling of P in aquatic systems. However, much of the P in nature is bonded to four oxygen (O) atoms as orthophosphate (PO{sub 4}{sup 3-}). The P-O bonds in orthophosphate are strongly resistant to inorganic hydrolysis and do not exchange oxygen with water without biological mediation (enzyme-mediated recycling). Thus, the oxygen isotopic composition of dissolved inorganic phosphate ({delta}{sup 18}O{sub p}) may be used as a tracer for phosphate sources and cycling in aquatic ecosystems. Recently, several studies have been conducted utilizing {delta}{sup 18}O{sub p} as a tracer for phosphate sources and cycling in various aquatic environments. Specifically, work to date indicates that {delta}{sup 18}O{sub p} is useful for determining sources of phosphate to aquatic systems if these sources have unique isotopic signatures and phosphate cycling within the system is limited compared to input fluxes. In addition, because various processes imprint specific fractionation effects, the {delta}{sup 18}O{sub p} tracer can be utilized to determine the degree of phosphorous cycling and processing through the biomass. This chapter reviews several of these studies and discusses the potential to utilize the {delta}{sup 18}O{sub p} of phosphate in rivers and streams. (author)

  5. Oxygen isotope systematics of chondrules in the Murchison CM2 chondrite and implications for the CO-CM relationship

    Science.gov (United States)

    Chaumard, Noël; Defouilloy, Céline; Kita, Noriko T.

    2018-05-01

    High-precision oxygen three-isotope measurements of olivine and pyroxene were performed on 29 chondrules in the Murchison CM2 chondrite by secondary ion mass spectrometry (SIMS). The oxygen isotope ratios of analyzed chondrules all plot very close to the primitive chondrule minerals (PCM) line. In each of 24 chondrules, the olivine and/or pyroxene grains analyzed show indistinguishable oxygen isotope ratios. Exceptions are minor occurrences of isotopically distinguished relict olivine grains, which were found in nine chondrules. The isotope homogeneity of these phenocrysts is consistent with a co-magmatic crystallization of olivine and pyroxene from the final chondrule melts and a significant oxygen isotope exchange between the ambient gas and the melts. Homogeneous type I chondrules with Mg#'s of 98.9-99.5 have host chondrule Δ17O values ranging from -6.0‰ to -4.1‰, with one exception (Δ17O: -1.2‰; Mg#: 99.6). Homogeneous chondrules with Mg#'s poor H2O ice (∼0.3-0.4× the CI dust; Δ17O > 0‰) and at dust enrichments of ∼300-2000×. Regarding the Mg# and oxygen isotope ratios, the chondrule populations sampled by CM and CO chondrites are similar and indistinguishable. The similarity of these 16O-rich components in CO and CM chondrites is also supported by the common Fe/Mn ratio of olivine in type II chondrules. Although they accreted similar high-temperature silicates, CO chondrites are anhydrous compared to CM chondrites, suggesting they derived from different parent bodies formed inside and outside the snow line, respectively. If chondrules in CO and CM chondrites formed at the same disk locations but the CM parent body accreted later than the CO parent body, the snow line might have crossed the common chondrule-forming region towards the Sun between the time of the CO and CM parent bodies accretion.

  6. 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

  7. 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

  8. Oxygen isotope fractionation between bird bone phosphate and drinking water

    Science.gov (United States)

    Amiot, Romain; Angst, Delphine; Legendre, Serge; Buffetaut, Eric; Fourel, François; Adolfssen, Jan; André, Aurore; Bojar, Ana Voica; Canoville, Aurore; Barral, Abel; Goedert, Jean; Halas, Stanislaw; Kusuhashi, Nao; Pestchevitskaya, Ekaterina; Rey, Kevin; Royer, Aurélien; Saraiva, Antônio Álamo Feitosa; Savary-Sismondini, Bérengère; Siméon, Jean-Luc; Touzeau, Alexandra; Zhou, Zhonghe; Lécuyer, Christophe

    2017-06-01

    Oxygen isotope compositions of bone phosphate (δ18Op) were measured in broiler chickens reared in 21 farms worldwide characterized by contrasted latitudes and local climates. These sedentary birds were raised during an approximately 3 to 4-month period, and local precipitation was the ultimate source of their drinking water. This sampling strategy allowed the relationship to be determined between the bone phosphate δ18Op values (from 9.8 to 22.5‰ V-SMOW) and the local rainfall δ18Ow values estimated from nearby IAEA/WMO stations (from -16.0 to -1.0‰ V-SMOW). Linear least square fitting of data provided the following isotopic fractionation equation: δ18Ow = 1.119 (±0.040) δ18Op - 24.222 (±0.644); R 2 = 0.98. The δ18Op-δ18Ow couples of five extant mallard ducks, a common buzzard, a European herring gull, a common ostrich, and a greater rhea fall within the predicted range of the equation, indicating that the relationship established for extant chickens can also be applied to birds of various ecologies and body masses. Applied to published oxygen isotope compositions of Miocene and Pliocene penguins from Peru, this new equation computes estimates of local seawater similar to those previously calculated. Applied to the basal bird Confuciusornis from the Early Cretaceous of Northeastern China, our equation gives a slightly higher δ18Ow value compared to the previously estimated one, possibly as a result of lower body temperature. These data indicate that caution should be exercised when the relationship estimated for modern birds is applied to their basal counterparts that likely had a metabolism intermediate between that of their theropod dinosaur ancestors and that of advanced ornithurines.

  9. Sources and Contributions of Oxygen During Microbial Pyrite Oxidation: the Triple Oxygen Isotopes of Sulfate

    Science.gov (United States)

    Ziegler, K.; Coleman, M. L.; Mielke, R. E.; Young, E. D.

    2008-12-01

    The triple isotopes of oxygen (Δ17O' = δ17O'-0.528 × δ18O' using logarithmic deltas) can trace the oxygen sources of sulfate produced during sulfide oxidation, an important biogeochemical process on Earth's surface and possibly also on Mars [1]. δ18OSO4 compositions are determined by the isotopic selectivity of the mechanism(s) responsible for their changes, and the δ18O value of the reactants (O2 vs. H2O). The relative proportional importance and contribution of each of those sources and mechanisms, as well as their associated isotopic fractionations, are not well understood. We are investigating the use of Δ 17O as a quantitative and qualitative tracer for the different processes and oxygen sources involved in sulfate production. Δ17O signatures are distinct fingerprints of these reservoirs, independent of fractionation factors that can be ambiguous. We conducted controlled abiotic and biotic (Acidithiobacillus ferrooxidans, A.f.) laboratory experiments in which water was spiked with 18O, allowing us to quantify the sources of sulfate oxygen and therefore the processes attending sulfate formation. Results of this Δ17O tracer study show that A.f. microbes initiate pyrite S-oxidation within hours of exposure, and that sulfate is produced from ~90% atmospheric oxygen. This initial lag-phase (behavior in the initial lag-phase will aid in the understanding of the ecological conditions required for microbial populations to establish and survive. An exponential phase of growth, facilitated by microbial Fe2+-oxidation, follows. The source of sulfate rapidly switches to abiotic sulfide oxidation during exponential growth and the source of oxygen switches from atmospheric O2 to nearly ~100% water. Pending acquisition of complimentary chemistry data (in progress), we interpret our isotope data to indicate that the biotic fractionation factor ɛ18OSO4-O2 of at least ~ -25 to - 35‰ is augmented by microbially induced kinetic fractionation; it is larger than

  10. 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.)

  11. 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)

  12. 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.)

  13. Effects of diagenesis on strontium, carbon, nitrogen and oxygen concentration and isotopic composition of bone

    Science.gov (United States)

    Nelson, Bruce K.; Deniro, Michael J.; Schoeninger, Margaret J.; De Paolo, Donald J.; Hare, P. E.

    1986-09-01

    Paleodietary analysis based on variations in the trace element and stable isotopic composition of inorganic and organic phases in fossil bone depends on the assumption that measured values reflect in vivo values. To test for postmortem alteration, we measured 87Sr /86Sr , 13C /12C , 18O /16O and 15N /14N ratios and Sr concentrations in modern and prehistoric (610 to 5470 yr old) bones of animals with marine or terrestrial diets from Greenland. Bones from modern terrestrial feeders have substantially lower Sr concentrations and more radiogenic 87Sr /86Sr ratios than those from modern marine feeders. This contrast was not preserved in the prehistoric samples, which showed almost complete overlap for both Sr concentration and isotopic composition in bones from the two types of animals. Leaching experiments, X-ray diffraction analysis and infrared spectroscopy indicate that alteration of the Sr concentration and isotopic composition in prehistoric bone probably results from nearly complete exchange with groundwater. Oxygen isotope ratios in fossil apatite carbonate also failed to preserve the original discrimination between modern terrestrial and marine feeders. The C isotope ratio of apatite carbonate did not discriminate between animals with marine or terrestrial diets in the modern samples. Even so, the ranges of apatite δ 13C values in prehistoric bone are more scattered than in modern samples for both groups, suggesting alteration had occurred. δ 13C and δ 15N values of collagen in modern bone are distinctly different for the two feeding types, and this distinction is preserved in most of the prehistoric samples. Our results suggest that postmortem alteration of dietary tracers in the inorganic phases of bone may be a problem at all archaeological sites and must be evaluated in each case. While collagen analyzed in this study was resistant to alteration, evaluation of the possibility of diagenetic alteration of its isotopic composition in bones from other

  14. 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.

  15. 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

  16. Quantifying tidally driven benthic oxygen exchange across permeable sediments

    DEFF Research Database (Denmark)

    McGinnis, Daniel F.; Sommer, Stefan; Lorke, Andreas

    2014-01-01

    Continental shelves are predominately (approximate to 70%) covered with permeable, sandy sediments. While identified as critical sites for intense oxygen, carbon, and nutrient turnover, constituent exchange across permeable sediments remains poorly quantified. The central North Sea largely consists...... of permeable sediments and has been identified as increasingly at risk for developing hypoxia. Therefore, we investigate the benthic O-2 exchange across the permeable North Sea sediments using a combination of in situ microprofiles, a benthic chamber, and aquatic eddy correlation. Tidal bottom currents drive...... the variable sediment O-2 penetration depth (from approximate to 3 to 8 mm) and the concurrent turbulence-driven 25-fold variation in the benthic sediment O-2 uptake. The O-2 flux and variability were reproduced using a simple 1-D model linking the benthic turbulence to the sediment pore water exchange...

  17. Oxygen isotope studies of the Salton Sea geothermal field

    International Nuclear Information System (INIS)

    Olson, E.R.

    1978-01-01

    Interbedded shales and sandstones were drilled to a depth of 1588 metres in Sinclair Number Four Well, Salton Sea Geothermal Field. Bottom hole temperatures are approximately 290 0 C. The oxygen dels of hydrothermal and detrital calcite have a systematic relationship at any depth in the geothermal reservoir. Typical values are: vein calcite, +6 0 / 00 ; calcite in white sandstone, +10 0 / 00 ; calcite in dark gray shale, +11 0 / 00 ; calcite in light gray shale, +17 0 / 00 ; calcite in red-brown shale, +20 0 / 00 . This succession represents decreasing water-rock interaction that is also indicated by the clay mineralogy of the shales. Permeability has a marked effect on the equilibration of water and rocks at any given temperature. Original differences in permeability have resulted in partial preservation of original detrital sedimentary compositions. The fluids in the Salton Sea Geothermal Field are probabaly partially evaporated Colorado River water, and their oxygen del values vary as much as 4 0 / 00 throughout the field. Truesdell's (1974) data suggest that dissolved salts may make the water oxygen activity del as much as 6 0 / 00 greater than the concentration del in the geothermal reservoir. Such an uncertainty is a serious impediment to precise isotope geothermometry in this system.(auth.)

  18. Triple oxygen isotopes in biogenic and sedimentary carbonates

    Science.gov (United States)

    Passey, Benjamin H.; Hu, Huanting; Ji, Haoyuan; Montanari, Shaena; Li, Shuning; Henkes, Gregory A.; Levin, Naomi E.

    2014-09-01

    The 17O anomaly (Δ17O) of natural waters has been shown to be sensitive to evaporation in a way analogous to deuterium excess, with evaporated bodies of water (e.g., leaf waters, lake waters, animal body waters) tending to have lower Δ17O than primary meteoric waters. In animal body water, Δ17O relates to the intake of evaporated waters, evaporative effluxes of water, and the Δ17O value of atmospheric O2, which itself carries signatures of global carbon cycling and photochemical reactions in the stratosphere. Carbonates have the potential to record the triple oxygen isotope compositions of parent waters, allowing reconstruction of past water compositions, but such investigations have awaited development of methods for high-precision measurement of Δ17O of carbonate. We describe optimized methods based on a sequential acid digestion/reduction/fluorination approach that yield Δ17O data with the high precision (∼0.010‰, 1σ) needed to resolve subtle environmental signals. We report the first high-precision Δ17O dataset for terrestrial carbonates, focusing on vertebrate biogenic carbonates and soil carbonates, but also including marine invertebrates and high-temperature carbonates. We determine apparent three-isotope fractionation factors between the O2 analyte derived from carbonate and the parent waters of the carbonate. These in combination with appropriate temperature estimates (from clumped isotope thermometry, or known or estimated body temperatures) are used to calculate the δ18O and Δ17O of parent waters. The clearest pattern to emerge is the strong 17O-depletion in avian, dinosaurian, and mammalian body water (from analyses of eggshell and tooth enamel) relative to meteoric waters, following expected influences of evaporated water (e.g., leaf water) and atmospheric O2 on vertebrate body water. Parent waters of the soil carbonates studied here have Δ17O values that are similar to or slightly lower than global precipitation. Our results suggest

  19. Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden-Popper phases?

    Science.gov (United States)

    Tomkiewicz, Alex C; Tamimi, Mazin A; Huq, Ashfia; McIntosh, Steven

    2015-01-01

    The possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A(n-1)A(2)'B(n)O(3n+1), A(n-1)A(2)'B(n)X(3n+1); LaSrCo(0.5)Fe(0.5)O(4-δ) (n = 1), La(0.3)Sr(2.7)CoFeO(7-δ) (n = 2) and LaSr3Co(1.5)Fe(1.5)O(10-δ) (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. This is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. We conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

  20. Do oxygen isotope values in collagen reflect the ecology and physiology of neotropical mammals?

    Directory of Open Access Journals (Sweden)

    Brooke eCrowley

    2015-11-01

    Full Text Available Stable isotope data provide insight into the foraging ecology of animals. Traditionally, carbon and nitrogen isotope values have been used to infer dietary and habitat preferences. Oxygen isotopes are used less frequently but may complement the ecological information provided by carbon and nitrogen, particularly in densely forested or arid environments. Additionally, because oxygen is preserved in both bioapatite and collagen, it is useful for paleoecological studies. To investigate the suitability of oxygen isotopes for complementing and building on ecological applications of carbon and nitrogen isotopes, we analyze all three isotopes in bone collagen for nearly identical assemblages of Costa Rican mammals in two ecologically distinct habitats - a evergreen rainforest and a seasonal dry forest. We assess the degree to which differences in habitat, activity pattern, diet, arboreality, and thermoregulation are revealed by each of the isotope systems. Our results highlight the potential of oxygen isotopes in modern and paleoecological contexts. In addition to reflecting habitat type, oxygen isotope values in collagen distinguish species on the basis of vertical habitat stratification and drinking behavior. Within a locality, individuals with low oxygen isotope values likely track meteoric water, whereas those with elevated values most likely consume evaporatively-enriched plant tissues, such as canopy leaves. These patterns will be useful in reconstructing paleoenvironments and interpreting ecological differences among taxa both extant and extinct.

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

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  2. Kalahari groundwaters: Their hydrogen, carbon and oxygen isotopes

    International Nuclear Information System (INIS)

    Mazor, E.; Verhagen, B.T.; Sellschop, J.P.F.; Robins, N.S.; Hutton, L.G.

    1974-01-01

    Tritium and 14 C measurements have revealed several cases of post-nuclear bomb-test rain recharge of local groundwaters, along with values indicating recharge over larger, yet hydrologically active, time scales. In general, recharge seems to follow rain distribution in being more intense in the northern rather than in the southern Kalahari. Initial δ 13 C values vary over a wide range and reveal some correlation to pH and chemical composition of the water. They cannot be used to correct for fossil carbon dilution in 14 C-age calculations. Radiocarbon-deduced ages range from recent to 30,000 years. Stable hydrogen and oxygen isotopes indicate recharge from direct rain infiltration. (author)

  3. The development of a completely automated oxygen isotope mass spectrometer

    International Nuclear Information System (INIS)

    Ahern, T.K.

    1980-01-01

    A completely automated mass spectrometer system has been developed to measure the oxygen isotope ratio of carbon dioxide samples. The system has an accuracy of 0.03 percent, and is capable of analyzing more than 100 samples a day. The system uses an Interdata minicomputer as the primary controller. The intelligence of the system is contained within hardware circuits, software within the minicomputer, and firmware written for a Motorola 6802 microprocessor. A microprocessor-based inlet system controller maximizes the throughput of carbon dioxide samples within the inlet system. The inlet system normally contains four different aliquots of carbon dioxide and introduces these samples to the mass spectrometer through a single admittance leak. The system has been used in the analysis of 111 samples of ice taken from the Steele glacier

  4. Correlation and Stacking of Relative Paleointensity and Oxygen Isotope Data

    Science.gov (United States)

    Lurcock, P. C.; Channell, J. E.; Lee, D.

    2012-12-01

    The transformation of a depth-series into a time-series is routinely implemented in the geological sciences. This transformation often involves correlation of a depth-series to an astronomically calibrated time-series. Eyeball tie-points with linear interpolation are still regularly used, although these have the disadvantages of being non-repeatable and not based on firm correlation criteria. Two automated correlation methods are compared: the simulated annealing algorithm (Huybers and Wunsch, 2004) and the Match protocol (Lisiecki and Lisiecki, 2002). Simulated annealing seeks to minimize energy (cross-correlation) as "temperature" is slowly decreased. The Match protocol divides records into intervals, applies penalty functions that constrain accumulation rates, and minimizes the sum of the squares of the differences between two series while maintaining the data sequence in each series. Paired relative paleointensity (RPI) and oxygen isotope records, such as those from IODP Site U1308 and/or reference stacks such as LR04 and PISO, are warped using known warping functions, and then the un-warped and warped time-series are correlated to evaluate the efficiency of the correlation methods. Correlations are performed in tandem to simultaneously optimize RPI and oxygen isotope data. Noise spectra are introduced at differing levels to determine correlation efficiency as noise levels change. A third potential method, known as dynamic time warping, involves minimizing the sum of distances between correlated point pairs across the whole series. A "cost matrix" between the two series is analyzed to find a least-cost path through the matrix. This least-cost path is used to nonlinearly map the time/depth of one record onto the depth/time of another. Dynamic time warping can be expanded to more than two dimensions and used to stack multiple time-series. This procedure can improve on arithmetic stacks, which often lose coherent high-frequency content during the stacking process.

  5. Bulk Oxygen Isotopic Composition of Ultracarbonaceous Antarctic Micrometeorites with the NanoSIMS

    Science.gov (United States)

    Kakazu, Y.; Engrand, C.; Duprat, J.; Briani, G.; Bardin, N.; Mostefaoui, S.; Duhamel, R.; Remusat, L.

    2014-09-01

    We analyzed the carbon and oxygen isotope ratios of two UCAMMs with the NanoSIMS in order to understand the origin and formation of UCAMMs. One UCAMM has 16O-rich composition and a highly heterogeneous oxygen isotopic distribution.

  6. Oxygen stable isotopes variation in water precipitation in Poland – anthropological applications

    Directory of Open Access Journals (Sweden)

    Lisowska-Gaczorek Aleksandra

    2017-03-01

    Full Text Available The main objective of oxygen isotope analysis is to determine the probable place of origin of an individual or the reconstruction of migration paths. The research are methodologically based on referencing oxygen isotope ratios of apatite phosphates (δ18Op to the range of environmental background δ18O, most frequently determined on the basis of precipitation.

  7. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Directory of Open Access Journals (Sweden)

    Hannah B Vander Zanden

    2016-03-01

    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  8. Dolomite clumped isotope constraints on the oxygen isotope composition of the Phanerozoic Sea

    Science.gov (United States)

    Ryb, U.; Eiler, J. M.

    2017-12-01

    The δ18O value of the Phanerozoic Sea has been debated several decades, largely motivated by an 8‰ increase in δ18O of sedimentary carbonates between the Cambrian and the present. Some previous studies have interpreted this increase to be a primary depositional signal, resulting from an increase in the 18O content of ocean water over time, or from a decrease in ocean temperature increasing the oxygen isotope fractionation between seawater and carbonates. In contrast, other studies have interpreted lower δ18O compositions as the products of diagenetic alteration at elevated burial temperatures. Here, we show that the Phanerozoic dolomite δ18O record overlaps with that of well-preserved calcite fossils, and use carbonate clumped isotope measurements of Cambrian to Pleistocene dolomites to calculate their formation temperatures and the isotopic compositions of their parent-waters. The observed variation in dolomite δ18O is largely explained by dolomite formation at burial temperatures of up to 158°C. The δ18O values of dolomite parent-waters range -2 to +12‰ and are correlated with formation temperatures. Such correlation is consistent with the modification of seawater (0±2‰, VSMOW) toward isotopically heavier compositions through water-rock reactions at elevated burial temperatures. The similarity between the dolomite and calcite δ18O records, and published clumped isotope-based calculations of water compositions, suggests that like dolomite, temporal variations of the calcite δ18O record may also be largely driven by diagenetic alteration. Finally, the relationship we observe between temperature of dolomitization and d18O of dolomite suggests platform carbonates generally undergo dolomitization through reaction with modified marine waters, and that there is no evidence those waters were ever significantly lower in d18O than the modern ocean.

  9. Deuterium isotope fractionation between ortho-alkyl substituted phenols and t-butylthiol in oxygen bases

    International Nuclear Information System (INIS)

    Wawer, A.; Jelenska-Kazimierczuk, M.; Szydlowski, J.

    1998-01-01

    Equilibrium isotope effect in the exchange reaction of deuterium between phenol(P), 2-isopropyl phenol (IPP), 2,6-diisopropyl phenol (DIPP), 2,6-diterbutyl phenol (DTBP) and tertbutylthiol (TBT) has been studied in 296 K. The fractionation factors (α) have been measured in cyclohexane and carbon tetrachloride solutions and in a few oxygen bases: acetone, 1,4-dioxane, ethyl formate, ethyl ether, tetrahydrofurane, N,N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide. Using chemical shifts of phenol OH protons, the thermodynamic parameters of complex formation with the oxygen bases have been determined. The experimental data show that lnα correlates with the formation enthalpy of the phenol-oxygen base complex in DIPP-TBT-base system but there is no simple correlation in IPP-TBT-base system. Furthermore, it was found that in DTBT-TBT-base system lnα depends linearly on the basicity of the solvent (DN parameters). On the other hand, lnα correlates with acidic parameters of the solvents (AN) in IPP-TBT-base and P-TBT-base systems. All above correlations are explained by taking into account two competition processes: self association of phenol molecules and their solvation by oxygen bases. (author)

  10. 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.

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

    International Nuclear Information System (INIS)

    Oi, Takao

    2004-01-01

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

  12. Growth history of cultured pearl oysters based on stable oxygen isotope analysis

    Science.gov (United States)

    Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

    2007-12-01

    We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

  13. 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

  14. Oxygen isotope fractionation between human phosphate and water revisited

    DEFF Research Database (Denmark)

    Daux, Valérie; Lécuyer, Christophe; Héran, Marie-Anne

    2008-01-01

    to investigate the impact of solid food consumption on the oxygen isotope composition of the total ingested water (drinking water+solid food water). The results, along with those from three, smaller published data sets, can be considered as random estimates of a unique delta18OW/delta18OP linear relationship...... collected at 12 sites located at latitudes ranging from 4 degrees N to 70 degrees N together with the corresponding oxygen composition of tap waters (delta18OW) from these areas. In addition, the delta18O of some raw and boiled foods were determined and simple mass balance calculations were performed......: delta18OW=1.54(+/-0.09)xdelta18OP-33.72(+/-1.51)(R2=0.87: p [H0:R2=0]=2x10(-19)). The delta18O of cooked food is higher than that of the drinking water. As a consequence, in a modern diet the delta18O of ingested water is +1.05 to 1.2 per thousand higher than that of drinking water in the area. In meat...

  15. Anatomy of the thriple oxygen isotope Terrestrial Fractionatoin Line

    Science.gov (United States)

    Sharp, Z. D.; Pack, A.

    2017-12-01

    In the triple oxygen isotope system, it is well established that the δ17O value of nearly all terrestrial materials is approximately ½ that of the corresponding δ18O value. In triple isotope space then, all samples plot on a slope 1/2 line, termed the Terrestrial Fractionation Line (TFL). It has recently been recognized that subtle, but significant departures from the TFL exist, given by Δ'17O = δ'17O -λ× δ'18O + γ, where λ is the slope of the TFL (γ is the y-intercept and assumed to be zero in most studies). There have been many published λ values, ranging from 0.52 to 0.5305. λ values determined from a best-fit to rock and mineral samples range from 0.5244 to 0.5266. λ values from meteoric waters are 0.527 to 0.528 (γ = 0.007 to 0.034), explained by equilibrium and kinetic processes. Extreme polar glacial samples define a λ >0.53. As pointed out by Matsuhisia et al. (GCA, 1978), there is no single factor that controls the δ17O-δ18O slope, and clearly there is no `correct' TFL line. However, some generalities can be noted. 1) Meteoric waters generally plot with a λ = 0.528 with a Δ'17O = 0.033. At both high and low δ18O values, the Δ'17O values of meteoritic waters decrease. Mantle derived samples plot in a limited δ space, with δ18O values of 5-9‰ and a Δ'17O of -0.05‰. Rock and mineral samples falling outside this narrow range have undergone interaction with meteoric or ocean water at some point in their history, either by alteration or neoform mineral growth. The quartz-water triple isotope fractionation factor varies with temperatures, ranging from 0.5237 to 0.5266 at 0°C and 200°C, respective. A fit to published rock data gives an overall λ = 0.5237-0.5240. These results are most likely explained by the sum of hydrothermal and low-temperature mineral-water fractionations. Attempting to place any significance on a TFL from a set of data in unwarranted without understanding the processes controlling the isotopic compositions of

  16. 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

  17. The oxygen isotope composition of earth's oldest rocks and evidence of a terrestrial magma ocean

    DEFF Research Database (Denmark)

    Rumble, D.; Bowring, S.; Iizuka, T.

    2013-01-01

    Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce....... But other sources of heat for global melting cannot be excluded such as bolide impacts during early accretion of proto-Earth, the decay of short-lived radioactive isotopes, or the energy released during segregation of core from mantle.......Analysis of Hadean and Archean rocks for O-16-O-17-O-18 isotopes demonstrates that the Terrestrial Mass Fractionation Line of oxygen isotopes has had the same slope and intercept for at least the past 4.0 and probably for as long as 4.2Ga. The homogenization of oxygen isotopes required to produce...... such long-lived consistency was most easily established by mixing in a terrestrial magma ocean. The measured identical oxygen isotope mass fractionation lines for Earth and Moon suggest that oxygen isotope reservoirs of both bodies were homogenized at the same time during a giant moon-forming impact...

  18. Preliminary results of oxygen isotope ratio measurement with a particle-gamma coincidence method

    Energy Technology Data Exchange (ETDEWEB)

    Borysiuk, Maciek, E-mail: maciek.borysiuk@pixe.lth.se; Kristiansson, Per; Ros, Linus; Abdel, Nassem S.; Elfman, Mikael; Nilsson, Charlotta; Pallon, Jan

    2015-04-01

    The possibility to study variations in the oxygen isotopic ratio with photon tagged nuclear reaction analysis (pNRA) is evaluated in the current work. The experiment described in the article was performed at Lund Ion Beam Analysis Facility (LIBAF) with a 2 MeV deuteron beam. Isotopic fractionation of light elements such as carbon, oxygen and nitrogen is the basis of many analytical tools in hydrology, geology, paleobiology and paleogeology. IBA methods provide one possible tool for measurement of isotopic content. During this experimental run we focused on measurement of the oxygen isotopic ratio. The measurement of stable isotopes of oxygen has a number of applications; the particular one driving the current investigation belongs to the field of astrogeology and specifically evaluation of fossil extraterrestrial material. There are three stable isotopes of oxygen: {sup 16}O, {sup 17}O and {sup 18}O. We procured samples highly enriched with all three isotopes. Isotopes {sup 16}O and {sup 18}O were easily detected in the enriched samples, but no significant signal from {sup 17}O was detected in the same samples. The measured yield was too low to detect {sup 18}O in a sample with natural abundances of oxygen isotopes, at least in the current experimental setup, but the spectral line from the reaction with {sup 16}O was clearly visible.

  19. 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

  20. 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)

  1. Oxygen isotope separation by isotopically selective infrared multiphoton dissociation of 2,3-dihydropyran

    International Nuclear Information System (INIS)

    Yokoyama, Atsushi; Ohba, Hironori; Akagi, Hiroshi; Yokoyama, Keiichi; Saeki, Morihisa; Katsumata, Keiichi

    2008-01-01

    Oxygen isotopic selectivity on infrared multiphoton dissociation of 2,3-dihydropyran has been studied by the examination of the effects of excitation frequency, laser fluence, and gas pressure on the dissociation probability of 2,3-dihydropyran and isotopic composition of products. Oxygen-18 was enriched in a dissociation product: 2-propenal. The enrichment factor of 18 O and the dissociation probability were measured at laser frequency between 1033.5 and 1057.3 cm -1 ; the laser fluence of 2.2 - 2.3 J/cm 2 ; and the 2,3-dihydropyran pressure of 0.27 kPa. The dissociation probability decreases as the laser frequency being detuned from the absorption peak of 2,3-dihydropyran around 1081 cm -1 . On the other hand, the enrichment factor increases with detuning the frequency. The enrichment factor of 18 O increases with increasing the 2,3-dihydropyran pressure at the laser fluence below 3 J/cm 2 and the laser frequency of 1033.5 cm -1 , whereas the yield of 2-propenal decreases with increasing the pressure. Very high enrichment factor of 751 was obtained by the irradiation of 0.53 kPa of 2,3-dihydropyran at 2.1 J/cm 2 . (author)

  2. Removal method of fluorescent dyes as pretreatment for measurement of major ion concentrations and hydrogen and oxygen isotopic ratios

    International Nuclear Information System (INIS)

    Nakata, Kotaro; Hasegawa, Takuma; Kashiwaya, Koki; Kodama, Hiroki; Miyajima, Tohru

    2011-01-01

    The major ion concentration and isotope ratio of hydrogen and oxygen can provide important information for migration of groundwater. Sometimes, quantitative estimation of these chemical and isotopic characteristics of solution is necessary for groundwater containing fluorescent dyes, which are used in drilling borehole and tracer experiments. However, sometimes correct estimation is disturbed by dyes and they become a cause of troubles for measurement equipments. Thus development of method to remove dyes is required so that the characteristics of groundwater can be estimated without the negative effect of dyes on measurement or equipments. In this study, removal of four representative dyes (Uranin, Eosin, Naphthalenesulfonic acid sodium(NAP) and Amino G acid potassium salt (AG)) was investigated. Uranin and Eosin were found to be removed by non-ionic synthetic resin: HP2MG. 99.99% of the dyes were removed from initial solutions containing dyes with 10 mg/L after contact with resin, while the contact had little effect on ion concentrations and oxygen and hydrogen isotope ratios. Thus the chemical and isotopic characteristics of groundwater samples containing Uranin and Eosin can be obtained by using the HP2MG resin. On the other hand, the NAP and AG were found to be difficult to remove by the HP2MG resin but they were able to be removed by anion exchange resin (Dowex 1x8). Though contact of solution with Dowex 1x8 did not affect cation concentrations and hydrogen and oxygen isotope ratios, anion concentrations were changed by the contact. Therefore the Dowex 1x8 is only applicable to estimation of the cation concentrations and isotope ratio of hydrogen and oxygen. When both anion and cation concentrations from the samples were necessary, Uranin or Eosin were recommended as a tracer in drilling or tracer experiments. (author)

  3. 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)

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

    International Nuclear Information System (INIS)

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

    1998-01-01

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

  5. 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.

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

    Science.gov (United States)

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

    2017-12-01

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

  7. 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%

  8. Accurate and precise measurement of oxygen isotopic fractions and diffusion profiles by selective attenuation of secondary ions (SASI).

    Science.gov (United States)

    Téllez, Helena; Druce, John; Hong, Jong-Eun; Ishihara, Tatsumi; Kilner, John A

    2015-03-03

    The accuracy and precision of isotopic analysis in Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) relies on the appropriate reduction of the dead-time and detector saturation effects, especially when analyzing species with high ion yields or present in high concentrations. Conventional approaches to avoid these problems are based on Poisson dead-time correction and/or an overall decrease of the total secondary ion intensity by reducing the target current. This ultimately leads to poor detection limits for the minor isotopes and high uncertainties of the measured isotopic ratios. An alternative strategy consists of the attenuation of those specific secondary ions that saturate the detector, providing an effective extension of the linear dynamic range. In this work, the selective attenuation of secondary ion signals (SASI) approach is applied to the study of oxygen transport properties in electroceramic materials by isotopic labeling with stable (18)O tracer and ToF-SIMS depth profiling. The better analytical performance in terms of accuracy and precision allowed a more reliable determination of the oxygen surface exchange and diffusion coefficients while maintaining good mass resolution and limits of detection for other minor secondary ion species. This improvement is especially relevant to understand the ionic transport mechanisms and properties of solid materials, such as the parallel diffusion pathways (e.g., oxygen diffusion through bulk, grain boundary, or dislocations) in electroceramic materials with relevant applications in energy storage and conversion devices.

  9. 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

  10. Stable isotope ratio measurements in hydrogen, nitrogen, and oxygen using Raman scattering

    International Nuclear Information System (INIS)

    Harney, R.C.; Bloom, S.D.; Milanovich, F.P.

    1975-01-01

    A method for measuring stable isotope ratios using laser Raman scattering was developed which may prove of significant utility and benefit in stable isotope tracer studies. Crude isotope ratio measurements obtained with a low-power laser indicate that with current technology it should be possible to construct an isotope ratio measurement system using laser Raman scattering that is capable of performing 0.1 percent accuracy isotope ratio measurements of 16 O/ 18 O in natural abundance oxygen gas or 14 N/ 15 N in natural abundance nitrogen gas in times less than two minutes per sample. Theory pertinent to the technique, designs of specific isotope ratio spectrometer systems, and data relating to isotope ratio measurements in hydrogen, nitrogen, and oxygen are presented. In addition, the current status of several studies utilizing this technique is discussed. (auth)

  11. Oxygen and hydrogen isotope studies of plutonic granitic rocks

    International Nuclear Information System (INIS)

    Taylor, H.P. Jr.

    1978-01-01

    The primary deltaD values of the biotites and hornblendes in granitic batholiths are remarkably constant at about -50 to -85, identical to the values in regional metamorphic rocks, marine sediments and greenstones, and most weathering products in temperate climates. Therefore the primary water in these igneous rocks is probably not 'juvenile', but is ultimately derived by dehydration and/or partial melting of the lower crust or subducted lithosphere. Most granitic rocks have delta 18 O = +7.0 to +10.0, probably indicating significant involvment of high- 18 O metasedimentary or altered volcanic rocks in the melting process; such an origin is demanded for many other granodiorites and tonalites that have delta 18 O = +10 to +13. Gigantic meteoric-hydrothermal convective circulation systems were established in the epizonal portions of all batholiths, locally producing very low delta 18 O values (particularly in feldspars) during subsolidus exchange. Some granitic plutons in such environments also were emplaced as low- 18 O magmas probably formed by melting or assimilation of hydrothermally altered roof rocks. However, the water/rock ratios were typically low enough that over wide areas the only evidence for meteoric water exchange in the batholiths is given by low D/H ratios (deltaK as low as -180); for example, because of latitudinal isotopic variations in meteoric waters, as one moves north through the Cordilleran batholiths of western North America an increasingly higher proportion of the granitic rocks have deltaD values lower than -120. The lowering of deltaD values commonly corelates with re-setting of K-Ar ages. (Auth.)

  12. 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

  13. Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species.

    Science.gov (United States)

    Lehmann, Marco M; Gamarra, Bruno; Kahmen, Ansgar; Siegwolf, Rolf T W; Saurer, Matthias

    2017-08-01

    Almost no δ 18 O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ 18 O relationship between leaf water and cellulose. We measured δ 18 O values of bulk leaf water (δ 18 O LW ) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ 18 O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally 18 O-enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε bio ) of more than 27‰ relative to δ 18 O LW , which might be explained by isotopic leaf water and sucrose synthesis gradients. δ 18 O LW and δ 18 O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε bio  = 25.1‰). Interestingly, damping factor p ex p x , which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ 18 O LW but not if modelled directly from δ 18 O of individual carbohydrates. We conclude that δ 18 O LW is not always a good substitute for δ 18 O of synthesis water due to isotopic leaf water gradients. Thus, compound-specific δ 18 O analyses of individual carbohydrates are helpful to better constrain (post-)photosynthetic isotope fractionation processes in plants. © 2017 John Wiley & Sons Ltd.

  14. Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

    Science.gov (United States)

    LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

    2009-06-01

    Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the

  15. Self-exchange of oxygen behind reflected shock waves

    International Nuclear Information System (INIS)

    Bopp, A.F.; Kern, R.D.; Niki, T.; Stack, G.M.

    1979-01-01

    The rate of isotopic exchange of equimolar mixtures of 32 O 2 + 36 O 2 dilute in Ne-1% Ar was studied over the temperature range 2625 to 3700 K. the reacting gas was analyzed from the reflected shock zone at 20-μs intervals with a time-of-flight mass spectrometer. Each experimental product profile obtained was compared to the corresponding computer-simulated profile calculation from an atomic mechanism by using previously published rate constants. It was observed that the growth of the exchange product exceeded that predicted by the atomic mechanism at the lower temperatures of this study. However, these differences diminished as the temperature increased. Static analysis of the gas mixtures investigated revealed that H 2 or D 2 if present were at a level of less than 2.5 ppM. Computer simulation of product profiles demonstrated that this impurity level was insufficient to affect the observed rate of product formation. It is proposed that contributions from molecular channels are operative at the lower temperatures while atomic pathways dominate at the higher temperatures

  16. 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.

  17. 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

  18. 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.

  19. CARBON AND OXYGEN ISOTOPIC RATIOS FOR NEARBY MIRAS

    Energy Technology Data Exchange (ETDEWEB)

    Hinkle, Kenneth H. [National Optical Astronomy Observatory P.O. Box 26732, Tucson, AZ 85726 (United States); Lebzelter, Thomas [Department of Astrophysics, University of Vienna Türkenschanzstrasse 17, A-1180 Vienna (Austria); Straniero, Oscar, E-mail: khinkle@noao.edu, E-mail: thomas.lebzelter@univie.ac.at, E-mail: straniero@oa-teramo.inaf.it [INAF, Osservatorio Astronomico di Collurania I-64100 Teramo (Italy)

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration–rotation first and second-overtone CO lines in 1.5–2.5 μ m spectra were measured to derive isotopic ratios for {sup 12}C/{sup 13}C, {sup 16}O/{sup 17}O, and {sup 16}O/{sup 18}O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M {sub ⊙} and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of {sup 16}O/{sup 17}O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2–2 M {sub ⊙} stars after the first dredge-up. In contrast, the {sup 16}O/{sup 18}O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the {sup 16}O/{sup 18}O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O

  20. Cross-continental triple oxygen isotope analysis of tropospheric CO2

    Science.gov (United States)

    Liang, M. C.; Rangarajan, R.; Newman, S.; Laskar, A. H.

    2016-12-01

    The abundance variations of near surface atmospheric CO2 isotopologues (primarily 16O12C16O, 16O13C16O, 17O12C16O, and 18O12C16O) represent an integrated signal from anthropogenic/biogeochemical processes, including fossil fuel burning, biospheric photosynthesis and respiration, hydrospheric isotope exchange with water, and stratospheric photochemistry. Oxygen isotopes, in particular, are affected by the carbon and water cycles. Being a useful tracer that directly probes governing processes in CO2 biogeochemical cycles, D17O (= ln(1+d17O) - 0.516´ln(1+d18O)) provides an alternative constraint on the strengths of the associated cycles involving CO2. Here, we report more than one year of data obtained from Taiwan (Taipei), South China Sea, and USA (Pasadena, CA and Palos Verdes, CA). On average, the D17O values from these locations are similar and show no significant influence from the 2014-2016 El Nino event, in contrast to what has been reported for the 1997-1998 El Nino from the CO2 data collected from La Jolla, CA. Implications for utilizing the new tracer D17O for carbon cycling studies will be made.

  1. 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)

  2. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest canopy...

  3. LBA-ECO CD-02 Carbon, Nitrogen, Oxygen Stable Isotopes in Organic Material, Brazil

    Data.gov (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports the measurement of stable carbon, nitrogen, and oxygen isotope ratios in organic material (plant, litter and soil samples) in forest...

  4. Ras Umm Sidd Oxygen Isotope (delta 18O) Data for 1750 to 1995

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Ras Umm Sidd bimonthly coral oxygen isotope data (coral core RUS-95). Notes on the data: File (Ras Umm Sidd d18O.txt.) includes columns for Year AD (bimonthly...

  5. Comparison of interglacial warm events since the marine oxygen isotope stage 11

    Digital Repository Service at National Institute of Oceanography (India)

    Oba, T.; Banakar, V.K.

    Large numbers of oxygen isotopic curves of benthic foraminifcral tests from deep-sea sediment cores have been published. The curves are well-established reliable proxies for past climate and relative sea level fluctuations. In order to understand...

  6. Palmyra Island Monthly Oxygen Isotope Data (delta 18O) for 1886-1998

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Palmyra Island Monthly Coral Oxygen Isotope Data. 112-yr, monthly-resolved coral record from Palmyra Island (5 deg 52 min N, 162 deg 8 min W). The coral was drilled...

  7. Oxygen isotope systematics of chondrules in the Allende CV3 chondrite: High precision ion microprobe studies

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; Ushikubo, T.; Nakashima, D.; Kita, N.T.

    grains and some of them were derived from precursors related to refractory inclusions. However, most relict olivine grains show oxygen isotope ratios that overlap with those in homogeneous chondrules. The delta sup(17)O values of four barred olivine...

  8. Spontaneous oxygen isotope exchange between carbon dioxide and\

    Czech Academy of Sciences Publication Activity Database

    Knížek, Antonín; Zukalová, Markéta; Kavan, Ladislav; Zukal, Arnošt; Kubelík, Petr; Rojík, P.; Skřehot, P.; Ferus, Martin; Civiš, Svatopluk

    2017-01-01

    Roč. 137, MAR 2017 (2017), s. 6-10 ISSN 0169-1317 R&D Projects: GA MŠk LD14115; GA ČR(CZ) GA14-12010S; GA ČR GA13-07724S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388955 Keywords : clay * carbon dioxide * FTIR spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.101, year: 2016

  9. EQUILIBRIUM AND KINETIC NITROGEN AND OXYGEN-ISOTOPE FRACTIONATIONS BETWEEN DISSOLVED AND GASEOUS N2O

    NARCIS (Netherlands)

    INOUE, HY; MOOK, WG

    1994-01-01

    Experiments were performed to determine the equilibrium as well as kinetic stable nitrogen and oxygen isotope fractionations between aqueous dissolved and gaseous N2O. The equilibrium fractionations, defined as the ratio of the isotopic abundance ratios (15R and 18R, respectively) of gaseous and

  10. Sulfur and Oxygen Isotope Fractionation During Bacterial Sulfur Disproportionation Under Anaerobic Haloalkaline Conditions

    NARCIS (Netherlands)

    Poser, Alexander; Vogt, Carsten; Knöller, Kay; Sorokin, Dimitry Y.; Finster, Kai W.; Richnow, Hans H.

    2016-01-01

    Sulfur and oxygen isotope fractionation of elemental sulfur disproportionation at anaerobic haloalkaline conditions was evaluated for the first time. Isotope enrichment factors of the strains Desulfurivibrio alkaliphilus and Dethiobacter alkaliphilus growing at pH 9 or 10 were −0.9‰ to −1‰ for

  11. 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)

  12. 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.

  13. 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)

  14. 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

  15. Oxygen Isotope Records in Modern Oyster Shells from Chi Ku, Tainan and Their Implication of Seasonality

    Science.gov (United States)

    Chen, Y. C.; Mii, H. S.; Li, K. T.

    2015-12-01

    To exam whether oxygen isotope records of Crassostrea gigasoysters can be used as proxies of environment, 133 cultivated oysters and 21 water samples were collected from Chi Ku area, Tainan City, southern Taiwan in December of 2012, and from March, 2013 to July, 2014. Instrumental air and water temperatures and precipitation records were obtained from a nearest Central Weather Bureau (CWB) station roughly 16 km north of Chi Ku. The oxygen and carbon isotope values of the ligamental area of the modern oyster shells are from -6.92‰ to -0.08‰ (-3.05 ± 1.17‰, N = 2280; 1σ; VPDB) and from -5.57‰ to 0.63‰ (-1.88 ± 0.81‰), respectively. Oxygen isotope values of the water samples are mainly between -0.28‰ and 0.74‰ (0.18 ± 0.29‰, N = 20; 1σ; VSMOW). However, water oxygen isotope value of -2.75‰ was observed for the water sample collected immediately after a typhoon heavy rainfall. Seasonal temperature fluctuation pattern of estimated oxygen isotope temperatures from modern shells is similar to that of CWB instrumental records. However, the oxygen isotope temperatures are respectively about 3 °C and 10°C higher than those of instrumental records for winter and summer. Higher estimated oxygen isotope temperatures are most likely caused by underestimated fraction of freshwater. We analyzed 5 archaeological oyster shells of Siraya culture (500~250B.P.) collected from Wu Chien Tuso North (WCTN) archaeological site of Tainan branch of Southern Taiwan Science Park to infer the harvest season of mollusks. Oxygen isotope values of the ligamental area of the archaeological oyster shells are between -5.98‰ and -1.26‰ (-3.34 ± 1.37‰, N = 60; 1σ), and carbon isotope values are between -3.21‰ and 0.60‰ (-2.04‰ ± 0.55‰). The oxygen isotope records of archaeological oyster shells also showed clear seasonality. Most of the oysters were collected in autumn and winter. Oxygen isotope values of archaeological oyster shells was 1‰ greater than that

  16. Application of carbon and oxygen stable isotopes to the study of Brazilian precambrian

    International Nuclear Information System (INIS)

    Torquato, J.R.F.

    1980-01-01

    Samples of carbonated rocks of precambrian age are studied. The stable carbon and oxygen isotopes are applied to the study of terrestrial materials considering the variations of some element isotopic composition in function of the environment of sedimentation. The isotopic analysis was done using mass spectrometers. The analytical results and the description of region geology of the site of each sample are presented. The isotopic data are interpreted aiming to the environment of sedimentation. New techniques for better improvement of carbon and oxygen ratios, are proposed, such as: to use the analysis of surface trend and the isotopic logging in mapping of surface and subsurface. A new method for approximated determination of the ages of precambrian carbonated rocks, considering the limitations of their new technique, is also presented. (M.C.K.) [pt

  17. Simultaneous determination of stable carbon, oxygen, and hydrogen isotopes in cellulose.

    Science.gov (United States)

    Loader, N J; Street-Perrott, F A; Daley, T J; Hughes, P D M; Kimak, A; Levanič, T; Mallon, G; Mauquoy, D; Robertson, I; Roland, T P; van Bellen, S; Ziehmer, M M; Leuenberger, M

    2015-01-06

    A technological development is described through which the stable carbon-, oxygen-, and nonexchangeable hydrogen-isotopic ratios (δ(13)C, δ(18)O, δ(2)H) are determined on a single carbohydrate (cellulose) sample with precision equivalent to conventional techniques (δ(13)C 0.15‰, δ(18)O 0.30‰, δ(2)H 3.0‰). This triple-isotope approach offers significant new research opportunities, most notably in physiology and medicine, isotope biogeochemistry, forensic science, and palaeoclimatology, when isotopic analysis of a common sample is desirable or when sample material is limited.

  18. 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.

  19. 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)

  20. Effects of Water Vapor on the Data Quality of the Stable Oxygen Isotopic Ratio of Atmospheric Carbon Dioxide

    Science.gov (United States)

    Evans, C. U.; White, J. W.; Vaughn, B.; Tans, P. P.; Pardo, L.

    2007-12-01

    The stable oxygen isotopic ratio of carbon dioxide can potentially track fundamental indicators of environmental change such as the balance between photosynthesis and respiration on regional to global scales. The Stable Isotope Laboratory (SIL) at the Institute of Arctic and Alpine Research (INSTAAR), University of Colorado at Boulder, has measured the stable isotopes of atmospheric carbon dioxide from more than 60 NOAA/Earth System Research Laboratory (ESRL) air flask-sampling sites since the early 1990s. If air is sampled without drying, oxygen can exchange between carbon dioxide and water in the flasks, entirely masking the desired signal. An attempt to investigate how water vapor is affecting the δ18O signal is accomplished by comparing the SIL measurements with specific humidity, calculated from the National Climatic Data Center (NCDC) global integrated surface hourly temperature and dew point database, at the time of sampling. Analysis of sites where samples have been collected initially without drying, and subsequently with a drying kit, in conjunction with the humidity data, has led to several conclusions. Samples that initially appear isotopically unaltered, in that their δ18O values are within the expected range, are being subtly influenced by the water vapor in the air. At Bermuda and other tropical to semi-tropical sites, the 'wet' sampling values have a seasonal cycle that is strongly anti-correlated to the specific humidity, while the 'dry' values have a seasonal cycle that is shifted earlier than the specific humidity cycle by 1-2 months. The latter phasing is expected given the seasonal phasing between climate over the ocean and land, while the former is consistent with a small, but measurable isotope exchange in the flasks. In addition, we note that there is a strong (r > 0.96) correlation between the average specific humidity and the percent of rejected samples for 'wet' sampling. This presents an opportunity for determining a threshold of

  1. 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

  2. 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)

  3. Stable carbon and oxygen isotope study on benthic foraminifera ...

    Indian Academy of Sciences (India)

    Ajoy K Bhaumik

    2017-07-24

    Jul 24, 2017 ... of a species for isotopic analysis has forced us to select multiple species from down-core samples. Thus ... microhabitat, climatic variability, bottom and pore ...... Trends, rhythms, and aberrations in global climate 65 Ma.

  4. 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.

  5. Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

    Science.gov (United States)

    Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

    2015-01-01

    The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

  6. 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

  7. 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.

  8. 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.)

  9. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    International Nuclear Information System (INIS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-01-01

    Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  10. 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

  11. 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

  12. 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.

  13. 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

  14. 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)

  15. The effect of phosphomonoesterases on the oxygen isotope composition of phosphate

    Science.gov (United States)

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

    2014-01-01

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

  16. Oxygen isotopic composition of mammal bones as a new tool for studying ratios of paleoenvironmental water and paleoclimates

    International Nuclear Information System (INIS)

    Longinelli, A.

    1984-04-01

    The purpose of this study is to try to establish quantitative relationships between the average oxygen isotopic composition of local meteoric water, the oxygen isotopic composition of mammal body water and the oxygen isotopic composition of phosphate in mammal bones. These relationships, after calibration of the method on living specimens, would allow quantitative paleoclimatological research based on the measurement of delta 18 O(PO 4 3- ) of fossil mammal bones

  17. Planetary fertility during the past 400 ka based on the triple isotope composition of atmospheric oxygen in trapped gases from the Vostok ice core

    Science.gov (United States)

    Blunier, T.; Bender, M. L.; Barnett, B.; von Fisher, J. C.

    2012-04-01

    The productivity of the biosphere leaves its imprint on the isotopic composition of atmospheric oxygen. Ultimately atmospheric oxygen, through photosynthesis, originates from seawater. Fractionations during the passage from seawater to atmospheric O2 and during respiration are mass dependent, affecting δ17O about half as much as δ18O. An "anomalous" (also termed mass independent) fractionation process changes δ17O about 1.7 times as much as δ18O during isotope exchange between O2 and CO2 in the stratosphere. The relative rates of biological O2 production and stratospheric processing determine the relationship between δ17O and δ18O of O2 in the atmosphere. Variations of this relationship thus allow us to estimate changes in the rate of mass dependent O2 production by photosynthesis versus the rate of mass independent O2-CO2 exchange in the stratosphere. However, the analysis of the 17O anomaly is complicated because each hydrological and biological process influencing δ17O and δ18O fractionates 17O and 18O in slightly different proportions. In this study we present oxygen data covering the last 400 kyr from the Vostok ice core. We reconstruct oxygen productivities from the triple isotope composition of atmospheric oxygen with a box model. Our steady state model for the oxygen cycle takes into account fractionation during photosynthesis and respiration of the land and ocean biosphere as well as fractionation when oxygen passes through the stratosphere. We consider changes of fractionation factors linked to climate variations taking into account the span of estimates of the main factors affecting our calculations. We find that ocean oxygen productivity was likely elevated relative to modern during glacials. However, this increase probably did not fully compensate for a reduction in land ocean productivity resulting in a slight reduction in total oxygen production during glacials.

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

    Science.gov (United States)

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

    2017-10-01

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

  19. 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

  20. The source of phosphate in the oxidation zone of ore deposits: Evidence from oxygen isotope compositions of pyromorphite

    Science.gov (United States)

    Burmann, Fabian; Keim, Maximilian F.; Oelmann, Yvonne; Teiber, Holger; Marks, Michael A. W.; Markl, Gregor

    2013-12-01

    , toothpaste and as a release of waste water treatment plants (Young et al., 2009). Anthropogenic effects will not be discussed further in the following. On this basis, we consider three different cases of pyromorphite formation as illustrated on the conceptual scheme of Fig. 1. Case 1: Pyromorphite grown recently (within the last hundreds of years) on rock surfaces in former mines. Both, phosphate released geochemically from igneous rocks and phosphate released biologically during leaching from litter/lysis of microbial cells and soil organic matter decomposition are possible sources. Case 2: Pyromorphite formation on mine dumps, below vegetation (recent, during tens to hundreds of years). Based on the specific setting of these samples investigated here (they were found exclusively below a large fern; see more details in the section on sample description), biologically-mediated P release provides the phosphate for pyromorphite growth. Case 3: Pyromorphite growth in the oxidized zones of ore bodies prior to human interference. Most samples of our study belong to this case.Phosphorus generally forms very strong covalent bonds (Huminicki and Hawthorne, 2002) and there is only negligible exchange of oxygen isotopes between phosphate and ambient water under most near-surface conditions without biological activity (Winter et al., 1940; Longinelli, 1965). The only important exchange of oxygen isotopes between phosphate and ambient water involves biological activity and the oxygen isotope composition of phosphate (δ18OP) may be modified by different enzymatic/cellular processes. Once phosphate is taken up by organisms, intracellular pyrophosphatase mediates internal P cycling. This is associated with a temperature-dependent equilibrium isotope fractionation due to the reversible exchange of O atoms between the phosphate molecule and cell water. As a result the δ18OP is equilibrated with the ambient water, and the equilibrium temperature can be calculated following the revised

  1. Biological fractionation of oxygen and carbon isotopes by recent benthic foraminifera

    International Nuclear Information System (INIS)

    Woodruff, F.; Douglas, R.G.

    1980-01-01

    Recent deep-sea benthic foraminifera from five East Pacific Rise box core tops have been analyzed for oxygen and carbon isotopic composition. The five equatorial stations, with water depths of between 3200 and 4600 m, yielded fourteen specific and generic taxonomic groups. Of the taxa analyzed, Uvigerina spp. most closely approaches oxygen isotopic equilibrium with ambient sea water. Pyrgo spp. was next closest to isotopic equilibrium, being on the average 0.59 per thousand depleted in 18 O relative to Uvigerina spp. Oridorsalis umbonatus also has relatively high delta 18 O values. Most other taxa were depleted in 18 O by large amounts. In no taxa was the carbon in the CaCO 3 secreted in carbon isotopic equilibrium with the dissolved HCO 3 - of ambient sea water. (Auth.)

  2. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M. F. [Centro de Estudios y Experimentacion de Obras Publicas (CEDEX), Madrid (Spain); Castano, S. [Geological Survey of Spain (IGME), Madrid (Spain)

    2013-07-15

    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a digital elevation model using GIS tools. Application of the resulting map to several groundwater case studies in spain has shown it to be useful as a reference of the input function to recharge. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is ongoing through comparison of model results with isotope data from the GNIP database and from isotope studies in hydrogeology and climate change taking place in spain. (author)

  3. 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)

  4. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Horner, D.A.

    1984-08-01

    The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO 2 + H 2 O right reversible H + + SHO 3 - . The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO 3 - ) and the other with the proton bonded to an oxygen (SO 3 H - ). (The symbol SHO 3 - in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO 3 H - , exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum

  5. 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.)

  6. 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.)

  7. Multiple taxon multiple locality approach to providing oxygen isotope evidence for warm-blooded theropod dinosaurs

    Science.gov (United States)

    Fricke, Henry C.; Rogers, Raymond R.

    2000-09-01

    Oxygen isotope ratios of fossil remains of coexisting taxa from several different localities can be used to help investigate dinosaur thermoregulation. Focusing on the Late Cretaceous, oxygen isotope ratios of crocodile tooth enamel from four separate localities exhibit less of a decrease with latitude than do ratios of tooth enamel from coexisting theropod dinosaurs. A shallower latitudinal gradient for crocodiles is consistent with how oxygen isotope ratios should vary for heterothermic animals having body temperatures coupled with their environments (“cold blooded”), while a steeper gradient for theropods is consistent with how these ratios should vary for homeothermic animals having constant body temperatures independent of their environments (“warm blooded”). This inferred homoethermy in theropods is likely due to higher rates of metabolic heat production relative to crocodiles and is not an artifact of body size.

  8. Oxygen isotope variations in phosphate of biogenic apatites. Pt. 2. Phosphorite rocks

    Energy Technology Data Exchange (ETDEWEB)

    Kolodny, Y; Luz, B; Shemesh, A [Hebrew Univ., Jerusalem (Israel). Dept. of Geology

    1983-09-01

    Phosphorites from sedimentary sequences ranging in age from Archaen to Recent were analysed for delta/sup 18/O in both the PO/sub 4/ (delta/sup 18/Osub(p)) and CO/sub 3/ (delta/sup 18/Osub(c)) in the apatite lattice. The oxygen isotope record is considerably better preserved in phosphates than in either carbonates or cherts. The use of the Longinelli and Nuti temperature equation yields temperatures for Recent phosphorites that are in good agreement with those measured in the field. The delta/sup 18/Osub(p) values of ancient phosphorites decrease with increasing age. These changes with time are not likely to be due to post-depositional exchange. Changes in delta/sup 18/O values of seawater and variations of temperatures with time can account for the delta/sup 18/Osub(p) time trend, but the latter explanation is preferred. In Ancient phosphorites delta/sup 18/Osub(c) in structurally bound carbonate in apatite is not a reliable geochemical indicator.

  9. Oxygen isotopic signature of CO2 from combustion processes

    NARCIS (Netherlands)

    Schumacher, M.; Werner, R. A.; Meijer, H. A. J.; Brand, W. A.; Geilmann, H.; Neubert, R. E. M.; Kaiser, J.; Jansen, Henk G.

    2011-01-01

    For a comprehensive understanding of the global carbon cycle precise knowledge of all processes is necessary. Stable isotope (C-13 and O-18) abundances provide information for the qualification and the quantification of the diverse source and sink processes. This study focuses on the delta O-18

  10. Placental Gas Exchange and the Oxygen Supply to the Fetus

    DEFF Research Database (Denmark)

    Carter, Anthony M

    2015-01-01

    The oxygen supply of the fetus depends on the blood oxygen content and flow rate in the uterine and umbilical arteries and the diffusing capacity of the placenta. Oxygen consumption by the placenta is a significant factor and a potential limitation on availability to the fetus. The relevance...... anaerobic conditions and even the fetus is adapted to a low oxygen environment. Nevertheless, there is a reserve capacity, and during acute hypoxia the fetus can counter a 50% reduction in oxygen delivery by increasing fractional extraction. During sustained hypoxia, on the other hand, fetal growth...

  11. 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

  12. 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.)

  13. Laser Spectroscopic Analysis of Liquid Water Samples for Stable Hydrogen and Oxygen Isotopes

    International Nuclear Information System (INIS)

    2009-01-01

    Stable isotope ratios of hydrogen and oxygen are tracers of choice for water cycle processes in hydrological, atmospheric and ecological studies. The use of isotopes has been limited to some extent because of the relatively high cost of isotope ratio mass spectrometers and the need for specialized operational skills. Here, the results of performance testing of a recently developed laser spectroscopic instrument for measuring stable hydrogen and oxygen isotope ratios of water samples are described, along with a procedure for instrument installation and operation. Over the last four years, the IAEA Water Resources Programme conducted prototype and production model testing of these instruments and this publication is the outcome of those efforts. One of the main missions of the IAEA is to promote the use of peaceful applications of isotope and nuclear methods in Member States and this publication is intended to facilitate the use of laser absorption based instruments for hydrogen and oxygen stable isotope analyses of liquid water samples for hydrological and other studies. The instrument uses off-axis integrated cavity output spectroscopy to measure absolute abundances of 2 HHO, HH 18 O, and HHO via laser absorption. Test results using a number of natural and synthetic water standards and samples with a large range of isotope values demonstrate adequate precision and accuracy (e.g. precisions of 1 per mille for δ 2 H and 0.2 per mille for δ 18 O). The laser instrument has much lower initial and maintenance costs than mass spectrometers and is substantially easier to operate. Thus, these instruments have the potential to bring about a paradigm shift in isotope applications by enabling researchers in all fields to measure isotope ratios by themselves. The appendix contains a detailed procedure for the installation and operation of the instrument. Using the procedure, new users should be able to install the instrument in less than two hours. It also provides step

  14. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    Science.gov (United States)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

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

    International Nuclear Information System (INIS)

    Tichomirowa, Marion; Junghans, Manuela

    2009-01-01

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

  16. Isotopic labeling study of oxygen diffusion in amorphous LaScO3 high-κ films on Si(100) and its effects on the electrical characteristics

    International Nuclear Information System (INIS)

    Lopes, J.M.J.; Littmark, U.; Roeckerath, M.; Durgun Oezben, E.; Lenk, S.; Schubert, J.; Mantl, S.; Breuer, U.; Besmehn, A.; Staerk, A.; Grande, P.L.; Sortica, M.A.; Radtke, C.

    2009-01-01

    The influence of post-deposition oxygen anneals on the properties of amorphous LaScO 3 films on Si(100) is reported. The use of an isotopically ( 18 O 2 ) enriched atmosphere allowed to investigate the 16 O- 18 O exchange and the oxygen diffusion across the dielectric layer. Such effects are connected to the formation of an interfacial layer. Oxygen annealing leads to nearly ideal capacitance-voltage curves, lower leakage currents and interface trap densities, as well as to κ-values up to 33 for the LaScO 3 films. These results are attributed to the suppression of oxygen-related trap centers and the achievement of a stoichiometric oxygen content. (orig.)

  17. The Oxygen Isotopic Composition of MIL 090001: A CR2 Chondrite with Abundant Refractory Inclusions

    Science.gov (United States)

    Keller, Lindsay P.; McKeegan, K. D.; Sharp, Z. D.

    2012-01-01

    MIL 090001 is a large (>6 kg) carbonaceous chondrite that was classified as a member of the CV reduced subgroup (CVred) that was recovered during the 2009-2010 ANSMET field season [1]. Based on the abundance of refractory inclusions and the extent of aqueous alteration, Keller [2] suggested a CV2 classification. Here we report additional mineralogical and petrographic data for MIL 090001, its whole-rock oxygen isotopic composition and ion microprobe analyses of individual phases. The whole rock oxygen isotopic analyses show that MIL 090001 should be classified as a CR chondrite.

  18. Isotopes of carbon and oxygen in the carbonate impurities of coal have potential as palaeoenvironmental indicators

    International Nuclear Information System (INIS)

    Verhagen, B.T.; Falcon, R.M.

    1990-01-01

    The nature and systematics of impurities such as carbonates need to be established in order to understand their provenance in coal seams with reference to mining, beneficiation and ultimately their elimination or reduction. To this end, mineralogical and carbon-13 and oxygen-18 isotopic studies were undertaken on carbonate occurrences in coal from the eastern Transvaal highveld. Isotopic variations of considerable amplitude and individual values of extreme ''lightness'' are to be found in the carbonates in coal of the Witbank and adjacent basins. The observed isotopic ratios have a clear bearing on the nature and origins of the carbonates. 1 tab., 1 fig

  19. 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

  20. 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)

  1. Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

    Science.gov (United States)

    Brookman, Tom H.; Ambrose, Stanley H.

    2012-09-01

    Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C3 and C4 vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ13C and δ18O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north-south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.

  2. 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)

  3. 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)

  4. 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.

  5. 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

  6. Orientation-Dependent Oxygen Evolution on RuO2 without Lattice Exchange

    DEFF Research Database (Denmark)

    Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel

    2017-01-01

    the potential involvement of lattice oxygen in the OER mechanism with online electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous...... work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by density functional theory, where more active facets bind oxygen more weakly. This new...

  7. 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)

  8. 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

  9. 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.

  10. 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)

  11. 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.)

  12. 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)

  13. 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...

  14. 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

  15. 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

  16. Oxygen exchange between C18O2 and ''acidic'' oxide and zeolite catalysts

    International Nuclear Information System (INIS)

    Peri, J.B.

    1975-01-01

    The exchange of oxygen between C 18 O 2 and several high-area oxides, including silica, γ-alumina, silica--alumina, and zeolite catalysts, was studied. Infrared spectra of adsorbed CO 2 and of surface ''carbonates'' were used to follow the rate of oxygen exchange and investigate the nature of unusually exchangeable surface oxide ions, present at low concentrations. Interaction of CO 2 with the surface typically produced initial exchange of one oxygen atom, as expected from interaction with a single oxide ion (CO 2 + O 2- reversible CO 3 2- ), and the number of exchangeable ions increased with increasing temperature. The rate of oxygen exchange did not correlate with chemisorption to form stable surface carbonates or with the extent of strong physical adsorption of CO 2 . With dry silica, exchange was insignificant below 600 0 ; with catalytically active zeolites and dry γ-alumina, it was detectable at 200 0 and fairly rapid at 300--400 0 . Silica--alumina required 100--150 0 higher temperature for exchange than did an active zeolite. Activity for cracking and other hydrocarbon reactions may be related to the ease of exchange of some surface oxide ions with CO 2 . Active zeolites have reactive oxide sites resembling those on dry γ-alumina, but such sites on zeolites are probably less-readily eliminated by chemisorption of H 2 O or other compounds. (U.S.)

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

    Science.gov (United States)

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

    2014-06-15

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

  18. 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.

  19. Chemical and oxygen isotope zonings in garnet from subducted continental crust record mineral replacement and metasomatism

    Science.gov (United States)

    Vho, Alice; Rubatto, Daniela; Regis, Daniele; Baumgartner, Lukas; Bouvier, Anne-Sophie

    2017-04-01

    Garnet is a key mineral in metamorphic petrology for constraining pressure, temperature and time paths. Garnet can preserve multiple growth stages due to its wide P-T stability field and the relatively slow diffusivity for major and trace elements at sub-solidus temperatures. Pressure-temperature-time-fluid paths of the host rock may be reconstructed by combining metamorphic petrology with microscale trace element and oxygen isotope measurements in garnet. Subduction zones represent relevant geological settings for geochemical investigation of element exchanges during aqueous fluid-rock interactions. The Sesia Zone consists of a complex continental sequence containing a variety of mono-metamorphic and poly-metamorphic lithologies such as metagranitoids, sediments and mafic boudins. The precursor Varisican-Permian amphibolite-facies basement (6-9 kbar 650-850°C; Lardeaux and Spalla, 1991; Robyr et al., 2013) experienced high pressure metamorphism (15-22 kbar 500-550°C; Regis, et al. 2014; Robyr et al., 2013) during Alpine subduction. In different lithologies of the Internal Complex (Eclogitic Micaschist Complex), including metabasites from the Ivozio Complex, Ti-rich metasediments from Val Malone and pre-Alpine Mn-quartzites associated to metagabbros from Cima Bonze, garnet is abundant and shows a variety of complex textures that cannot be reconciled with typical growth zoning, but indicate resorption and replacement processes and possible metasomatism. In-situ, microscale oxygen isotopes analysis of garnet zones was performed by ion microprobe with the SwissSIMS Cameca IMS 1280-HR at University of Lausanne and SHRIMP-SI at the Australian National University. Each sample has a distinct δ18O composition, and the δ18O values show different degrees of variation between domains. Homogeneously low values of < 5‰ are measured in the garnets from the Ivozio Complex metagabbro. Intragrain variations of up to 3.5‰ in the porphyroblasts from Val Malone metasediments

  20. Interannual variability in the oxygen isotopes of atmospheric CO2 driven by El Nino

    NARCIS (Netherlands)

    Welp, Lisa R.; Keeling, Ralph F.; Meijer, Harro A. J.; Bollenbacher, Alane F.; Piper, Stephen C.; Yoshimura, Kei; Francey, Roger J.; Allison, Colin E.; Wahlen, Martin

    2011-01-01

    The stable isotope ratios of atmospheric CO2 (O-18/O-16 and C-13/C-12) have been monitored since 1977 to improve our understanding of the global carbon cycle, because biosphere-atmosphere exchange fluxes affect the different atomic masses in a measurable way(1). Interpreting the O-18/O-16

  1. 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)

  2. 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)

  3. Oxygen and hydrogen isotope ratios in tree rings: how well do models predict observed values?

    CSIR Research Space (South Africa)

    Waterhouse, JS

    2002-07-30

    Full Text Available . Cosmo- chim. Acta 46 (1982) 955^965. [35] W.M. Buhay, T.W.D. Edwards, Climate in southwestern Ontario, Canada, between AD 1610 and 1885 inferred from oxygen and hydrogen isotopic measurements of wood cellulose from trees in di?erent hydrological set...

  4. Estimating of gas transfer velocity using triple isotopes of dissolved oxygen.

    Digital Repository Service at National Institute of Oceanography (India)

    Sarma, V.V.S.S.; Abe, O.; Honda, M.; Saino, T.

    variations in oxygen isotopes are found to be higher than the direct estimations at low wind speed (<5 m s sup(-1)) and lower at high wind speeds (>13 m s sup(-1)) and showed significant spatial variability. The method presented here can be used to derive...

  5. A Quantitative, Time-Dependent Model of Oxygen Isotopes in the Solar Nebula: Step one

    Science.gov (United States)

    Nuth, J. A.; Paquette, J. A.; Farquhar, A.; Johnson, N. M.

    2011-01-01

    The remarkable discovery that oxygen isotopes in primitive meteorites were fractionated along a line of slope I rather than along the typical slope 0,52 terrestrial fractionation line occurred almost 40 years ago, However, a satisfactory, quantitative explanation for this observation has yet to be found, though many different explanations have been proposed, The first of these explanations proposed that the observed line represented the final product produced by mixing molecular cloud dust with a nucleosynthetic component, rich in O-16, possibly resulting from a nearby supernova explosion, Donald Clayton suggested that Galactic Chemical Evolution would gradually change the oxygen isotopic composition of the interstellar grain population by steadily producing O-16 in supernovae, then producing the heavier isotopes as secondary products in lower mass stars, Thiemens and collaborators proposed a chemical mechanism that relied on the availability of additional active rotational and vibrational states in otherwise-symmetric molecules, such as CO2, O3 or SiO2, containing two different oxygen isotopes and a second, photochemical process that suggested that differential photochemical dissociation processes could fractionate oxygen , This second line of research has been pursued by several groups, though none of the current models is quantitative,

  6. A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

    NARCIS (Netherlands)

    Teranes, J.L.; McKenzie, J.A.; Bernasconi, S.M.; Lotter, A.F.; Sturm, M.

    1999-01-01

    Abstract—In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in

  7. Oxygen and carbon isotope analyses of a Late Quaternary core in the Zaire (Congo) fan

    International Nuclear Information System (INIS)

    Olausson, E.

    1984-01-01

    Oxygen and carbon isotope analyses have been carried out on samples from a core of the Angola Basin (6 0 50'S, 10 0 45'E, depth 2100 m). The pelagic foraminifer Globigerinoides ruber, a species with a shallow water habitat, and two benthic species Uvigerina peregrina and Bulimina aculeata have been analysed. The data are given relative to PDB. (Auth.)

  8. ANALYTICAL EMPLOYMENT OF STABLE ISOTOPES OF CARBON, NITROGEN, OXYGEN AND HYDROGEN FOR FOOD AUTHENTICATION

    Directory of Open Access Journals (Sweden)

    E. Novelli

    2011-04-01

    Full Text Available Stable isotopes of carbon, nitrogen, oxygen and hydrogen were used for analytical purposes for the discrimination of the type of production (farming vs. fishing in the case of sea bass and for geographical origin in the case of milk. These results corroborate similar experimental evidences and confirm the potential of this analytical tool to support of food traceability.

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

    Science.gov (United States)

    De Bénédittis, J; Bertrand-Krajewski, J L

    2005-01-01

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

  10. Intracrystalline oxygen isotope effects in CuSO4.5H2O and their dependence on crystallization temperature

    International Nuclear Information System (INIS)

    Heinzinger, K.

    1976-01-01

    In copper sulphate pentahydrate the water molecules occupy three different sites, connected with different oxygen isotope ratios. Results of measurements of the change of these isotope ratios with crystallization temperature are reported. The temperature dependence found here provides the basis for the determination of crystallization temperatures of hydrated crystals from such intracrystalline oxygen isotope fractionation. Suppositions necessary for the application of this method are discussed. (author)

  11. 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)

  12. 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

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

    International Nuclear Information System (INIS)

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

    1985-01-01

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

  14. Tritium enrichment in aqueous phase by catalytic isotopic exchange

    International Nuclear Information System (INIS)

    Schindewolf, U.

    1983-01-01

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

  15. 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

  16. 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

  17. 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

  18. 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%

  19. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-06-17

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

  1. Controls of oxygen isotope ratios of nitrate formed during nitrification in soils

    International Nuclear Information System (INIS)

    Mayer, B.; Bollwerk, S.M.; Vorhoff, B.; Mansfeldt, T.; Veizer, J.

    1999-01-01

    The isotopic composition of nitrate is increasingly used to determine sources and transformations of nitrogen in terrestrial and aquatic ecosystems. Oxygen isotope ratios of nitrate appear to be particularly useful, since they allow the differentiation between nitrate from atmospheric deposition (δ 18 O nitrate between +25 and +70 per mille), nitrate from fertilizers (δ 18 O nitrate +23 per mille), and nitrate derived from nitrification processes in soils (δ 18 O nitrate 3 molecule derive from H 2 O (with negative δ 18 O values dependent upon location) and one oxygen derives from atmospheric O 2 (δ 18 O = +23.5 per mille).. The objective of this study was to experimentally determine the extent to which water oxygen controls the δ 18 O value of nitrate, which is formed during nitrification in soils

  2. Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

    Science.gov (United States)

    Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

    2013-10-01

    We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

  3. Meteoric water in normal fault systems: Oxygen and hydrogen isotopic measurements on authigenic phases in brittle fault rocks

    Science.gov (United States)

    Haines, S. H.; Anderson, R.; Mulch, A.; Solum, J. G.; Valley, J. W.; van der Pluijm, B. A.

    2009-12-01

    The nature of fluid circulation systems in normal fault systems is fundamental to understanding the nature of fluid movement within the upper crust, and has important implications for the on-going controversy about the strength of faults. Authigenic phases in clay gouges and fault breccias record the isotopic signature of the fluids they formed in equilibrium with, and can be used to understand the ‘plumbing system’ of brittle fault environments. We obtained paired oxygen and hydrogen isotopic measurements on authigenic illite and/or smectite in clay gouge from normal faults in two geologic environments, 1.) low-angle normal faults (Ruby Mountains detachment, NV; Badwater Turtleback, CA; Panamint range-front detachment; CA; Amargosa detachment; CA; Waterman Hills detachment, CA), and 2.) An intracratonic high-angle normal fault (Moab Fault, UT). All authigenic phases in these clay gouges are moderately light isotopically with respect to oxygen (illite δ18O -2.0 - + 11.5 ‰ SMOW, smectite δ18O +3.6 and 17.9 ‰) and very light isotopically with respect to hydrogen (illite δD -148 to -98 ‰ SMOW, smectite δD -147 to -92 ‰). Fluid compositions calculated from the authigenic clays at temperatures of 50 - 130 ○C (as indicated by clay mineralogy) indicate that both illite and smectite in normal fault clay gouge formed in the presence of near-pristine to moderately-evolved meteoric fluids and that igneous or metamorphic fluids are not involved in clay gouge formation in these normal fault settings. We also obtained paired oxygen and hydrogen isotopic measurements on chlorites derived from footwall chlorite breccias in 4 low-angle normal fault detachment systems (Badwater and Mormon Point Turtlebacks, CA, the Chemehuevi detachment, CA, and the Buckskin-Rawhide detachment, AZ). All chlorites are isotopically light to moderately light with respect to oxygen (δ18O +0.29 to +8.1 ‰ SMOW) and very light with respect to hydrogen (δD -97 to -113 ‰) and indicate

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

    Science.gov (United States)

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

    2013-12-01

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

  5. 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

  6. 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

  7. Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition

    Science.gov (United States)

    Jones, Sam P.; Ogée, Jérôme; Sauze, Joana; Wohl, Steven; Saavedra, Noelia; Fernández-Prado, Noelia; Maire, Juliette; Launois, Thomas; Bosc, Alexandre; Wingate, Lisa

    2017-12-01

    The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting

  8. Kinetics of the exchange of oxygen between carbon dioxide and carbonate in aqueous solution

    International Nuclear Information System (INIS)

    Tu, C.K.; Silverman, D.N.

    1975-01-01

    A kinetic analysis of the exchange of oxygen between carbon dioxide and carbonate ion in alkaline, aqueous solutions is presented. The exchange was observed by placing 18 O-labeled carbonate, not enriched in 13 C, into solution with 13 C-enriched carbonate, not enriched in 18 O. The rate of depletion of 18 O from the 12 C-containing species and the rate of appearance of 18 O in the 13 C-containing species was measured by mass spectrometry. From these data, the second-order rate constant for the reaction between carbon dioxide and carbonate which results in the exchange of oxygen at 25 0 is 114 +- 11 M -1 sec -1 . It is emphasized that this exchange of oxygen between species of CO 2 in solution must be recognized in studies using 18 O labels to determine the fate of CO 2 in biochemical and physiological processes. (auth)

  9. Oxygen isotope effect in 55Mn and 95Mo NMR spectra of the permanganate and molybdate ion

    International Nuclear Information System (INIS)

    Buckler, K.U.; Haase, A.R.; Lutz, O.; Mueller, M.; Nolle, A.

    1977-01-01

    By Fourier transform NMR spectroscopy the 55 Mn and 95 Mo resonance lines in the different permanganate and molybdate species Mn 16 Osub(4-n) 18 Osub(n) - and Mo 16 Osub(4-n) 18 Osub(n) 2- (n = 0,1,2,3,4) have been resolved in aqueous solutions of potassium permanganate and sodium molybdate. An isotopic effect on the Larmor frequency for 55 Mn of (0.59+-0.02)ppm and for 95 Mo of (0.25+-0.01)ppm to lower frequency has been found for the substitution of one 16 O atom by one 18 O atom. The relaxation rates 1/T 1 of 55 Mn in the different lines of the permanganate solution are equal within the limits of error. The oxygen exchange rate for the water-permanganate system has been evaluated. (orig.) [de

  10. 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.

  11. 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)

  12. 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)

  13. Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica

    Directory of Open Access Journals (Sweden)

    J. Savarino

    2007-01-01

    Full Text Available Throughout the year 2001, aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d'Urville (DDU (66°40' S, l40°0' E, 40 m above mean sea level. The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth. In association with concentration measurements, the isotope ratios delineate four distinct periods, broadly consistent with previous studies on Antarctic coastal areas. During austral autumn and early winter (March to mid-July, nitrate concentrations attain a minimum between 10 and 30 ng m−3 (referred to as Period 2. Two local maxima in August (55 ng m−3 and November/December (165 ng m−3 are used to assign Period 3 (mid-July to September and Period 4 (October to December. Period 1 (January to March is a transition period between the maximum concentration of Period 4 and the background concentration of Period 2. These seasonal changes are reflected in changes of the nitrogen and oxygen isotope ratios. During Period 2, which is characterized by background concentrations, the isotope ratios are in the range of previous measurements at mid-latitudes: δ18Ovsmow=(77.2±8.6‰; Δ17O=(29.8±4.4‰; δ15Nair=(−4.4±5.4‰ (mean ± one standard deviation. Period 3 is accompanied by a significant increase of the oxygen isotope ratios and a small increase of the nitrogen isotope ratio to δ18Ovsmow=(98.8±13.9‰; Δ17O=(38.8±4.7‰ and δ15Nair=(4.3±8.20‰. Period 4 is characterized by a minimum 15N/14N ratio, only matched by one prior study of Antarctic aerosols, and oxygen isotope ratios similar to Period 2: δ18Ovsmow=(77.2±7.7‰; Δ17O=(31.1±3.2‰; δ15Nair=(−32.7±8.4‰. Finally, during Period 1, isotope ratios reach minimum values for oxygen and intermediate values for nitrogen: δ18Ovsmow=63.2±2.5‰; Δ17O=24.0±1.1‰; δ15Nair=−17.9±4.0‰. Based on the measured

  14. 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.

  15. Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

    International Nuclear Information System (INIS)

    Buchardt, B.; Hansen, H.J.

    1977-01-01

    In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After corrections variations for temperature with depth, characteristic 18 O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera. (author)

  16. Oxygen isotope fractionation and algal symbiosis in benthic foraminifera from the Gulf of Elat, Israel

    Energy Technology Data Exchange (ETDEWEB)

    Buchardt, B; Hansen, H J [Copenhagen Univ. (Denmark)

    1977-01-01

    In order to investigate possible isotopic fractionations due to algal symbiosis the oxygen and carbon isotope compositions of shell carbonate from symbiont-free and symbiont-bearing benthic foraminifera have been compared to that of molluscs living at the same locality. The material was collected over a depth profile in the Gulf of Elat (Aqaba), Israel, covering the interval from 4 to 125 metres. After correcting for variations of temperature with depth, characteristic /sup 18/O-depletions were observed in the foraminiferal shell carbonate when compared to the molluscs. These depletions are interpreted as 1) a constant vital effect seen in all the foraminifera studied and 2) an additional, light-dependent vital effect observed in the symbiont-bearing forms only, caused by incorporation of photosynthetic oxygen formed by the symbiotic algae. This additional vital effect emphasizes the difficulties in applying foraminifera to oxygen isotope palaeotemperature analyses. No well-defined differences in carbon isotope compositions are observed between symbiont-bearing and symbiont-free foraminifera.

  17. Steel reinforced composite silicone membranes and its integration to microfluidic oxygenators for high performance gas exchange.

    Science.gov (United States)

    Matharoo, Harpreet; Dabaghi, Mohammadhossein; Rochow, Niels; Fusch, Gerhard; Saraei, Neda; Tauhiduzzaman, Mohammed; Veldhuis, Stephen; Brash, John; Fusch, Christoph; Selvaganapathy, P Ravi

    2018-01-01

    Respiratory distress syndrome (RDS) is one of the main causes of fatality in newborn infants, particularly in neonates with low birth-weight. Commercial extracorporeal oxygenators have been used for low-birth-weight neonates in neonatal intensive care units. However, these oxygenators require high blood volumes to prime. In the last decade, microfluidics oxygenators using enriched oxygen have been developed for this purpose. Some of these oxygenators use thin polydimethylsiloxane (PDMS) membranes to facilitate gas exchange between the blood flowing in the microchannels and the ambient air outside. However, PDMS is elastic and the thin membranes exhibit significant deformation and delamination under pressure which alters the architecture of the devices causing poor oxygenation or device failure. Therefore, an alternate membrane with high stability, low deformation under pressure, and high gas exchange was desired. In this paper, we present a novel composite membrane consisting of an ultra-thin stainless-steel mesh embedded in PDMS, designed specifically for a microfluidic single oxygenator unit (SOU). In comparison to homogeneous PDMS membranes, this composite membrane demonstrated high stability, low deformation under pressure, and high gas exchange. In addition, a new design for oxygenator with sloping profile and tapered inlet configuration has been introduced to achieve the same gas exchange at lower pressure drops. SOUs were tested by bovine blood to evaluate gas exchange properties. Among all tested SOUs, the flat design SOU with composite membrane has the highest oxygen exchange of 40.32 ml/min m 2 . The superior performance of the new device with composite membrane was demonstrated by constructing a lung assist device (LAD) with a low priming volume of 10 ml. The LAD was achieved by the oxygen uptake of 0.48-0.90 ml/min and the CO 2 release of 1.05-2.27 ml/min at blood flow rates ranging between 8 and 48 ml/min. This LAD was shown to increase the

  18. Intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite measured by thermal dehydroxylation and partial fluorination

    Science.gov (United States)

    Girard, Jean-Pierre; Savin, Samuel M.

    1996-02-01

    Thermal dehydroxylation and partial fluorination techniques were used to measure intracrystalline fractionation of oxygen isotopes between hydroxyl and non-hydroxyl sites in kaolinite. Several aliquots of a well characterized, fine-grained (rates, and target temperatures. Measured δ18O values of both the liberated water and the dehydroxylated residue are consistent over a wide range of temperatures (550 850°C) when dehydroxylation is performed in a single-step fashion at a rapid heating rate (>50°C/min.). Similar dehydroxylation experiments indicate that brucite dehydroxylation occurs without any significant isotopic fractionation of the oxygen isotopes. By extrapolation we postulate that no significant fractionation occurs during single-step thermal dehydroxylation of fine-grained kaolinite, provided that dehydroxylation is performed under well controlled conditions. In contrast, gibbsite dehydroxylation is accompanied by substantial isotopic fractionation. This is probably the result of the complex, multi-pathway dehydroxylation reaction of this mineral. Similarly, thermal dehydroxylation of coarsegrained (>1 μm) kaolinites and dickites of weathering and hydrothermal origin yield results that are dependent on the temperature of dehydroxylation. We suggest that this effect may be caused by isotopic exchange during diffusion of water molecules through coarse particles. Partial fluorination of fine-grained kaolinite in the presence of excess F2 at low temperatures (rate of reaction of hydroxyl oxygen than of non-hydroxyl oxygen, but examination of the isotopic data as well as XRD and IR analyses of the residues after partial fluorination indicates that the separation between the two types of oxygen is not complete. The results, therefore, do not yield a reliable δ18O value of the hydroxyl oxygen. The results of this study suggest that the thermal dehydroxylation technique may be appropriate for analysis of OH groups in fine-grained kaolinite. The partial

  19. CO self-shielding as the origin of oxygen isotope anomalies in the early solar nebula.

    Science.gov (United States)

    Lyons, J R; Young, E D

    2005-05-19

    The abundances of oxygen isotopes in the most refractory mineral phases (calcium-aluminium-rich inclusions, CAIs) in meteorites have hitherto defied explanation. Most processes fractionate isotopes by nuclear mass; that is, 18O is twice as fractionated as 17O, relative to 16O. In CAIs 17O and 18O are nearly equally fractionated, implying a fundamentally different mechanism. The CAI data were originally interpreted as evidence for supernova input of pure 16O into the solar nebula, but the lack of a similar isotope trend in other elements argues against this explanation. A symmetry-dependent fractionation mechanism may have occurred in the inner solar nebula, but experimental evidence is lacking. Isotope-selective photodissociation of CO in the innermost solar nebula might explain the CAI data, but the high temperatures in this region would have rapidly erased the signature. Here we report time-dependent calculations of CO photodissociation in the cooler surface region of a turbulent nebula. If the surface were irradiated by a far-ultraviolet flux approximately 10(3) times that of the local interstellar medium (for example, owing to an O or B star within approximately 1 pc of the protosun), then substantial fractionation of the oxygen isotopes was possible on a timescale of approximately 10(5) years. We predict that similarly irradiated protoplanetary disks will have H2O enriched in 17O and 18O by several tens of per cent relative to CO.

  20. Modelling and Mapping Oxygen-18 Isotope Composition of Precipitation in Spain for Hydrologic and Climatic Applications

    International Nuclear Information System (INIS)

    Rodriguez-Arevalo, J.; Diaz-Teijeiro, M.F.; Castano, S.

    2011-01-01

    A simple multiple regression model based on two geographic factors (latitude and elevation) has been developed that reproduces reasonably well the spatial distribution of the current mean oxygen-18 isotope composition in precipitation over Spain. In a preliminary analysis, additional geographic and climatic factors do not improve the performance of the model. A continuous digital map of oxygen-18 isotope composition in precipitation has been produced by combining the polynomial model with a Digital Elevation Model using GIS tools. Application of the resulting map to several case studies in Spain has shown it to be useful as a reference of the isotope input function to groundwater recharge and surface runoff. The results obtained so far show a good fit between modelled stable isotope values and those measured in surface and ground waters from different aquifers and recharge areas. The GIS tools applied to a continuous digital layer of spatial isotope are able to provide accurate information at detailed scales that are not affordable by other means. Further validation of the model, and further testing of its usefulness in surface hydrology and climatic studies, is going on.

  1. Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

    Science.gov (United States)

    Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

    2017-08-01

    Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

  2. 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)

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

    Science.gov (United States)

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

    2004-01-01

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

  4. 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)

  5. 18O isotopic tracer studies of silicon oxidation in dry oxygen

    International Nuclear Information System (INIS)

    Han, C.J.

    1986-01-01

    Oxidation of silicon in dry oxygen has been an important process in the integrated circuit industry for making gate insulators on metal-oxide-semiconductory (MOS) devices. This work examines this process using isotopic tracers of oxygen to determine the transport mechanisms of oxygen through silicon dioxide. Oxides were grown sequentially using mass-16 and mass-18 oxygen gas sources to label the oxygen molecules from each step. The resulting oxides are analyzed using secondary ion mass spectrometry (SIMS). The results of these analyses suggest two oxidant species are present during the oxidation, each diffuses and oxidizes separately during the process. A model from this finding using a sum of two linear-parabolic growth rates, each representing the growth rate from one of the oxidants, describes the reported oxidation kinetics in the literature closely. A fit of this relationship reveals excellent fits to the data for oxide thicknesses ranging from 30 A to 1 μm and for temperatures ranging from 800 to 1200 0 C. The mass-18 oxygen tracers also enable a direct observation of the oxygen solubility in the silicon dioxide during a dry oxidation process. The SIMS profiles establish a maximum solubility for interstitial oxygen at 1000 0 C at 2 x 10 20 cm -3 . Furthermore, the mass-18 oxygen profiles show negligible network diffusion during an 1000 0 C oxidation

  6. Oxygen isotope signature of UV degradation of glyphosate and phosphonoacetate: Tracing sources and cycling of phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Department of Chemistry, University of Sierra Leone, Freetown (Sierra Leone); Blake, Ruth E., E-mail: ruth.blake@yale.edu [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Chang, Sae Jung [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); Jun, Yao, E-mail: yaojun@ustb.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China); Yu, Chan [Department of Geology and Geophysics, Yale University, P.O. Box 208109, New Haven, CT 06520-8109 (United States); School of Civil and Environmental Engineering, and National “International Cooperation Base on Environment and Energy”, University of Science and Technology Beijing, Beijing 100084 (China)

    2013-09-15

    Highlights: • Phosphonate (phon) hydrolysis by UVR (1.2 kW) attained ≥90% completion in 84 h. • Isotope study reveals both ambient H{sub 2}O and O{sub 2} involvements in phon C-P bond cleavage. • Mechanistic models proposed for phon C-P bond cleavage based on O-isotope analysis. • Model equations used to calculate δ{sup 18}O{sub P-org} of original phon P-moiety-useful as a tracer. • Study shows relevance in tracing phon sources and cycling in the environment. -- Abstract: The degradation of phosphonates in the natural environment constitutes a major route by which orthophosphate (Pi) is regenerated from organic phosphorus and recently implicated in marine methane production, with ramifications to environmental pollution issues and global climate change concerns. This work explores the application of stable oxygen isotope analysis in elucidating the C-P bond cleavage mechanism(s) of phosphonates by UV photo-oxidation and for tracing their sources in the environment. The two model phosphonates used, glyphosate and phosphonoacetic acid were effectively degraded after exposure to UV irradiation. The isotope results indicate the involvement of both ambient water and atmospheric oxygen in the C-P bond cleavage and generally consistent with previously posited mechanisms of UV-photon excitation reactions. A model developed to calculate the oxygen isotopic composition of the original phosphonate P-moiety, shows both synthetic phosphonates having distinctly lower values compared to naturally derived organophosphorus compounds. Such mechanistic models, based on O-isotope probing, are useful for tracing the sources and reactions of phosphonates in the environment.

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

    Science.gov (United States)

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

    2013-04-01

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

  8. Measurement of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen

    International Nuclear Information System (INIS)

    Wiedenbeck, M.E.; Greiner, D.E.; Bieser, F.S.; Crawford, H.J.; Heckman, H.H.; Lindstrom, P.J.

    1979-06-01

    The results of an investigation of the isotopic composition of galactic cosmic ray carbon, nitrogen and oxygen (E approx. 80 to 230 MeV/amu) made using the U.C. Berkeley HKH instrument aboard the ISEE-3 spacecraft are reported. The combination of high mass resolution and a large statistical sample makes possible a precise determination of the relative isotopic abundances for these elements. In local interplanetary space we find: 13 C/C = 0.067 +- 0.008, 15 N/N = 0.54 +- 0.03, 17 O/O 18 O/O = 0.019 +- 0.003

  9. Water relations link carbon and oxygen isotope discrimination to phloem sap sugar concentration in eucalyptus globulus

    International Nuclear Information System (INIS)

    Cernusak, L.A.; Farquhar, G.D.; Arthur, D.J; Pate, J.S.

    2002-01-01

    Full text: The carbon isotope ratio of phloem sap sugars has been previously observed to correlate strongly with the phloem sap sugar concentration in Eucalyptus globulus. We hypothesized that the correspondence between these two parameters results from co-linearity in their responses to variation in plant water potential. Carbon isotope discrimination is expected to decrease with decreasing plant water potential due to the influence of stomatal conductance on the ratio of intercellular to ambient CO 2 , concentrations (c 1 /c a ). Conversely, we expected the phloem sap sugar concentration to increase with decreasing plant water potential, thereby maintaining positive turgor pressure within the sieve tubes. The study comprised 40 individual Eucalyptus globulus trees growing in three plantations situated on opposing ends of a rainfall gradient in southwestern Australia. A strong correlation was observed between the carbon isotope ratio in phloem sap sugars and phloem sap sugar concentration. Carbon isotope discrimination correlated positively with shoot water potential, whereas phloem sap sugar concentration correlated negatively with shoot water potential. The relationship between carbon isotope discrimination measured in phloem sap sugars collected from the stem and c 1 /c a measured instantaneously on subtending leaves was close to that theoretically predicted. Accordingly, a strong, negative relationship was observed between instantaneous c 1 /c a and the phloem sap sugar concentration. Oxygen isotope discrimination in phloem sap sugars also correlated strongly with phloem sap sugar concentration. A theoretical model suggested that the observed variation in stomatal conductance was sufficient to account for the variation observed in oxygen isotope discrimination across the study. Results strongly support the contention that water relations form a mechanistic link between phloem sap sugar concentration and both instantaneous and integrated measures of the

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  11. 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

  12. 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

  13. Oxygen isotope variability in snow from western Dronning Maud Land, Antarctica and its relation to temperature

    International Nuclear Information System (INIS)

    Helsen, M.M.; Wal, R.S.W. van de; Broeke, M.R. van den; As, D. van; Reijmer, C.H.; Meijer, H.A.J.

    2005-01-01

    This paper presents (delta) 18 O records from snow pits from four locations in Dronning Maud Land, Antarctica that contain at least four annual cycles. The aim of the study was to analyse in detail these records as well as the prevailing temperatures during accumulation in order to infer to what extent isotopic composition in this area can be interpreted as temperature information. The original seasonal amplitudes of the isotope records were reconstructed by use of a simple back-diffusion model. Automatic weather station data were used to describe the accumulation history and the near-surface temperatures; the temperatures at the atmospheric level of snow formation were inferred from a regional climate model. The results show that the strongly intermittent nature of the accumulation in this area can result in the exclusion of entire seasons from the isotope records. The temperature records also reveal that the oxygen isotope records in these snow pits are biased towards higher temperatures, since snowfall conditions are associated with higher temperatures. This effect is greatest at low temperatures. A comparison between the seasonal extreme isotopic and temperature values points out that on timescales of seasons to several years, isotopic variability cannot be interpreted with confidence as temperature changes at the accumulation sites

  14. Oxygen, hydrogen, sulfur, and carbon isotopes in the Pea Ridge magnetite-apatite deposit, southeast Missouri, and sulfur isotope comparisons to other iron deposits in the region

    Science.gov (United States)

    Johnson, Craig A.; Day, Warren C.; Rye, Robert O.

    2016-01-01

    Oxygen, hydrogen, sulfur, and carbon isotopes have been analyzed in the Pea Ridge magnetite-apatite deposit, the largest historic producer among the known iron deposits in the southeast Missouri portion of the 1.5 to 1.3 Ga eastern granite-rhyolite province. The data were collected to investigate the sources of ore fluids, conditions of ore formation, and provenance of sulfur, and to improve the general understanding of the copper, gold, and rare earth element potential of iron deposits regionally. The δ18O values of Pea Ridge magnetite are 1.9 to 4.0‰, consistent with a model in which some magnetite crystallized from a melt and other magnetite—perhaps the majority—precipitated from an aqueous fluid of magmatic origin. The δ18O values of quartz, apatite, actinolite, K-feldspar, sulfates, and calcite are significantly higher, enough so as to indicate growth or equilibration under cooler conditions than magnetite and/or in the presence of a fluid that was not entirely magmatic. A variety of observations, including stable isotope observations, implicate a second fluid that may ultimately have been meteoric in origin and may have been modified by isotopic exchange with rocks or by evaporation during storage in lakes.Sulfur isotope analyses of sulfides from Pea Ridge and seven other mineral deposits in the region reveal two distinct populations that average 3 and 13‰. Two sulfur sources are implied. One was probably igneous melts or rocks belonging to the mafic- to intermediate-composition volcanic suite that is present at or near most of the iron deposits; the other was either melts or volcanic rocks that had degassed very extensively, or else volcanic lakes that had trapped rising magmatic gases. The higher δ34S values correspond to deposits or prospects where copper is noteworthy—the Central Dome portion of the Boss deposit, the Bourbon deposit, and the Vilander prospective area. The correspondence suggests that (1) sulfur either limited the deposition

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1998-03-01

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

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

    International Nuclear Information System (INIS)

    1984-01-01

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

  17. Air-water oxygen exchange in a large whitewater river

    Science.gov (United States)

    Hall, Robert O.; Kennedy, Theodore A.; Rosi-Marshall, Emma J.

    2012-01-01

    Air-water gas exchange governs fluxes of gas into and out of aquatic ecosystems. Knowing this flux is necessary to calculate gas budgets (i.e., O2) to estimate whole-ecosystem metabolism and basin-scale carbon budgets. Empirical data on rates of gas exchange for streams, estuaries, and oceans are readily available. However, there are few data from large rivers and no data from whitewater rapids. We measured gas transfer velocity in the Colorado River, Grand Canyon, as decline in O2 saturation deficit, 7 times in a 28-km segment spanning 7 rapids. The O2 saturation deficit exists because of hypolimnetic discharge from Glen Canyon Dam, located 25 km upriver from Lees Ferry. Gas transfer velocity (k600) increased with slope of the immediate reach. k600 was -1 in flat reaches, while k600 for the steepest rapid ranged 3600-7700 cm h-1, an extremely high value of k600. Using the rate of gas exchange per unit length of water surface elevation (Kdrop, m-1), segment-integrated k600 varied between 74 and 101 cm h-1. Using Kdrop we scaled k600 to the remainder of the Colorado River in Grand Canyon. At the scale corresponding to the segment length where 80% of the O2 exchanged with the atmosphere (mean length = 26.1 km), k600 varied 4.5-fold between 56 and 272 cm h-1 with a mean of 113 cm h-1. Gas transfer velocity for the Colorado River was higher than those from other aquatic ecosystems because of large rapids. Our approach of scaling k600 based on Kdrop allows comparing gas transfer velocity across rivers with spatially heterogeneous morphology.

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

    International Nuclear Information System (INIS)

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

    1999-01-01

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

  19. 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.

  20. 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)

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

    Science.gov (United States)

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

    2014-01-01

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

  2. Non-mass-dependent fractionation of sulfur and oxygen isotopes during UV photolysis of sulfur dioxide

    Science.gov (United States)

    Pen, Aranh

    Since the discovery of anomalous sulfur isotope abundance in the geological record in sulfate and sulfide minerals (Farquhar et al., 2000), much effort has been put into understanding their origin to provide new insights into the environmental conditions on the early Earth (Farquhar et al., 2001; Pavlov and Kasting, 2002; Ono et al., 2003; Zahnle et al., 2006; Farquhar et al., 2007; Lyons, 2007; Lyons, 2008). This discovery gained immense interest because of its implications for both the lack of oxygen in the atmosphere during the Archean era 2.5-3.8 Gya (billion years ago), and for rise of oxygen, or the "Great Oxidation Event", that occurred 2.2-2.4 Gya (Holland, 2002). These signatures are believed to be produced in an anticorrelation to oxygen abundance in the early atmosphere, which will aid in quantifying the rate of oxygenation during the "Great Oxidation Event". According to Farquhar et al. (2000), the non-mass-dependent (NMD), or anomalous, fractionation signatures were produced by photochemical reactions of volcanic sulfur species in Earth's early atmosphere (> 2.3 Gya) due to the lack of an oxygen and ozone shield, resulting in an atmosphere transparent to solar ultraviolet (UV) radiation (Farquhar et al., 2001). Interpretation of the anomalous rock records, though, depends on the identification of (1) chemical reactions that can produce the NMD signature (Farquhar and Wing, 2003); and (2) conditions necessary for conversion of the gas-phase products into solid minerals (Pavlov and Kasting, 2002). The focus of my research addresses the first step, which is to determine whether the chemical reactions that occurred in Earth's early atmosphere, resulting in NMD fractionation of sulfur isotopes, were due to broadband UV photochemistry, and to test isotopic self-shielding as the possible underlying mechanism. In this project, our goals were to test isotopic self-shielding during UV photolysis as a possible underlying mechanism for anomalous sulfur isotopic

  3. Technical note: Consistent calculation of aquatic gross production from oxygen triple isotope measurements

    Directory of Open Access Journals (Sweden)

    J. Kaiser

    2011-07-01

    Full Text Available Oxygen triple isotope measurements can be used to calculate aquatic gross oxygen production rates. Past studies have emphasised the appropriate definition of the 17O excess and often used an approximation to derive production rates from the 17O excess. Here, I show that the calculation can be phrased more consistently and without any approximations using the relative 17O/16O and 18O/16O isotope ratio differences (delta values directly. I call this the "dual delta method". The 17O excess is merely a mathematical construct and the derived production rate is independent of its definition, provided all calculations are performed with a consistent definition. I focus on the mixed layer, but also show how time series of triple isotope measurements below the mixed layer can be used to derive gross production.

    In the calculation of mixed layer productivity, I explicitly include isotopic fractionation during gas invasion and evasion, which requires the oxygen supersaturation s to be measured as well. I also suggest how bubble injection could be considered in the same mathematical framework. I distinguish between concentration steady state and isotopic steady state and show that only the latter needs to be assumed in the calculation. It is even possible to derive an estimate of the net production rate in the mixed layer that is independent of the assumption of concentration steady state.

    I review measurements of the parameters required for the calculation of gross production rates and show how their systematic uncertainties as well as the use of different published calculation methods can cause large variations in the production rates for the same underlying isotope ratios. In particular, the 17O excess of dissolved O2 in equilibrium with atmospheric O2 and the 17O excess of photosynthetic O2 need to

  4. Oxygen isotope variations at the margin of a CAI records circulation within the solar nebula.

    Science.gov (United States)

    Simon, Justin I; Hutcheon, Ian D; Simon, Steven B; Matzel, Jennifer E P; Ramon, Erick C; Weber, Peter K; Grossman, Lawrence; DePaolo, Donald J

    2011-03-04

    Micrometer-scale analyses of a calcium-, aluminum-rich inclusion (CAI) and the characteristic mineral bands mantling the CAI reveal that the outer parts of this primitive object have a large range of oxygen isotope compositions. The variations are systematic; the relative abundance of (16)O first decreases toward the CAI margin, approaching a planetary-like isotopic composition, then shifts to extremely (16)O-rich compositions through the surrounding rim. The variability implies that CAIs probably formed from several oxygen reservoirs. The observations support early and short-lived fluctuations of the environment in which CAIs formed, either because of transport of the CAIs themselves to distinct regions of the solar nebula or because of varying gas composition near the proto-Sun.

  5. Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

    Science.gov (United States)

    Longinelli, Antonio

    1984-02-01

    Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ18O of body water has been shown to vary linearly with the mean δ18O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ18O( PO3-4) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ18O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.

  6. Assessment of nitrogen and oxygen isotopic fractionation during nitrification and its expression in the marine environment.

    Science.gov (United States)

    Casciotti, Karen L; Buchwald, Carolyn; Santoro, Alyson E; Frame, Caitlin

    2011-01-01

    Nitrification is a microbially-catalyzed process whereby ammonia (NH(3)) is oxidized to nitrite (NO(2)(-)) and subsequently to nitrate (NO(3)(-)). It is also responsible for production of nitrous oxide (N(2)O), a climatically important greenhouse gas. Because the microbes responsible for nitrification are primarily autotrophic, nitrification provides a unique link between the carbon and nitrogen cycles. Nitrogen and oxygen stable isotope ratios have provided insights into where nitrification contributes to the availability of NO(2)(-) and NO(3)(-), and where it constitutes a significant source of N(2)O. This chapter describes methods for determining kinetic isotope effects involved with ammonia oxidation and nitrite oxidation, the two independent steps in the nitrification process, and their expression in the marine environment. It also outlines some remaining questions and issues related to isotopic fractionation during nitrification. Copyright © 2011 Elsevier Inc. All rights reserved.

  7. The Largs high-latitude oxygen isotope anomaly (New Zealand) and climatic controls of oxygen isotopes in magma

    International Nuclear Information System (INIS)

    Blattner, P.; Williams, J.G.

    1991-01-01

    In northern Fiordland the Brook Street terrane of New Zealand consists of two units - the predominantly basaltic Plato and the predominantly andesitic Largs terrane. The Permian Plato terrane has normal to slightly enriched δ 18 O values, whereas the Largs terrane, which is of similar pre-early Triassic age, has not yielded a single normal δ 18 O SMOW result, with all of 17 total rocks showing less than 3.2per mille, seven less than -4per mille, and two less than -9per mille. These strongly anomalous data confirm an earlier suggested terrestrial character of Largs deposition, and demand the presence of Permo-Triassic geothermal systems running on subAntarctic to Antarctic meteoric water. The skewed data spectrum suggests a relatively immature flow system and likely values for the recharge water are -20per mille δ 18 O or less. For a climate distribution similar to the present one, inlcuding polar ice caps, this would indicate over 70deg of southern latitude. Rafts and xenoliths of Largs rocks have been entrained within Mackay Intrusives in the early Triassic. On field evidence the Mackay magmas have also intruded an early Darran Complex, but this complex has been substantially reactivated in the Cretaceous. It has δ 18 O values near 5.0per mille, which is distinctly low for island arc magmas. Since the complex is isotopically homogenous, its δ 18 O is unlikely to be a direct effect of the relatively shallow Largs terrane. More probable is a climate related slight depression of the δ 18 O of magma sources, in which other high-latitude, low-δ 18 O sediments and geothermal systems have been involved. (orig.)

  8. Oxygen isotopic abundances in the atmospheres of seven red giant stars

    International Nuclear Information System (INIS)

    Harris, M.J.; Lambert, D.L.

    1984-01-01

    Abundances ratios of the oxygen isotopes have been measured in α Tau, β And, μ Gem, α Her, β Peg, γ Dra, and α Boo. In all the stars the 16 O/ 18 O ratios are similar; the mean value is 475, which is consistent with the solar system value 16 O/ 18 O = 490. The 16 O/ 17 O ratios range from approx.1000 for β Peg and α Boo to 16 O/ 17 O = 160 for β And

  9. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    OpenAIRE

    Ziveri, P.; Thoms, S.; Probert, I.; Geisen, M.; Langer, H.

    2012-01-01

    The oxygen isotopic composition (δ18O) of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy c...

  10. Synopsis of oxygen isotopes in geothermal solids and fluids of New Zealand

    International Nuclear Information System (INIS)

    Blattner, P.

    1982-01-01

    Geothermal minerals serve as downhole probes of oxygen isotope compositions and thus of parameters of geothermal hydrology. ''Deep'' wells (2500 m) in New Zealand show no sign of Δ 18 O values ''bottoming out''. Ngawha differs from other systems both in the level and profile details of Δ 18 O values. The reservoir fluid at Ngawha hydrogeology may or may not be suited for development of a high-throughput surface recharge system

  11. Oxygen isotopic composition of relict olivine grains in cosmic spherules: Links to chondrules from carbonaceous chondrites

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; ShyamPrasad, M.; Nagashima, K.; Jones, R.H.

    aluminium rich inclusions (CAIs), amoeboid olivine aggregates (AOAs), and some porphyritic chondrules from carbonaceous chondrites. These grains appear to have recorded the initial oxygen isotopic composition of the inner solar nebula. Three olivine... to the major components of meteorites such as chondrules and calcium-aluminium-rich inclusions (CAIs). CAIs, the first solar system objects in the solar nebula, are formed by condensation of refractory minerals at high temperatures. They are 16O...

  12. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    Science.gov (United States)

    Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.

    2012-01-01

    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

  13. Permafrost oxygen isotope ratios and chronology of three cores from Antarctica

    International Nuclear Information System (INIS)

    Stuiver, M.; Yang, I.C.; Denton, G.H.

    1976-01-01

    It is stated that permafrost core sediments, associated with the last intrusion of the Ross Ice Shelf in the New Harbour region, were deposited in marine (0 - 85 m deep) as well as freshwater environments (100 - 125 m). Oxygen isotope ratio measurements on these cores provide palaeoclimatic information and show that the extension of the Ross Ice Shelf predates 150,000 yr BP, whereas the radiocarbon date of its retreat is about 5,800 yr b.p. (author)

  14. Fractionation of hydrogen and oxygen isotopes between hydrated and free water molecules in aqueous urea solution

    International Nuclear Information System (INIS)

    Kakiuchi, M.; Matsuo, S.

    1985-01-01

    Ratios of D/H and 18 O/ 16 O in the vapor phase in equilibrium with aqueous urea solution with different urea molalities were measured at 15 and 25 0 C. Under the assumption that urea solutions consist of two species, i.e., the urea-water cluster and free water, the results are interpreted to give the average hydration number, i.e., the number of water molecules per urea molecule in the urea-water cluster. Good agreement was obtained for the hydration number estimated independently from hydrogen and oxygen isotopic fractions. On the basis of hydrogen isotopic data at 25 0 C, the average hydration number of urea in the cluster is 6.3 +/- 0.8 at 2.1 m and 2.75 +/- 0.08 at saturation (20.15 m). The corresponding average hydration numbers based on oxygen isotopic data were calculated to be 6.7 +/- 2.4 at 2.1 m and 2.75 +/- 0.25 at urea saturation. HD 16 O is enriched in the urea-water cluster and H 2 18 O is enriched in free water. Isotopic partitioning between the cluster and free water is markedly different from those between hydration spheres and free water in aqueous electrolyte solutions. 29 references, 6 figures, 5 tables

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

    International Nuclear Information System (INIS)

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

    2012-01-01

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

  16. Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

    Science.gov (United States)

    Kang, J.; Buyanjargal, A.; Jeen, S. W.

    2017-12-01

    Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

  17. Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

    Science.gov (United States)

    Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.

    2002-01-01

    Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  18. Oxygen isotope analyses of ground ice from North of West Siberia, from Yakutia and from Chukotka

    International Nuclear Information System (INIS)

    Vaikmaee, R.; Vassilchuk, Y.

    1991-01-01

    The aim of the present work is to make the large amount of original factual material obtained by studying the oxygen isotope composition in different types of permafrost and ground ice available to specialists. The samples analysed were systematically collected over a period of many years from different permafrost areas of the Soviet Union with the aim of elucidating and studying the regularities of isotope composition formation in different types of ground ice and selecting the most promising objects for paleoclimatic reconstructions. Much attention was paid on methodical problems of isotopic analysis starting with the collection, transportation and storage of samples up to the interpretation of the results obtained. Besides permafrost isotope data covering a large geographical area, a good deal of data concerns the isotopic composition of precipitation and surface water in permafrost areas. This is of great consequence as regards the understanding of the regularities of isotope compositions formation in permafrost. The largest chapter gives a brief account of the isotopic composition in different types of ground ice. The conclusion has been reached that in terms of paleoclimatic research syngenetic ice wedges are most promising. Grounding on the representative data bank it may be maintained with certainty that the isotopic composition provides a reliable basis for the differentiation of ice wedges originating in different epochs , however, it also reveals regional regularities. Much more complicated is the interpretation of textural ice isotopic composition. In some cases it is possible to use the distribution of 18 O in vertical sections of textural ice for their stratigraphic division. One has to consider here different mechanisms of textural ice formation as a result of which the initial isotopic composition of the ice-forming water can be in some cases highly modified. A problem of its own is the investigation of 18 O variations in the section of massive

  19. Oxygen exchange and transport in dual phase ceramic composite electrodes.

    Science.gov (United States)

    Druce, John; Téllez, Helena; Ishihara, Tatsumi; Kilner, John A

    2015-01-01

    Composites consisting of a perovskite-based electronic or mixed conductor with a fluorite-structured ionic conductor are often used as electrodes in solid oxide electrochemical energy conversion devices. After sintering the materials, there is often evidence for inter-reaction between the two phases, or inter-diffusion of cations or impurities between the two phases. We studied the (18)O exchange properties of a composite consisting of CGO and LSCF in a 50 : 50 ratio. High resolution ToF-SIMS mapping reveals that the (18)O fraction at the very outer surface of grains of the CGO phase is much higher than expected from D* and k* values for the single-phase parent material. Surface compositional analysis by ToF-SIMS and low energy ion scattering (LEIS) spectroscopy suggests that the surfaces of the CGO grains in the composite do not show the impurities which typically segregate to the surface in single-phase CGO. Thus, the "cleaning" of impurities from the CGO surface by dissolution into the perovskite phase may be one explanation for the apparent enhanced surface exchange for CGO in these composites.

  20. 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'.

  1. Measurements of tritium recycling and isotope exchange in TFTR

    International Nuclear Information System (INIS)

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

    1996-05-01

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

  2. The effect of storage time of human red cells on intestinal microcirculatory oxygenation in a rat isovolemic exchange model

    NARCIS (Netherlands)

    Raat, N. J.; Verhoeven, A. J.; Mik, E. G.; Gouwerok, C. W.; Verhaar, R.; Goedhart, P. T.; de Korte, D.; Ince, C.

    2005-01-01

    Objective: To determine whether the storage time of human leukodepleted red blood cell concentrates compromises intestinal microvascular oxygen concentration oxygen (muPo(2)) during isovolemic exchange transfusion at low hematocrit. Design: Prospective, randomized, controlled study. Setting:

  3. Fluxes and exchange rates of radon and oxygen across an air-sea interface

    International Nuclear Information System (INIS)

    Duenas, C.; Fernandez, M.C.; La Torre, M. de

    1986-01-01

    The flux of 222 Rn and O 2 from shallow water off the Bay of Malaga has been measured. The mean value of flux of 222 Rn is evaluated to be 74 atoms/m 2 · s. The Bay is a weak source of oxygen to the atmosphere, where the net production of oxygen is found to be 1.82 mol/m 2 · y. Moreover, the gas exchange rates of 222 Rn and O 2 across the air-sea interface has been determined by the radon method. The gas exchange rates and the wind speed have been estimated. (author)

  4. 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

  5. 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

  6. 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

  7. 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)

  8. 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)

  9. 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)

  10. 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

  11. 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.)

  12. 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)

  13. 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)

  14. Carbon, hydrogen oxygen isotope studies on imbedded old tree ring and paleoclimate reconstruction

    International Nuclear Information System (INIS)

    Sun Yanrong; Mu Zhiguo; Cui Haiting

    2002-01-01

    Tree ring is a kind of natural archives, on which the isotopic analysis is important to study global climate and environmental change. The authors mainly provide a comprehensive introduction to the fractionation models of carbon, hydrogen and oxygen isotope in plants, their research technique and the extract methods from cellulose. That results show isotopic tracer can record the message of climatic variation and has become a powerful tool for paleoclimate reconstruction and for the modern environment changing research. Especially studying on PAGES. the cellulose isotopic analyses of imbedded old tree ring have become the mainly quantitative means of environmental evolvement. In addition, China is a typical monsoon country, research in tree ring stable isotope seasonal variation can give a lot of important information on that. Up to now, the research techniques and works on tree ring in China are still in its earlier stage, and remain many limitations. It needs further accumulate basic research materials, intensity regional contrast and intercross studies on relative subjects

  15. 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)

  16. 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)

  17. 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.

  18. 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

  19. 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)

  20. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup

    2013-10-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  1. Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

    KAUST Repository

    Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

    2013-01-01

    The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry. © 2013 Elsevier B.V.

  2. 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

  3. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

    Science.gov (United States)

    McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.

    2002-12-01

    Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

  4. Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

    Science.gov (United States)

    Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

    2016-12-30

    Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision

  5. 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)

  6. Kinetic bottlenecks to chemical exchange rates for deep-sea animals - Part 1: Oxygen

    Science.gov (United States)

    Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

    2012-10-01

    Ocean warming will reduce dissolved oxygen concentrations which can pose challenges to marine life. Oxygen limits are traditionally reported simply as a static concentration thresholds with no temperature, pressure or flow rate dependency. Here we treat the oceanic oxygen supply potential for heterotrophic consumption as a dynamic molecular exchange problem analogous to familiar gas exchange processes at the sea surface. A combination of the purely physico-chemical oceanic properties temperature, hydrostatic pressure, and oxygen concentration defines the ability of the ocean to supply oxygen to any given animal. This general oceanic oxygen supply potential is modulated by animal specific properties such as the diffusive boundary layer thickness to define and limit maximal oxygen supply rates. Here we combine all these properties into formal, mechanistic equations defining novel oceanic properties that subsume various relevant classical oceanographic parameters to better visualize, map, comprehend, and predict the impact of ocean deoxygenation on aerobic life. By explicitly including temperature and hydrostatic pressure into our quantities, various ocean regions ranging from the cold deep-sea to warm, coastal seas can be compared. We define purely physico-chemical quantities to describe the oceanic oxygen supply potential, but also quantities that contain organism-specific properties which in a most generalized way describe general concepts and dependencies. We apply these novel quantities to example oceanic profiles around the world and find that temperature and pressure dependencies of diffusion and partial pressure create zones of greatest physical constriction on oxygen supply typically at around 1000 m depth, which coincides with oxygen concentration minimum zones. In these zones, which comprise the bulk of the world ocean, ocean warming and deoxygenation have a clear negative effect for aerobic life. In some shallow and warm waters the enhanced diffusion and

  7. Constraints on the nature of the projectile using siderophile elements and triple-oxygen isotopes: Zhamanshin impact structure, Kazakhstan

    Czech Academy of Sciences Publication Activity Database

    Jonášová, Šárka; Ackerman, Lukáš; Žák, Karel; Skála, Roman; Magna, T.; Pack, A.; Deutsch, A.

    2016-01-01

    Roč. 51, SI, Supplement 1 (2016), A358-A358 ISSN 1086-9379. [Annual Meeting of the Meteoritical Society /79./. 07.08.2016-12.08.2016, Berlin] Institutional support: RVO:67985831 Keywords : impact glass * irghizites * geochemistry * meteoritic component * siderophile elements * osmium isotopes * triple-oxygen Isotopes * Zhamanshin Subject RIV: DD - Geochemistry

  8. [Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

    Science.gov (United States)

    Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie

    2013-04-01

    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  9. Oxygen isotope thermometry of quartz-Al2SiO5veins in high-grade metamorphic rocks on Naxos island (Greece)

    Science.gov (United States)

    Putlitz, Benita; Valley, John; Matthews, Alan; Katzir, Yaron

    2002-04-01

    Diffusion models predict that peak metamorphic temperatures are best recorded by the oxygen isotope fractionation between minerals in a bi-mineralic rock in which a refractory accessory mineral with slow oxygen diffusion rate is modally minor to a mineral with a faster diffusion rate. This premise is demonstrated for high-grade metamorphism on the island of Naxos, Greece, where quartz-kyanite oxygen isotope thermometry from veins in high-grade metamorphic pelites gives temperatures of 635-690 °C. These temperatures are in excellent agreement with independent thermometry for the regional M2 peak metamorphic conditions and show that the vein minerals isotopically equilibrated at the peak of metamorphism. Quartz-sillimanite fractionations in the same veins give similar temperatures (680+/-35 °C) and suggest that the veins grew near to the kyanite-sillimanite boundary, corresponding to pressures of 6.5 to 7.5 kbar for temperatures of 635-685 °C. By contrast, quartz-kyanite and quartz-biotite pairs in the host rocks yield lower temperature estimates than the veins (590-600 and 350-550 °C, respectively). These lower apparent temperatures are also predicted from calculations of diffusional resetting in the polyphase host-rock system. The data demonstrate that bimineralic vein assemblages can be used as accurate thermometers in high-temperature rocks whereas retrograde exchange remains a major problem in many polymineralic rocks.

  10. Relationship of leaf oxygen and carbon isotopic composition with transpiration efficiency in the C4 grasses Setaria viridis and Setaria italica.

    Science.gov (United States)

    Ellsworth, Patrick Z; Ellsworth, Patrícia V; Cousins, Asaph B

    2017-06-15

    Leaf carbon and oxygen isotope ratios can potentially provide a time-integrated proxy for stomatal conductance (gs) and transpiration rate (E), and can be used to estimate transpiration efficiency (TE). In this study, we found significant relationships of bulk leaf carbon isotopic signature (δ13CBL) and bulk leaf oxygen enrichment above source water (Δ18OBL) with gas exchange and TE in the model C4 grasses Setaria viridis and S. italica. Leaf δ13C had strong relationships with E, gs, water use, biomass, and TE. Additionally, the consistent difference in δ13CBL between well-watered and water-limited plants suggests that δ13CBL is effective in separating C4 plants with different availability of water. Alternatively, the use of Δ18OBL as a proxy for E and TE in S. viridis and S. italica was problematic. First, the oxygen isotopic composition of source water, used to calculate leaf water enrichment (Δ18OLW), was variable with time and differed across water treatments. Second, water limitations changed leaf size and masked the relationship of Δ18OLW and Δ18OBL with E. Therefore, the data collected here suggest that δ13CBL but not Δ18OBL may be an effective proxy for TE in C4 grasses. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  11. 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

  12. The effect of different oxygen exchange layers on TaO x based RRAM devices

    Science.gov (United States)

    Alamgir, Zahiruddin; Holt, Joshua; Beckmann, Karsten; Cady, Nathaniel C.

    2018-01-01

    In this work, we investigated the effect of the oxygen exchange layer (OEL) on the resistive switching properties of TaO x based memory cells. It was found that the forming voltage, SET-RESET voltage, R off, R on and retention properties are strongly correlated with the oxygen scavenging ability of the OEL, and the resulting oxygen vacancy formation ability of this layer. Higher forming voltage was observed for OELs having lower electronegativity/lower Gibbs free energy for oxide formation, and devices fabricated with these OELs exhibited an increased memory window, when using similar SET-RESET voltage range.

  13. Salinity-dependent limitation of photosynthesis and oxygen exchange in microbial mats

    DEFF Research Database (Denmark)

    Garcia-Pichel, F.; Kühl, Michael; Nübel, U.

    1999-01-01

    was specific for each community and in accordance with optimal performance at the respective salinity of origin. This pattern was lost after long-term exposure to varying salinities when responses to salinity were found to approach a general pattern of decreasing photosynthesis and oxygen exchange capacity...... with increasing salinity. Exhaustive measurements of oxygen export in the light, oxygen consumption in the dark and gross photosynthesis indicated that a salinity-dependent limitation of all three parameters occurred. Maximal values for all three parameters decreased exponentially with increasing salinity...

  14. Stratigraphy on Oxygen and Carbon Isotope of Paciran Formation East Java

    International Nuclear Information System (INIS)

    Premonowati; R P Koesoemadinata; Harsono-Pringgoprawiro; Wahyoe-S-Hantoro

    2004-01-01

    Paleotemperature fluctuation in tropical zone (centennial and decad al scale) has been known. It's based on stable isotopic analysis from each of unconformity zones. Those boundaries have derived on reef units of shallows marine reef complex of Paciran Formation, Tuban area in Northeast Java Basin. From 25 samples have been choosen on undeformed calcite and analyzed by oxygen and carbon stable isotope. It used to validizing a sea level changes during the formation to Reef 1 to Reef 17 from Paciran formation with sea surface temperature (SST) since 4 Ma until now. On early forming of Reef 1 to Reef 3 (since 4 Ma - 2,88 Ma), sea level occurred marine flooding surface. Since the formation of reef 4 (2,59 Ma) to Reef 8 (1,4 Ma) occurred stagnant temperature and almost to warmer condition. Then, δ 18 O have arise up drastically to 5 0/00 and shows warmer condition to Reef 8 formation, in contrary, the sea level have been arised to Reef 10 formation (0,7 Ma). The temperature have been fluctuated between 0,5 o and 1 o C until the formation of Reef 17 (Early Holocene) and continued to Reef 17 formation at 2 o C based on the rapidity sampling of Po rites sp. Wholly, in centennial scale, since the formation of Reef 4 (2,59 Ma) to Reef 17 (1 Ma), the curve of oxygen stable isotope shows decrease or cooler condition. Those condition have conducted to sea level drop since the formation to Reef 7 and Reef 8. There are 4 periods of interglacial since the formation of Reef 4. The warmer condition indicated since the formation of Reef 9, Reef 11 and Reef 17. Recently, a curve of oxygen isotopes reveals warmer drastically or sea level have been arisen. (author)

  15. INVESTIGATION OF DISSOLVED SULPHATE IN VARIOUS GEOTHERMAL FIELDS OF SUMATRA USING OXYGEN AND SULPHUR ISOTOPES

    Directory of Open Access Journals (Sweden)

    E. Ristin Pujiindiyati

    2010-06-01

    Full Text Available There are at least 30 high temperature systems; eleven active volcanoes, five degassing volcanoes and one caldera volcano controlled by Sumatra Fault Zone over a length of 1700 km. To understand this geothermal field system, some information about geochemistry including isotope composition in its fluid is needed. Sulphur-34 and oxygen-18 isotopes in dissolved sulphate pair have been used to determine the origin of acidic fluid of sulphate and to evaluate the process involved. The fluids from eight hot springs, two fumaroles, four deep wells and crater have been collected in along Sumatra geothermal fields. Sulphur-34 (d 34S (SO4, 0/00 CDT and oxygen-18 (d 18O (SO4, 0/00 SMOW in sulphate is analyzed according to Robinson-Kusakabe and Rafter method, respectively. The d 34S (SO4 values from Sibayak wells are more enriched of 16.8 0/00 to 18.2 0/0 that may indicate the dissolution of anhydrite minerals or isotope partitioning in hydration of SO2. The d 34S (SO4 values from two fumaroles (Pusuk Bukit - North Sumatra and Rantau Dadap - South Sumatra are at depleted value of -0.150/00 and 1.80/00, those are close to d 34S from magmatic sulphur.  In general, the d 34S (SO4 of springs spread in a wide range of 5.250/00 to14.20/00 and show a mixing process between atmospheric sulphate and sulphate from deep wells. The d 18O (SO4 from wells exhibits depleted value around -3.60/00 suggesting that 87.5% of sulphate oxygen is derived from groundwater oxygen and 12.5% is derived from atmospheric molecular oxygen in sulphide oxidation reaction. In the other hand, hot springs (except Semurup, crater and fumaroles have enriched value of d 18O (SO4. These enriched values suggest that a higher percentage of atmospherically derived oxygen compared to those from the depth.   Keywords: isotope, geothermal, Sumatra

  16. Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

    Science.gov (United States)

    Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

    2018-03-01

    The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

  17. 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

  18. 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.)

  19. 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)

  20. 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

  1. Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

    Science.gov (United States)

    Michael, Dimitra-Ermioni; Dotsika, Elissavet

    2017-12-01

    Even though many isotopic studies have been conducted on ancient populations from Greece for the purpose of dietary reconstruction; mostly through carbon and nitrogen isotopic signals of bone collagen, less attention has been given to the utility of apatite signatures (oxygen and carbon) as dietary and palaeoenvironmental tools. Moreover, until recently the isotopic signal of tooth enamel for both the purposes of environmental and dietary reconstructions has been rarely assessed in ancient Greek societies. Therefore, the present study aims to provide with novel isotopic information regarding Edessa; a town in Northern Greece, during the Roman period. The current study primarily aims to explore the possible differentiation between the present climatic conditions in Edessa in relation to those occurring at the Roman period. Secondly, this study aims to reveal the significant utility of enamel isotopic signatures (carbon and oxygen) in palaeoenvironmental and palaeodietary studies regarding ancient human remains. The isotopic analyses have been conducted at the Stable Isotope and Radiocarbon Unit of INN, NCSR “Demokritos”. The population of Roman Edessa (2nd-4th c. AD) consists of 22 individuals, providing with 19 bone samples and 16 enamel ones. The mean enamel oxygen value is at -7.7 ±1.1 %0, the bone apatite mean oxygen value at -9.2 ±1.9 %0, and finally the mean carbon enamel value is at -11.7 ±1.2 %0. Oxygen values probably indicate that Edessa had a cooler climate during the Roman times in relation to present conditions, even though more research should be carried out in order to be more certain. In addition, the possible existence of non-local individuals has been revealed through the oxygen teeth enamel-bone apatite spacing. Finally, the carbon enamel signature has pointed out possible differentiations between the adult and the juvenile diet. Based on Edessa’s findings, the stated study strongly encourages the enamel oxygen and carbon isotopic signals

  2. 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

  3. USGS42 and USGS43: Human-hair stable hydrogen and oxygen isotopic reference materials and analytical methods for forensic science and implications for published measurement results

    Science.gov (United States)

    Coplen, T.B.; Qi, H.

    2012-01-01

    Because there are no internationally distributed stable hydrogen and oxygen isotopic reference materials of human hair, the U.S. Geological Survey (USGS) has prepared two such materials, USGS42 and USGS43. These reference materials span values commonly encountered in human hair stable isotope analysis and are isotopically homogeneous at sample sizes larger than 0.2 mg. USGS42 and USGS43 human-hair isotopic reference materials are intended for calibration of δ(2)H and δ(18)O measurements of unknown human hair by quantifying (1) drift with time, (2) mass-dependent isotopic fractionation, and (3) isotope-ratio-scale contraction. While they are intended for measurements of the stable isotopes of hydrogen and oxygen, they also are suitable for measurements of the stable isotopes of carbon, nitrogen, and sulfur in human and mammalian hair. Preliminary isotopic compositions of the non-exchangeable fractions of these materials are USGS42(Tibetan hair)δ(2)H(VSMOW-SLAP) = -78.5 ± 2.3‰ (n = 62) and δ(18)O(VSMOW-SLAP) = +8.56 ± 0.10‰ (n = 18) USGS42(Indian hair)δ(2)H(VSMOW-SLAP) = -50.3 ± 2.8‰ (n = 64) and δ(18)O(VSMOW-SLAP) = +14.11 ± 0.10‰ (n = 18). Using recommended analytical protocols presented herein for δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurements, the least squares fit regression of 11 human hair reference materials is δ(2)H(VSMOW-SLAP) = 6.085δ(2)O(VSMOW-SLAP) - 136.0‰ with an R-square value of 0.95. The δ(2)H difference between the calibrated results of human hair in this investigation and a commonly accepted human-hair relationship is a remarkable 34‰. It is critical that readers pay attention to the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) of isotopic reference materials in publications, and they need to adjust the δ(2)H(VSMOW-SLAP) and δ(18)O(VSMOW-SLAP) measurement results of human hair in previous publications, as needed, to ensure all results on are on the same scales.

  4. Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

    Directory of Open Access Journals (Sweden)

    Alberta Silvestri

    2017-01-01

    Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

  5. Quasi-free one nucleon knockout reactions on neutron-rich oxygen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Atar, Leyla; Aumann, Thomas [TU Darmstadt, Darmstadt (Germany); GSI, Darmstadt (Germany); Bertulani, Carlos [Texas A and M University-Commerce, Commerse (United States); Paschalis, Stefanos [TU Darmstadt, Darmstadt (Germany); Nociforo, Chiara [GSI, Darmstadt (Germany); Collaboration: R3B-Collaboration

    2015-07-01

    Recent experiments have shown a reduction of spectroscopic strengths to about 60-70% for stable nuclei. When going to drip lines this tendency is changing, loosely bound nucleons have spectroscopic strengths close unity while deeply bound nucleons have a large reduction of the strength. We aim to make a systematic study of spectroscopic factors (SF) of the Oxygen isotopes using quasi-free (p,2p) and (p,pn) knockout reactions in inverse kinematics. Quasi-free knockout reactions are a direct tool to study the occupancy and the location of valance and deeply bound single particle states. The Oxygen isotopes offer a large variation of separation energies which will allow us to obtain a qualitative and quantitative understanding of SF in a large variation of isospin asymmetry. For this we performed an experiment at the R3B-LAND setup at the GSI with secondary beams containing {sup 14-24}O. The {sup 16-18}O and {sup 21-23}O isotopes have been analyzed and the preliminary results will be presented. The results include the partial cross sections, gamma ray spectra of the residual fragments in coincidence, and the SF obtained via comparison with theory.

  6. Covariance of oxygen and hydrogen isotopic composition in plant water: Species effects

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, L.W.; DeNiro, M.J. (Univ. of California, Los Angeles (United States))

    1989-12-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leaf water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.

  7. In situ oxygen isotope compositions in olivines of different types of cosmic spherules: An assessment of relationships to chondritic particles

    Digital Repository Service at National Institute of Oceanography (India)

    Rudraswami, N.G.; ShyamPrasad, M.; Jones, R.H.; Nagashima, K.

    bearing cosmic spherules (Rudraswami et al., 2015b). In addition, some Mg-rich relict olivine grains are very 16O-rich, with 17O ranging from −21.9 to -18.7‰, similar to oxygen isotopic compositions observed in calcium aluminium rich inclusions (CAIs... isotope analyses of the olivine grains are provided in Appendix B and Table 1, respectively. 5    Four scoriaceous spherules namely, AAS62-61-P64, AAS62-9-P43, AAS62-9-P51 and AAS62-9- P54 were identified for oxygen isotope studies (Fig. 1a...

  8. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    Science.gov (United States)

    Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

    2012-01-01

    of ZnS by O 2, an estimated 8% of sulfate-oxygen was derived from O 2, which is enriched in 18O relative to water, thus resulting in a larger apparent ?? 18OSO 4-H 2O value of 9.5???. Based on the data presented we hypothesize that the similar ?? 18OSO 4-H 2O values of ~8??? from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite (SO3-) intermediate and H 2O. Our results indicate that the ??18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ?? 18OSO 4-H 2O values of ~8??? measured here are distinctly higher than ?? 18OSO 4-H 2O values of ~4??? previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured ?? 18OSO 4 values. ?? 2011 Elsevier Ltd.

  9. 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

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

    Science.gov (United States)

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

    1999-09-01

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

  11. Gas exchange efficiency of an oxygenator with integrated pulsatile displacement blood pump for neonatal patients.

    Science.gov (United States)

    Schlanstein, Peter C; Borchardt, Ralf; Mager, Ilona; Schmitz-Rode, Thomas; Steinseifer, Ulrich; Arens, Jutta

    2014-01-01

    Oxygenators have been used in neonatal extracorporeal membrane oxygenation (ECMO) since the 1970s. The need to develop a more effective oxygenator for this patient cohort exists due to their size and blood volume limitations. This study sought to validate the next design iteration of a novel oxygenator for neonatal ECMO with an integrated pulsatile displacement pump, thereby superseding an additional blood pump. Pulsating blood flow within the oxygenator is generated by synchronized active air flow expansion and contraction of integrated silicone pump tubes and hose pinching valves located at the oxygenator inlet and outlet. The current redesign improved upon previous prototypes by optimizing silicone pump tube distribution within the oxygenator fiber bundle; introduction of an oval shaped inner fiber bundle core, and housing; and a higher fiber packing density, all of which in combination reduced the priming volume by about 50% (50 to 27 mL and 41 to 20 mL, respectively). Gas exchange efficiency was tested for two new oxygenators manufactured with different fiber materials: one with coating and one with smaller pore size, both capable of long-term use (OXYPLUS® and CELGARD®). Results demonstrated that the oxygen transfer for both oxygenators was 5.3-24.7 mlO2/min for blood flow ranges of 100-500 mlblood/min. Carbon dioxide transfer for both oxygenators was 3.7-26.3 mlCO2/min for the same blood flow range. These preliminary results validated the oxygenator redesign by demonstrating an increase in packing density and thus in gas transfer, an increase in pumping capacity and a reduction in priming volume.

  12. Stable hydrogen, oxygen and sulfur isotopes composition in different tissues of cattle

    International Nuclear Information System (INIS)

    Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming

    2012-01-01

    In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

  13. Holocene climate variability revealed by oxygen isotope analysis of Sphagnum cellulose from Walton Moss, northern England

    Science.gov (United States)

    Daley, T. J.; Barber, K. E.; Street-Perrott, F. A.; Loader, N. J.; Marshall, J. D.; Crowley, S. F.; Fisher, E. H.

    2010-07-01

    Stable isotope analyses of Sphagnum alpha-cellulose, precipitation and bog water from three sites across northwestern Europe (Raheenmore, Ireland, Walton Moss, northern England and Dosenmoor, northern Germany) over a total period of 26 months were used to investigate the nature of the climatic signal recorded by Sphagnum moss. The δ18O values of modern alpha-cellulose tracked precipitation more closely than bog water, with a mean isotopic fractionation factor αcellulose-precipitation of 1.0274 ± 0.001 (1 σ) (≈27‰). Sub-samples of isolated Sphagnum alpha-cellulose were subsequently analysed from core WLM22, Walton Moss, northern England yielding a Sphagnum-specific isotope record spanning the last 4300 years. The palaeo-record, calibrated using the modern data, provides evidence for large amplitude variations in the estimated oxygen isotope composition of precipitation during the mid- to late Holocene. Estimates of palaeotemperature change derived from statistical relationships between modern surface air temperatures and δ18O precipitation values for the British Isles give unrealistically large variation in comparison to proxies from other archives. We conclude that use of such relationships to calibrate mid-latitude palaeo-data must be undertaken with caution. The δ18O record from Sphagnum cellulose was highly correlated with a palaeoecologically-derived index of bog surface wetness (BSW), suggesting a common climatic driver.

  14. Understanding the circulation of geothermal waters in the Tibetan Plateau using oxygen and hydrogen stable isotopes

    International Nuclear Information System (INIS)

    Tan, Hongbing; Zhang, Yanfei; Zhang, Wenjie; Kong, Na; Zhang, Qing; Huang, Jingzhong

    2014-01-01

    Highlights: • Unique geothermal resources in Tibetan Plateau were discussed. • Isotopes were used to trace circulation of geothermal water. • Magmatic water mixing dominates geothermal water evolution. - Abstract: With the uplift of the Tibetan Plateau, many of the world’s rarest and most unique geothermal fields have been developed. This study aims to systematically analyze the characteristics of the hydrogen and oxygen isotopic data of geothermal, river, and lake waters to understand the circulation of groundwater and to uncover the mechanism of geothermal formation in the Tibetan Plateau. Field observations and isotopic data show that geothermal water has higher temperatures and hydraulic pressures, as well as more depleted D and 18 O isotopic compositions than river and lake waters. Thus, neither lakes nor those larger river waters are the recharge source of geothermal water. Snow-melt water in high mountains can vertically infiltrate and deeply circulate along some stretching tensile active tectonic belts or sutures and recharge geothermal water. After deep circulation, cold surface water evolves into high-temperature thermal water and is then discharged as springs at the surface again in a low area, under high water-head difference and cold–hot water density difference. Therefore, the large-scale, high-temperature, high-hydraulic-pressure geothermal systems in the Tibetan Plateau are developed and maintained by rapid groundwater circulation and the heat source of upwelled residual magmatic water. Inevitably, the amount of geothermal water will increase if global warming accelerates the melting of glaciers in high mountains

  15. Hydrogen and oxygen stable isotope ratios of milk in the United States.

    Science.gov (United States)

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

    2010-02-24

    Models of hydrogen and oxygen incorporation in human tissues recognize the impact of geographic location on the isotopic composition of fluid intake, but inputs can include nonlocal beverages, such as milk. Milk and cow drinking water were collected from dairies, and commercially available milk was purchased from supermarkets and fast food restaurants. It was hypothesized that milk water delta(2)H and delta(18)O values record geographic location information. Correlations between milk water isotope ratios and purchase location tap water were significant. However, the amount of variation in milk delta(2)H and delta(18)O values explained by tap water was low, suggesting a single estimation of fluid input isotope ratios may not always be adequate in studies. The delta(2)H and delta(18)O values of paired milk and cow drinking water were related, suggesting potential for geographical origin assignment using stable isotope analysis. As an application example, milk water delta(18)O values were used to predict possible regions of origin for restaurant samples.

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

    International Nuclear Information System (INIS)

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

    2004-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-10-13

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

  18. 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.)

  19. Application of oxygen and hydrogen isotopes of waters in Tengchong hydrothermal systems of China

    International Nuclear Information System (INIS)

    Shen Minzi; Hou Fagao; Lin Ruifen; Ni Baoling

    1988-01-01

    This paper summarizes the results obtained for hydrothermal systems in Tengchong by using deuterium, oxygen-18 and tritium as natural tracers. On the basis of deuterium and oxygen-18 analyses of 69 thermal springs and some other meteoric, surface and underground water samples it has been confirmed that all geothermal waters are originally meteoric, but the δD of hot spring waters is often lighter than that of local surface and underground waters. It seems that the recharging water is from higher elevations and far from the thermal areas. The differences in oxygen-18 and deuterium contents between thermal springs and deep thermal waters have been calculated for single-stage steam separation from 276 deg. C to 96 deg. C. The oxygen isotope shift of deep thermal water produced by water-rock reactions is of 1.57 per mille and part of the observed oxygen isotope shift of thermal springs seems to have occurred due to subsurface boiling. The tritium content ( 18 O three subsurface processes would have been distinguished, they are subsurface boiling, mixing-subsurface boiling and subsurface boiling-mixing. The springs formed by subsurface boiling have tritium content of less than 5 TU. The tritium content of 5-10 TU is for springs formed by mixing-subsurface boiling and 10-20 TU is for subsurface boiling-mixing. The tritium content of geothermal water in Hot Sea, geothermal field seems higher than that of the Geysers U.S.A. and Wairakei N.Z. It would show that the circulation time of the thermal water in Hot Sea geothermal system is not so long, the reservoir is quite good with percolation and the recharging water is sufficiently enough. The most important applications of oxygen and hydrogen isotopes of water in geothermal study are in two ways, as tracers of water origins and as tracers of reservoir processes. This paper discussed these two aspects of Tengchong hydrothermal systems. 6 refs, 6 figs, 5 tabs

  20. Covariance of oxygen and hydrogen isotopic compositions in plant water: species effects

    International Nuclear Information System (INIS)

    Cooper, L.W.; DeNiro, M.J.

    1989-01-01

    Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species—specific factors on leaf water enrichment of D and 18 O have not been studied for different plants growing together. Accordingly, to learn whether leaf water enrichment patterns and processes for D and 18 O are different for individual species growing under the same environmental conditions we tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show higher slopes (m in the leaf water equation °D = m ° 18 O + b) than in C 3 plants. We determined the relationships between the stable hydrogen (°D) and oxygen (° 18 O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. Slopes (m in the above leaf water equation) ranged from 1.50 to 3.21, compared to °8 for meteoric water, but differences in slope could not be attributed to carboxylation pathway (CAM vs. C 3 ) nor climate (coastal California vs. Sonoran Desert). Higher slopes were correlated with greater overall ranges of leaf water enrichment of D and 18 O. Water in plants with higher slopes also differed most from unaltered meteoric water. Leaf water isotope ratios in plants with lower slopes were better correlated with temperature and humidity. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes

  1. Growth patterns of an intertidal gastropod as revealed by oxygen isotope analysis

    Science.gov (United States)

    Bean, J. R.; Hill, T. M.; Guerra, C.

    2007-12-01

    The size and morphology of mollusk shells are affected by environmental conditions. As a result, it is difficult to assess growth rate, population age structure, shell morphologies associated with ontogenetic stages, and to compare life history patterns across various environments. Oxygen isotope analysis is a useful tool for estimating minimum ages and growth rates of calcium carbonate secreting organisms. Calcite shell material from members of two northern California populations of the intertidal muricid gastropod Acanthinucella spirata was sampled for isotopic analysis. Individual shells were sampled from apex to margin, thus providing a sequential record of juvenile and adult growth. A. spirata were collected from a sheltered habitat in Tomales Bay and from an exposed reef in Bolinas. Abiotic factors, such as temperature, wave exposure, and substrate consistency, and biotic composition differ significantly between these sites, possibly resulting in local adaptations and variation in life history and growth patterns. Shell morphology of A. spirata changes with age as internal shell margin thickenings of denticle rows associated with external growth bands are irregularly accreted. It is not known when, either seasonally and/or ontogentically, these thickenings and bands form or whether inter or intra-populational variation exists. Preliminary results demonstrate the seasonal oxygen isotopic variability present at the two coastal sites, indicating 5-6 degC changes from winter to summertime temperatures; these data are consistent with local intertidal temperature records. Analysis of the seasonal patterns indicate that: 1) differences in growth rate and seasonal growth patterns at different ontogenetic stages within populations, and 2) differences in growth patterns and possibly age structure between the two A. spirata populations. These findings indicate that isotopic analyses, in addition to field observations and morphological measurements, are necessary to

  2. 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

  3. Oxygen isotope regional pattern in granitoids from the Cachoeirinha Belt, northeast Brazil

    International Nuclear Information System (INIS)

    Sial, A.N.

    1984-01-01

    Four groups of granitoids are present within the Cachoeirinha belt and in the adjacent migmatitic basement, between 37 0 and 40 0 W long. and 7 0 and 8 0 15' S lat., States of Pernambuco and Paraiba: a) K 2 O - enriched, very porphyritic; b) a calc-alkalic slightly porphyritic group; c) group with trondjemitic affinities; and d) peralkalic group. Petrology and oxygen isotope geochemistry for over 100 samples from these groups were studied. Almost all plutons for which 5 or more samples were analyzed, exhibit a total range of gamma 18 O less than 2% o. A broad range of mean oxygen isotope composition is observed, varying from 6.93 to 12.79% o. There is a systematic regional trend in which the calc-alkalic granitoids (conceicao-type) found within the Cachoeirinha space are the most 18 O - enriched rocks (10.6 to 12.9% o) while the lowest mean gamma 18 O values (4.5 to 9.7% o) are found in the K 2 O - enriched granitoids (Itaporanga-type). Intermediate gamma 18 O values were recorded in the bodies with trondhjemitic affinities (8.9 to 9.8% o) which intruded metasediments of the Salgueiro Group and in the peralkalic granitoids of Catingueira (8.1 to 9.8% o) which intruded Cachoeirinha metamorphics. Among the potassic granitoids, mean gamma 18 O increases from Bodoco to Itaporanga (from west to east). As a whole, the W.R. gamma 18 O of these plutons correlate with the type of grade of metamorphism of the host rocks and, therefore, with the tectonic framework, increasing from those which intruded the gneiss-migmatites to those which intruded the low-grade metamorphics of the Cachoeirinha Group. The possible origin of each rock group is discussed in light of the oxygen isotope geochemistry. (Author) [pt

  4. Oxygen Isotopes in Intra-Back Arc Basalts from the Andean Southern Volcanic Zone

    Science.gov (United States)

    Parks, B. H.; Wang, Z.; Saal, A. E.; Frey, F. A.; Blusztajn, J.

    2013-12-01

    The chemical compositions of volcanic rocks from the Andean Southern Volcanic Zone (SVZ) reflect complex and dynamic interactions among the subducting oceanic lithosphere, the mantle wedge, and the overlying continental crust. Oxygen isotope ratios of olivine phenocrysts can be a useful means to identifying their relative contributions to the arc magmatism. In this study, we report high-precision oxygen-isotope ratios of olivine phenocrysts in a set of intra-back arc basalts from the SVZ. The samples were collected from monogenetic cinder cones east of the volcanic front (35-39 degrees S), and have been geochemically well-characterized with major and trace element contents, and Sr-Nd-Pb isotope compositions. Compared to lavas from the volcanic front, these intra-back arc lavas have similar radiogenic isotope, and a more alkalic and primitive (higher MgO content) chemical composition. We determined the oxygen-isotope ratios using the CO2-laser-fluorination method set up at the Department of Geology and Geophysics, Yale University following the techniques reported in Wang et al (2011). The samples were analyzed with standards of Gore Mountain Garnet (5.77×0.12‰ 1σ; Valley et al., 1995) and Kilbourne Hole Olivine (5.23×0.07‰ 1σ; Sharp, 1990) in order to account for minor changes in the vacuum line during analyses. The obtained δ18OSMOW values of olivine phenocrysts from the intra-back arc basalts vary from 4.98×0.01 to 5.34×0.01‰. This range, surprisingly, is similar to the δ18O values of olivines from mantle peridotites (5.2×0.2‰). Preliminary results indicate significant correlations of 87Sr/86Sr, 143Nd/144Nd and trace element ratios of the basaltic matrix with the δ18O values of olivine phenocrysts, indicating at least three components involved in the formation of the arc volcanism. By comparing the δ18O with the variations of major and trace element contents (e.g., MgO, TiO2 and Ni), and trace element ratios (e.g. Ba/Nb), we evaluate the effects

  5. Oxygen isotope ratios in the shell of Mytilus edulis: Archives of glacier meltwater in Greenland?

    DEFF Research Database (Denmark)

    Versteegh, E.A.A.; Blicher, M.E.; Mortensen, J.

    2012-01-01

    Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models...... these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and archaeological shell middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We...

  6. Oxygen 18 isotopic analysis of sub-glacial concentrations of the Laurentide Ice Sheet

    Energy Technology Data Exchange (ETDEWEB)

    Hillaire-Marcel, C [Quebec Univ., Montreal (Canada); Cailleux, A [Observatoire de Paris, Section de Meudon, 92 (France); Soucy, J

    1979-07-01

    Calcareous concretions occuring on Grenvillian gneiss have been discovered north of Hull, Quebec. Their structure and isotopic composition (delta/sub PDB//sup 18/O approximately equal to -26%; delta/sub PDB//sup 13/C approximately equal to 0%; /sup 14/C age > 35,000 BP) indicate subglacial conditions of precipitation. It is concluded that they were deposited at the base of the Laurentide ice sheet. Assuming equilibrium conditions with the subglacial film of water during precipitation of calcite, it is possible to define a -27.5 to -31.8% (vs. 'standard mean ocean water' (SMOW)) range for the oxygen-18 content of ice.

  7. 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/.

  8. 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.

  9. The oxygen isotopic composition of phytolith assemblages from tropical rainforest soil tops (Queensland, Australia: validation of a new paleoenvironmental tool

    Directory of Open Access Journals (Sweden)

    A. Alexandre

    2012-02-01

    Full Text Available Phytoliths are micrometric particles of amorphous silica that form inside or between the cells of higher plant tissues throughout the life of a plant. With plant decay, phytoliths are either incorporated into soils or exported to sediments via regional watersheds. Phytolith morphological assemblages are increasingly used as proxy of grassland diversity and tree cover density in inter-tropical areas. Here, we investigate whether, along altitudinal gradients in northeast Queensland (Australia, changes in the δ18O signature of soil top phytolith assemblages reflect changes in mean annual temperature (MAT and in the oxygen isotopic composition of precipitation (δ18Oprecipitation, as predicted by equilibrium temperature coefficients previously published for silica. Oxygen isotopic analyses were performed on 16 phytolith samples, after controlled isotopic exchange (CIE, using the IR Laser-Heating Fluorination Technique. Long-term mean annual precipitation (MAP and MAT values at the sampled sites were calculated by the ANUCLIM software. δ18Oprecipitation estimates were calculated using the Bowen and Wilkinson (2002 model, slightly modified. An empirical temperature-dependant relationship was obtained: δ18Owood phytolith-precipitation (‰ vs. VSMOW = −0.4 (±0.2 t (°C + 46 (±3 (R2 = 0.4, p < 0.05; n = 12. Despite the various unknowns introduced when estimating δ18Oprecipitation values and the large uncertainties on δ18Owood phytolith values, the temperature coefficient (−0.4 ± 0.2‰ °C−1 is in the range of values previously obtained for natural quartz, fresh and sedimentary diatoms and harvested grass phytoliths (from −0.2 to −0.5‰ °C−1. The consistency supports the reliability of δ18Owood phytolith signatures for recording

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

    International Nuclear Information System (INIS)

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

    1985-01-01

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

  11. Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign

    Directory of Open Access Journals (Sweden)

    J. Savarino

    2016-03-01

    Full Text Available Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO2 = NOx. The unique and distinctive 17O excess (Δ17O = δ17O − 0.52 × δ18O of ozone, which is transferred to NOx via oxidation, is a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O excess within the NOx cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NOx, O3, OH, HO2, RO2, etc. and direct observations of the transferrable Δ17O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO2 pathway and using concurrent measurements of OH and NO2, we calculated a Δ17O signature for nitrate on the order of (21–22 ± 3 ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ17O(NO3− values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded.

  12. Kinetics of the high temperature oxygen exchange reaction on {sup 238}PuO{sub 2} powder

    Energy Technology Data Exchange (ETDEWEB)

    Whiting, Christofer E., E-mail: chris.whiting@udri.udayton.edu [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States); Du, Miting; Felker, L. Kevin; Wham, Robert M. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Barklay, Chadwick D.; Kramer, Daniel P. [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States)

    2015-12-15

    Oxygen exchange reactions performed on PuO{sub 2} suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO{sub 2}. Previous CeO{sub 2} surrogate studies exhibit similar behavior, confirming that CeO{sub 2} is a good qualitative surrogate for PuO{sub 2}, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO{sub 2} oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO{sub 2} Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  13. 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)

  14. 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.

  15. Electrolytic separation factors for oxygen isotopes in light and heavy water solutions

    International Nuclear Information System (INIS)

    Gulens, J.; Olmstead, W.J.; Longhurst, T.H.; Gale, K.L.; Rolston, J.H.

    1987-01-01

    The electrolytic separation factor, α, has been measured for /sup 17/O and /sup 18/O at Pt and Ni anodes in both light and heavy water solutions of 6M KOH as a function of current density. For oxygen-17, isotopic separation effects were not observed, within the experimental uncertainty of +-2%, under all conditions studied. For oxygen-18, there is a small difference of 2% in α values between Pt and Ni in both light and heavy water solutions, but there is no significant difference in α values between light and heavy water solutions. In light waters solutions, the separation factor at Pt is small, α(/sup 18/O) ≤ 1.02 for i ≥ 0.1 A/cm/sub 2/. This value agrees reasonably well with theoretical estimates

  16. 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)

  17. Controlling exchange bias in Co-CoOx nanoparticles by oxygen content

    International Nuclear Information System (INIS)

    Kovylina, Miroslavna; Muro, Montserrat GarcIa del; Konstantinovic, Zorica; Iglesias, Oscar; Labarta, AmIlcar; Batlle, Xavier; Varela, Manuel

    2009-01-01

    We report on the occurrence of exchange bias on laser-ablated granular thin films composed of Co nanoparticles embedded in an amorphous zirconia matrix. The deposition method allows one to control the degree of oxidation of the Co particles by tuning the oxygen pressure at the vacuum chamber (from 2 x 10 -5 to 10 -1 mbar). The nature of the nanoparticles embedded in the nonmagnetic matrix is monitored from metallic, ferromagnetic (FM) Co to antiferromagnetic (AFM) CoO x , with a FM/AFM intermediate regime for which the percentage of the AFM phase can be increased at the expense of the FM phase, leading to the occurrence of exchange bias in particles of about 2 nm in size. For an oxygen pressure of about 10 -3 mbar the ratio between the FM and AFM phases is optimum with an exchange bias field of about 900 Oe at 1.8 K. The mutual exchange coupling between the AFM and FM is also at the origin of the induced exchange anisotropy on the FM leading to high irreversible hysteresis loops, and the blocking of the AFM clusters due to proximity to the FM phase.

  18. Oxygen isotope study of the Long Valley magma system, California: isotope thermometry and convection in large silicic magma bodies

    Science.gov (United States)

    Bindeman, Ilya; Valley, John

    2002-07-01

    Products of voluminous pyroclastic eruptions with eruptive draw-down of several kilometers provide a snap-shot view of batholith-scale magma chambers, and quench pre-eruptive isotopic fractionations (i.e., temperatures) between minerals. We report analyses of oxygen isotope ratio in individual quartz phenocrysts and concentrates of magnetite, pyroxene, and zircon from individual pumice clasts of ignimbrite and fall units of caldera-forming 0.76 Ma Bishop Tuff (BT), pre-caldera Glass Mountain (2.1-0.78 Ma), and post-caldera rhyolites (0.65-0.04 Ma) to characterize the long-lived, batholith-scale magma chamber beneath Long Valley Caldera in California. Values of δ18O show a subtle 1‰ decrease from the oldest Glass Mountain lavas to the youngest post-caldera rhyolites. Older Glass Mountain lavas exhibit larger ( 1‰) variability of δ18O(quartz). The youngest domes of Glass Mountain are similar to BT in δ18O(quartz) values and reflect convective homogenization during formation of BT magma chamber surrounded by extremely heterogeneous country rocks (ranging from 2 to +29‰). Oxygen isotope thermometry of BT confirms a temperature gradient between "Late" (815 °C) and "Early" (715 °C) BT. The δ18O(quartz) values of "Early" and "Late" BT are +8.33 and 8.21‰, consistent with a constant δ18O(melt)=7.8+/-0.1‰ and 100 °C temperature difference. Zircon-melt saturation equilibria gives a similar temperature range. Values of δ18O(quartz) for different stratigraphic units of BT, and in pumice clasts ranging in pre-eruptive depths from 6 to 11 km (based on melt inclusions), and document vertical and lateral homogeneity of δ18O(melt). Worldwide, five other large-volume rhyolites, Lava Creek, Lower Bandelier, Fish Canyon, Cerro Galan, and Toba, exhibit equal δ18O(melt) values of earlier and later erupted portions in each of the these climactic caldera-forming eruptions. We interpret the large-scale δ18O homogeneity of BT and other large magma chambers as evidence

  19. Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel; Rao, Reshma R.; Frydendal, Rasmus; Qiao, Liang; Wang, Xiao Renshaw; Halck, Niels Bendtsen; Rossmeisl, Jan; Hansen, Heine A.; Vegge, Tejs; Stephens, Ifan E. L.; Koper, Marc T. M.; Shao-Horn, Yang

    2017-03-15

    RuO2 catalysts exhibit record activities towards the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO2 OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online 3 electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER on crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by DFT, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO2 nanoparticles by facet engineering.

  20. 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

  1. Thromboxane plays a role in postprandial jejunal oxygen uptake and capillary exchange.

    Science.gov (United States)

    Alemayehu, A; Chou, C C

    1990-09-01

    The effects of a thromboxane A2 (TxA2)-endoperoxide receptor antagonist, SQ 29548, on jejunal blood flow, oxygen uptake, and capillary filtration coefficient (Kfc) were determined in anesthetized dogs under resting conditions and during the presence of predigested food in the jejunal lumen in three series of experiments. In series 1, 2.0 micrograms intra-arterial administration of SQ 29548 was found to abolish completely the vasoconstrictor action of graded doses (0.05-2.0 micrograms) of intra-arterial injection of a TxA2-endoperoxide analogue, U44069. SQ 29548 (2.0 micrograms ia) per se did not significantly alter resting jejunal blood flow, oxygen uptake, capillary pressure, or Kfc. Before SQ 29548, placement of food plus bile into the jejunal lumen increased blood flow +42 +/- 9%, oxygen uptake +28 +/- 7%, and Kfc +24 +/- 6%. After SQ 29548, the food placement increased blood flow +37 +/- 8%, oxygen uptake +52 +/- 11%, and Kfc +63 +/- 20%. The food-induced increases in oxygen uptake and Kfc after SQ 29548 were significantly greater than those induced before the blocking of TxA2-endoperoxide receptors by SQ 29548. Our study indicates that endogenous thromboxane does not play a role in regulating jejunal blood flow, capillary filtration, and oxygen uptake under resting conditions. However, it plays a role in limiting the food-induced increases in jejunal oxygen uptake and capillary exchange capacity without influencing the food-induced hyperemia.

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

    Science.gov (United States)

    Juillet-Leclerc, A.; Reynaud, S.

    2009-04-01

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

  3. 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)

  4. 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)

  5. 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)

  6. 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.)

  7. 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

  8. Growth of the European abalone ( Haliotis tuberculata L.) in situ: Seasonality and ageing using stable oxygen isotopes

    Science.gov (United States)

    Roussel, Sabine; Huchette, Sylvain; Clavier, Jacques; Chauvaud, Laurent

    2011-02-01

    The ormer, Haliotis tuberculata is the only European abalone species commercially exploited. The determination of growth and age in the wild is an important tool for fisheries and aquaculture management. However, the ageing technique used in the past in the field is unreliable. The stable oxygen isotope composition ( 18O/ 16O) of the shell depends on the temperature and oxygen isotope composition of the ambient sea water. The stable oxygen isotope technique, developed to study paleoclimatological changes in shellfish, was applied to three H. tuberculata specimens collected in north-west Brittany. For the specimens collected, the oxygen isotope ratios of the shell reflected the seasonal cycle in the temperature. From winter-to-winter cycles, estimates of the age and the annual growth increment, ranging from 13 to 55 mm per year were obtained. This study shows that stable oxygen isotopes can be a reliable tool for ageing and growth studies of this abalone species in the wild, and for validating other estimates.

  9. Design of a formaldehyde photodissociation process for carbon and oxygen isotope separation

    International Nuclear Information System (INIS)

    Stern, R.C.; Scheibner, K.F.

    1993-01-01

    The current shortage of 18 O has revived interest in using one step UV photodissociation of formaldehyde to enrich 13 C, 17 O and 18 O. The frequency doubled output of the copper laser pumped dye laser system currently in operation at LLNL can be used to drive this dissociation. The authors use a simple kinetics model and their experience with Atomic Vapor Laser Isotope Separation (AVLIS) process design to examine the relative merits of different designs for a formaldehyde photodissociation process. Given values for the molecular photoabsorption cross section, partition function, spectroscopic selectivity, collisional exchange and quenching cross sections (all as parameters), they perform a partial optimization in the space of illuminated area, formaldehyde pressure in each stage, and formaldehyde residence time in each stage. They examine the effect of cascade design (heads and tails staging) on molecule and photon utilization for each of the three isotope separation missions, and look in one case at the system's response to different ratios of laser to formaldehyde costs. Finally, they examine the relative cost of enrichment as a function of isotope and product assay. Emphasis is as much on the process design methodology, which is general, as on the specific application to formaldehyde

  10. 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

  11. 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.

  12. Devonian climate and reef evolution: Insights from oxygen isotopes in apatite

    Science.gov (United States)

    Joachimski, M. M.; Breisig, S.; Buggisch, W.; Talent, J. A.; Mawson, R.; Gereke, M.; Morrow, J. R.; Day, J.; Weddige, K.

    2009-07-01

    Conodonts, microfossils composed of carbonate-fluor apatite, are abundant in Palaeozoic-Triassic sediments and have a high potential to preserve primary oxygen isotope signals. In order to reconstruct the palaeotemperature history of the Devonian, the oxygen isotope composition of apatite phosphate was measured on 639 conodont samples from sequences in Europe, North America and Australia. The Early Devonian (Lochkovian; 416-411 Myr) was characterized by warm tropical temperatures of around 30 °C. A cooling trend started in the Pragian (410 Myr) with intermediate temperatures around 23 to 25 °C reconstructed for the Middle Devonian (397-385 Myr). During the Frasnian (383-375 Myr), temperatures increased again with temperatures to 30 °C calculated for the Frasnian-Famennian transition (375 Myr). During the Famennian (375-359 Myr), surface water temperatures slightly decreased. Reconstructed Devonian palaeotemperatures do not support earlier views suggesting the Middle Devonian was a supergreenhouse interval, an interpretation based partly on the development of extensive tropical coral-stromatoporoid communities during the Middle Devonian. Instead, the Devonian palaeotemperature record suggests that Middle Devonian coral-stromatoporoid reefs flourished during cooler time intervals whereas microbial reefs dominated during the warm to very warm Early and Late Devonian.

  13. Temperature measurements of Transdanubian Mesozoic rocks by the oxygen isotope method

    International Nuclear Information System (INIS)

    Cornides, I.; Csaszar, G.; Haas, J.; Jochane Edelenyi, E.

    1979-01-01

    Subjected to paleotemperature measurements with the use of oxygen and carbon isotopes were Upper Triassic, Jurassic and Cretaceous sedimentary rocks and their fossils from the Transdanubian Central Mountains, the Mecsek and the Villany Mts. In determining formation temperature, an important parameter of the environment of formation, the authors relied on the fact that the oxygen isotope composition of calcium carbonate precipitating from its aqueous solution deviates, in dependence on the temperature of the solution concerned, from that of the water. Consequently, the temperature of the water of the one-time seas must have been recorded by the 18 O/ 16 O ratio in the calcite of fossils or sediments. The results reported indicate smaller changes in temperature as compared to international results. In the Jurassic the values of temperature remain consistently below those quoted for Swiss and French territories, being around the values reported from/sroe/thern Germany. These u curves have their maxima in the Toarcian, Aalenian, sediments for which unfortunately no Hungarian results are available. The few results of Cretaceous belemnites are values higher than their international counterparts. The high temperature value obtained for the Albian correlates very well with the formation of rocks known from this stratigraphic stage (red clays, bauxites). (A.L.)

  14. Carbon 13 and oxygen 18 isotope record of the early eocene nammal formation, salt range, pakistan

    International Nuclear Information System (INIS)

    Ghazi, S.; Sajid, Z.

    2014-01-01

    The Nammal Formation is the lowermost unit of the Early Eocene succession in the Salt Range, Pakistan. It is well exposed throughout the Salt Range. The Nammal Formation having 30 to 35 meters thickness is predominantly composed of nodular limestone interbedded with marl and shale. The present study was focussed on stable carbon 13 and oxygen 18 isotopic analysis based on data from two stratigraphically important sections. The samples from the Nilawahan section provided with the delta 13C values varied between 1.34 to -1.56 (VPDB) and values of delta 18O fluctuated between -4.47 to -6.59 (VPDB). Likewise the sample analysis of BadshahPur section exhibited that the delta 13C values changes from 1.09 to -1.65 (VPDB) and delta 18O values range from -4.17 to -6.85 (VPDB). The isotopic records of carbon 13 and oxygen 18 indicated the shallow marine deposition of the Nammal Formation under tropical conditions. It highlighted the palaeo climatic and diagenetic conditions of the Nammal Formation at the time of deposition in the Salt Range region. (author)

  15. Hydrogen and oxygen isotope constraints on hydrothermal alteration of the Trinity peridotite, Klamath Mountains, California

    Science.gov (United States)

    Liakhovitch, V.; Quick, J.E.; Gregory, R.T.

    2005-01-01

    The Trinity peridotite represents a rare opportunity to examine a relatively fertile plagioclase peridotite that was exhumed and later subjected to intrusive events in a seafloor environment, followed by its emplacement and incorporation into a continent. Over 250 stable isotopic determinations on whole rocks and minerals elucidate the hydrothermal evolution of the Trinity complex. All three serpentine polymorphs are present in the Trinity peridotite; these separate on the basis of their ??D values: antigorite, -46 serpentinization, or overprinting of earlier low-temperature seafloor serpentinization. Regionally, contours of ??D values exhibit bull's-eye patterns associated with the gabbroic plutons, with ??D maxima coinciding with the blackwall alteration at the margins on the plutons. In contrast to the hydrogen isotope behavior, oxygen isotope values of the three polymorphs are indistinguishable, spanning the range 5.3 history: (1) lithospheric emplacement and cooling of the peridotite in an oceanic environment ??? 472 Ma; (2) intrusion of gabbroic plutons into cold peridotite in an arc environment between 435 and 404 Ma; and finally (3) intrusion of felsic plutons between 171 and 127 Ma, long after the peridotite was incorporated into the continental crust. Copyright ?? 2005 by V. H. Winston & Son, Inc. All rights reserved.

  16. Characterizing the oxygen isotopic composition of phosphate sources to aquatic ecosystems

    Science.gov (United States)

    Young, M.B.; McLaughlin, K.; Kendall, C.; Stringfellow, W.; Rollog, M.; Elsbury, K.; Donald, E.; Paytan, A.

    2009-01-01

    The oxygen isotopic composition of dissolved inorganic phosphate (δ18Op) in many aquatic ecosystems is not in isotopic equilibrium with ambient water and, therefore, may reflect the source δ18Op. Identification of phosphate sources to water bodies is critical for designing best management practices for phosphate load reduction to control eutrophication. In order for δ18O p to be a useful tool for source tracking, the δ18Op of phosphate sources must be distinguishable from one another; however, the δ18Op of potential sources has not been well characterized. We measured the δ18O p of a variety of known phosphate sources, including fertilizers, semiprocessed phosphorite ore, particulate aerosols, detergents, leachates of vegetation, soil, animal feces, and wastewater treatment plant effluent. We found a considerable range of δ18Op values (from +8.4 to +24.9‰) for the various sources, and statistically significant differences were found between several of the source types. δ18Op measured in three different fresh water systems was generally not in equilibrium with ambient water. Although there is overlap in δ18Op values among the groups of samples, our results indicate that some sources are isotopically distinct and δ18Op can be used for identifying phosphate sources to aquatic systems.

  17. Separation of isotopes of nitrogen and oxygen by low temperature distillation of nitrogen oxide

    Energy Technology Data Exchange (ETDEWEB)

    Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato

    1987-02-01

    In general, the distillation parameters, such as the number of theoretical plate (NTP) and the height equivalent to a theoretical plate (HETP), can be obtained from the operation at the steady state. However, it is time-consuming to achieve the steady state especially in the case of isotope separation. In this paper, with the purpose of simultaneous separation of isotopes of nitrogen and oxygen by NO distillation, we tried to determine the distillation parameters by an analytical method through the transient-state operation. It was confirmed that the results from the analysis were in good agreement with those observed for the operation at the steady state. Enrichment of the isotopes was carried out using a distillation column with a height of 1 m and inside diameter of 12 mm. The dependence of HETP on liquid flow rate was measured by the proposed method. The obtained HETP values were from 2 to 4 cm. The operation time of about 5 h was found to be long enough to determine the distillation parameters.

  18. Separation of isotopes of nitrogen and oxygen by low temperature distillation of nitrogen oxide

    International Nuclear Information System (INIS)

    Isomura, Shohei; Tonooka, Yasuhiko; Kaetsu, Hayato

    1987-01-01

    In general, the distillation parameters, such as the number of theoretical plate (NTP) and the height equivalent to a theoretical plate (HETP), can be obtained from the operation at the steady state. However, it is time-consuming to achieve the steady state especially in the case of isotope separation. In this paper, with the purpose of simultaneous separation of isotopes of nitrogen and oxygen by NO distillation, we tried to determine the distillation parameters by an analytical method through the transient-state operation. It was confirmed that the results from the analysis were in good agreement with those observed for the operation at the steady state. Enrichment of the isotopes was carried out using a distillation column with a height of 1 m and inside diameter of 12 mm. The dependence of HETP on liquid flow rate was measured by the proposed method. The obtained HETP values were from 2 to 4 cm. The operation time of about 5 h was found to be long enough to determine the distillation parameters. (author)

  19. Do oxygen stable isotopes track precipitation moisture source in vascular plant dominated peatlands?

    Science.gov (United States)

    Charman, D.; Amesbury, M. J.; Newnham, R.; Loader, N.; Goodrich, J. P.; Gallego-Sala, A. V.; Royles, J.; Keller, E. D.; Baisden, W. T.

    2014-12-01

    Variations in the isotopic composition of precipitation are determined by fractionation processes which occur during temperature and humidity dependent phase changes associated with evaporation and condensation. Oxygen stable isotope ratios have therefore been frequently used as a source of palaeoclimate data from a variety of proxy archives. Exploitation of this record from ombrotrophic peatlands, where the source water used in cellulose synthesis is derived solely from precipitation, has been mostly limited to Northern Hemisphere Sphagnum-dominated bogs, with limited application in the Southern Hemisphere (SH) or in peatlands dominated by vascular plants. Throughout New Zealand (NZ), the preserved root matrix of the restionaceous wire rush (Empodisma spp.) forms deep peat deposits. NZ provides an ideal location to undertake empirical research into oxygen isotope fractionation in vascular peatlands because sites are ideally suited to single taxon analysis, preserve potentially high resolution full Holocene palaeoclimate records and are situated in the climatically sensitive SH mid-latitudes. Crucially, large gradients exist in the mean isotopic composition of precipitation across NZ, caused primarily by the relative influence of different climate modes. We test the capacity for δ18O analysis of Empodisma alpha cellulose from ombrotrophic restiad peatlands in NZ to provide a methodology for developing palaeoclimate records. We took surface plant, water and precipitation samples over spatial (six sites spanning >10° latitude) and temporal (monthly measurements over one year) gradients. We found a strong link between the isotopic compositions of surface root water, the most likely source water for plant growth, and precipitation in both datasets. Back-trajectory modelling of precipitation moisture source for rain days prior to sampling showed clear seasonality in the temporal data that was reflected in surface root water. The link between source water and plant

  20. Simulated oxygen isotopes in cave drip water and speleothem calcite in European caves

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth

    2012-11-01

    Full Text Available Interpreting stable oxygen isotope18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

  1. Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime.

    Science.gov (United States)

    Fielitz, Peter; Borchardt, Günter

    2016-08-10

    In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.

  2. Untangling surface oxygen exchange effects in YBa2Cu3O6+x thin films by electrical conductivity relaxation.

    Science.gov (United States)

    Cayado, P; Sánchez-Valdés, C F; Stangl, A; Coll, M; Roura, P; Palau, A; Puig, T; Obradors, X

    2017-05-31

    The kinetics of oxygen incorporation (in-diffusion process) and excorporation (out-diffusion process), in YBa 2 Cu 3 O 6+x (YBCO) epitaxial thin films prepared using the chemical solution deposition (CSD) methodology by the trifluoroacetate route, was investigated by electrical conductivity relaxation measurements. We show that the oxygenation kinetics of YBCO films is limited by the surface exchange process of oxygen molecules prior to bulk diffusion into the films. The analysis of the temperature and oxygen partial pressure influence on the oxygenation kinetics has drawn a consistent picture of the oxygen surface exchange process enabling us to define the most likely rate determining step. We have also established a strategy to accelerate the oxygenation kinetics at low temperatures based on the catalytic influence of Ag coatings thus allowing us to decrease the oxygenation temperature in the YBCO thin films.

  3. Modeling Approach for Oxygen Exchange in the Human Lung under Hypobaric Conditions

    Science.gov (United States)

    2001-06-01

    Operational Medical Issues in Hypo-and Hyperbaric Conditions [les Questions medicales a caractere oprationel liees aux conditions hypobares ou hyperbares ] To...under Hypobaric Conditions DISTRIBUTION: Approved for public release, distribution unlimited This paper is part of the following report: TITLE...Approach for Oxygen Exchange in the Human Lung under Hypobaric Conditions Ing J.P.F. Lindhout*, Drs M. van de Graaff*, Ir Drs R.C. van de Graaff*, Dr

  4. 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.

  5. 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)

  6. 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.

  7. 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.)

  8. 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)

  9. Environmental isotopes in New Zealand hydrology ; 4. Oxygen isotope variations in subsurface waters of the Waimea Plains, Nelson

    International Nuclear Information System (INIS)

    Stewart, M.K.; Dicker, M.J.I.; Johnston, M.R.

    1981-01-01

    Oxygen isotope measurements of ground and surface waters of the Waimea Plains, Nelson, have been used to identify sources of water in aquifers beneath the plains. Major rivers flowing onto the plains are from higher-altitude catchments (maximum altitude 2000 m) and have delta O 18 approximately equal to -7.2%, whereas rainfall on the plains and adjacent low-altitude catchment streams have delta O 18 approximately equal to -6.2%. The delta O 18 measurements indicate that the 3 major aquifer units, the ''Lower Confined Aquifers'' and the ''Upper Confined Aquifers'' in the Hope Gravel (Late Pleistocene) and the ''Unconfined Aquifers'' in the Appleby Gravel (Holocene) are recharged from different sources. The ''Lower Confined Aquifers'' probably receive slow recharge in the south near Brightwater. The ''Upper Confined Aquifers'' are recharged, in the south, from the Wairoa River and locally in the north are connected with the unconfined aquifers. The ''Unconfined Aquifers'' are recharged from the Waimea River and, away from the river, from rainfall. Intermixing of water, via multiple screened wells, between the various aquifers is also indicated. (author). 5 refs., 5 figs., 1 tab

  10. ENSO variability reflected in precipitation oxygen isotopes across the Asian Summer Monsoon region

    Science.gov (United States)

    Cai, Zhongyin; Tian, Lide; Bowen, Gabriel J.

    2017-10-01

    Oxygen isotope signals (δ18O) from paleo-archives are important proxies for past Asian Summer Monsoon (ASM) climate reconstruction. However, causes of interannual variation in the δ18O values of modern precipitation across the ASM region remain in argument. We report interannual δ18O variation in southern Tibetan Plateau precipitation based on long-term observations at Lhasa. These data, together with precipitation δ18O records from five Global Network of Isotopes in Precipitation (GNIP) stations and two ice core δ18O records, were used to define a regional metric of ASM precipitation δ18O (ASMOI). Back-trajectory analyses for rainy season precipitation events indicate that moisture sources vary little between years with relatively high and low δ18O values, a result that is consistent for the south (Lhasa), southeast (Bangkok), and east ASM regions (Hong Kong). In contrast, δ18O values at these three locations are significantly correlated with convection in the estimated source regions and along transport paths. These results suggest that upstream convection, rather than moisture source change, causes interannual variation in ASM precipitation δ18O values. Contrasting values of the ASMOI in El Niño and La Niña years reveal a positive isotope-El Niño Southern Oscillation (ENSO) response (e.g., high values corresponding to warm phases), which we interpret as a response to changes in regional convection. We show that the isotope-ENSO response is amplified at high elevation sites and during La Niña years. These findings should improve interpretations of paleo-δ18O data as a proxy for past ASM variation and provide new opportunities to use data from this region to study paleo-ENSO activity.

  11. Preliminary study on the characteristics of carbon and oxygen isotopes in the Shiziping geothermal field groundwater in Emei Mountain

    International Nuclear Information System (INIS)

    Yu Xiujing; Jia Shuyuan

    2000-01-01

    Emei Mountain is a well-known scenic tourism spot in China. In order to promote the development of tourist trade, the authors have explored the hydrothermal water in Emei Mountain. At the beginning of 1998, the hydrothermal water was successfully drilled from the Shiziping geothermal field. In the process of prospecting the hydrothermal water, the authors adopted the geochemical method such as carbon and oxygen isotopes. The result indicates that the groundwater of different genetic types has different constitution characteristics of carbon and oxygen isotopes. This provides the important basis for finding out the forming conditions of underground hydrothermal water. So, it is prospective to study the growth characteristics of hydrothermal water with the carbon and oxygen isotopes of HCO 3 in groundwater

  12. Seasonal Variations in Stable Isotope Ratios of Oxygen and Hydrogen in Two Tundra Rivers in NE European Russia

    Energy Technology Data Exchange (ETDEWEB)

    Huitu, E.; Arvola, L. [Lammi Biological Station, University of Helsinki (Finland); Sonninen, E. [Radiocarbon Dating Laboratory, University of Helsinki (Finland)

    2013-07-15

    The variability in stable isotope ratios of oxygen and hydrogen ({delta} {sup 18}O and {delta}{sup 2}H values) in river waters in northeast European Russia was studied for the period from July 2007 to october 2008. Exceptional isotope composition in precipitation obtained during the sampling period was clearly traced in the composition of river waters. Water from permafrost thawing did not make a great contribution to river flow. (author)

  13. 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...

  14. 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

  15. 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)

  16. 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

  17. Phosphorus cycling in forest ecosystems: insights from oxygen isotopes in phosphate

    Science.gov (United States)

    Pistocchi, Chiara; Tamburini, Federica; Bünemann, Else; Frossard, Emmanuel

    2015-04-01

    The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sa