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Sample records for hydrogen isotope fractionation

  1. Hydrogen isotope fractionation in methane plasma

    OpenAIRE

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

    2017-01-01

    Large variations in light element isotope ratios (H, N, C) are routinely observed in meteorite organic matter. The origin of these so-called anomalies is not accounted for by the classical theory of isotope fractionation. In the case of H, micrometer-size areas within the insoluble organic matter (IOM) isolated from meteorites by acid treatment, exhibit extreme deuterium enrichment. They are generally interpreted as components exogenous to the solar system and attributed to surviving interste...

  2. [Fractionation of hydrogen stable isotopes in the human body].

    Science.gov (United States)

    Siniak, Iu E; Grigor'ev, A I; Skuratov, V M; Ivanova, S M; Pokrovskiĭ, B G

    2006-01-01

    Fractionation of hydrogen stable isotopes was studied in 9 human subjects in a chamber with normal air pressure imitating a space cabin. Mass-spectrometry of isotopes in blood, urine, saliva, and potable water evidenced increases in the contents of heavy H isotope (deuterium) in the body liquids as compared with water. These results support one of the theories according to which the human organism eliminates heavy stable isotopes of biogenous chemical elements.

  3. Hydrogen isotope fractionation in methane plasma

    Science.gov (United States)

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

    2017-01-01

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

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

    Science.gov (United States)

    Pahlevan, K.; Karato, S. I.

    2016-12-01

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

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

    Science.gov (United States)

    Dirghangi, S. S.; Pagani, M.

    2010-12-01

    Lipids form an important class of proxies for paleoclimatological research, and hydrogen isotope ratios of lipids are being increasingly used for understanding changes in the hydrological system. Proper understanding of hydrogen isotope fractionation during lipid biosynthesis is therefore important and attention has been directed toward understanding the magnitude of hydrogen isotope fractionation that occurs during lipid biosynthesis in various organisms. Hydrogen isotope ratios of lipids depend on the hydrogen isotopic composition of the ambient water, hydrogen isotopic composition of NADPH used during biosynthesis, growth conditions, pathways of lipid biosynthesis, and substrates in the case of heterotrophic organisms. Recently it has been observed that NADPH contributes a significant part of the hydrogen in fatty acids synthesized by bacteria during heterotrophic growth (Zhang et al, 2009). As NADPH is formed by reduction of NADP+ during metabolism of substrates, different metabolic pathways form NADPH with different D/H ratios, which in turn results in variation in D/H ratios of lipids (Zhang et al, 2009). Therefore, substrates play a significant role in hydrogen isotopic compositions of lipids. For this study, we are investigating the effects of substrates on hydrogen isotope fractionation during biosynthesis of isoprenoidal lipids by heterotrophically growing halophilic archaea. Haloarcula marismortui is a halophilic archaea which synthesizes Archaeol (a diether lipid) and other isoprenoidal lipids. We have grown Haloarcula marismortui in pure cultures on three different substrates and are in the process of evaluating isotopic variability of Archaeol and other lipids associated with substrate and the D/H composition of ambient water. Our results will be helpful for a better understanding of hydrogen isotope fractionations during lipid synthesis by archaea. Also, halophilic archaea are the only source of archaeol in hypersaline environments. Therefore, our

  6. Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

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    F. Keppler

    2018-05-01

    Full Text Available Chloromethane (CH3Cl is an important provider of chlorine to the stratosphere but detailed knowledge of its budget is missing. Stable isotope analysis is a potentially powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog chamber at 293 ± 1 K. We measured the stable hydrogen isotope values of the unreacted CH3Cl using compound-specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −264±45 and −280±11 ‰, respectively. For comparison, we performed similar experiments using methane (CH4 as the target compound with OH and obtained a fractionation constant of −205±6 ‰ which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

  7. Fractionation of hydrogen isotopes by sulfate- and nitrate-reducing bacteria

    OpenAIRE

    Magdalena Rose Osburn; Katherine S Dawson; Marilyn L Fogel; Alex Sessions

    2016-01-01

    Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen –protium and deuterium –that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ2H provides a potential basis f...

  8. Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

    International Nuclear Information System (INIS)

    Schoeller, D.A.; Leitch, C.A.; Brown, C.

    1986-01-01

    The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO 2 excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37 0 C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water, local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O 2 and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO 2 production

  9. Carbon and hydrogen isotope fractionation during aerobic biodegradation of quinoline and 3-methylquinoline.

    Science.gov (United States)

    Cui, Mingchao; Zhang, Wenbing; Fang, Jun; Liang, Qianqiong; Liu, Dongxuan

    2017-08-01

    Compound-specific isotope analysis has been used extensively to investigate the biodegradation of various organic pollutants. To date, little isotope fractionation information is available for the biodegradation of quinolinic compounds. In this study, we report on the carbon and hydrogen isotope fractionation during quinoline and 3-methylquinoline aerobic microbial degradation by a Comamonas sp. strain Q10. Degradation of quinoline and 3-methylquinoline was accompanied by isotope fractionation. Large hydrogen and small carbon isotope fractionation was observed for quinoline while minor carbon and hydrogen isotope fractionation effects occurred for 3-methylquinoline. Bulk carbon and hydrogen enrichment factors (ε bulk ) for quinoline biodegradation were -1.2 ± 0.1 and -38 ± 1‰, respectively, while -0.7 ± 0.1 and -5 ± 1‰ for 3-methylquinoline, respectively. This reveals a potential advantage for employing quinoline as the model compound and hydrogen isotope analysis for assessing aerobic biodegradation of quinolinic compounds. The apparent kinetic isotope effects (AKIE C ) values of carbon were 1.008 ± 0.0005 for quinoline and 1.0048 ± 0.0005 for 3-methylquinoline while AKIE H values of hydrogen of 1.264 ± 0.011 for quinoline and 1.0356 ± 0.0103 for 3-methylquinoline were obtained. The combined evaluation of carbon and hydrogen isotope fractionation yields Λ values (Λ = Δδ 2 H/Δδ 13 C ≈ εH bulk /εC bulk ) of 29 ± 2 for quinoline and 8 ± 2 for 3-methylquinoline. The results indicate that the substrate specificity may have a significant influence on the isotope fractionation for the biodegradation of quinolinic compounds. The substrate-specific isotope enrichment factors would be important for assessing the behavior and fate of quinolinic compounds in the environment.

  10. 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

  11. Fractionation of hydrogen isotopes by sulfate- and nitrate-reducing bacteria

    Directory of Open Access Journals (Sweden)

    Magdalena Rose Osburn

    2016-08-01

    Full Text Available Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen –protium and deuterium –that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ2H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ2H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ2H suggest much potential as an environmental recorder of metabolism.

  12. Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria.

    Science.gov (United States)

    Osburn, Magdalena R; Dawson, Katherine S; Fogel, Marilyn L; Sessions, Alex L

    2016-01-01

    Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen-protium and deuterium-that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ(2)H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ(2)H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ(2)H suggest much potential as an environmental recorder of metabolism.

  13. Salinity dependent hydrogen isotope fractionation in alkenones produced by coastal and open ocean haptophyte algae

    NARCIS (Netherlands)

    M'boule, D.; Chivall, D.; Sinke-Schoen, D.; Sinninghe Damsté, J.S.; Schouten, S.; van der Meer, M.T.J.

    2014-01-01

    The hydrogen isotope fractionation in alkenones produced by haptophyte algae is a promising new proxy for paleosalinity reconstructions. To constrain and further develop this proxy the coastal haptophyte Isochrysis galbana and the open ocean haptophyte alga Emiliania huxleyi were cultured at

  14. Large effect of irradiance on hydrogen isotope fractionation of alkenones in Emiliania huxleyi

    Science.gov (United States)

    van der Meer, Marcel T. J.; Benthien, Albert; French, Katherine L.; Epping, Eric; Zondervan, Ingrid; Reichart, Gert-Jan; Bijma, Jelle; Sinninghe Damsté, Jaap S.; Schouten, Stefan

    2015-07-01

    The hydrogen isotopic (δD) composition of long-chain alkenones produced by certain haptophyte algae has been suggested as a potential proxy for reconstructing paleo sea surface salinity. However, environmental parameters other than salinity may also affect the δD of alkenones. We investigated the impact of the level of irradiance on hydrogen isotopic fractionation of alkenones versus growth water by cultivating two strains of the cosmopolitan haptophyte Emiliania huxleyi at different light intensities. The hydrogen isotope fractionation decreased by approximately 40‰ when irradiance was increased from 15 to 200 μmol photons m-2 s-1 above which it was relatively constant. The response is likely a direct effect of photosystem I and II activity as the relationship of the fractionation factor α versus light intensity can be described by an Eilers-Peeters photosynthesis model. This irradiance effect is in agreement with published δD data of alkenones derived from suspended particulate matter collected from different depths in the photic zone of the Gulf of California and the eastern tropical North Pacific. However, haptophyte algae tend to bloom at relatively high light intensities (>500 μmol photons m-2 s-1) occurring at the sea surface, at which hydrogen isotope fractionation is relatively constant and not affected by changes in light intensity. Alkenones accumulating in the sediment are likely mostly derived from these surface water haptophyte blooms, when the largest amount of biomass is produced. Therefore, the observed irradiance effect is unlikely to affect the applicability of the hydrogen isotopic composition of sedimentary long chain alkenones as a proxy for paleosalinity.

  15. EXPERIMENTAL INVESTIGATION OF IRRADIATION-DRIVEN HYDROGEN ISOTOPE FRACTIONATION IN ANALOGS OF PROTOPLANETARY HYDROUS SILICATE DUST

    Energy Technology Data Exchange (ETDEWEB)

    Roskosz, Mathieu; Remusat, Laurent [IMPMC, CNRS UMR 7590, Sorbonne Universités, Université Pierre et Marie Curie, IRD, Muséum National d’Histoire Naturelle, CP 52, 57 rue Cuvier, Paris F-75231 (France); Laurent, Boris; Leroux, Hugues, E-mail: mathieu.roskosz@mnhn.fr [Unité Matériaux et Transformations, Université Lille 1, CNRS UMR 8207, Bâtiment C6, F-59655 Villeneuve d’Ascq (France)

    2016-11-20

    The origin of hydrogen in chondritic components is poorly understood. Their isotopic composition is heavier than the solar nebula gas. In addition, in most meteorites, hydrous silicates are found to be lighter than the coexisting organic matter. Ionizing irradiation recently emerged as an efficient hydrogen fractionating process in organics, but its effect on H-bearing silicates remains essentially unknown. We report the evolution of the D/H of hydrous silicates experimentally irradiated by electrons. Thin films of amorphous silica, amorphous “serpentine,” and pellets of crystalline muscovite were irradiated at 4 and 30 keV. For all samples, irradiation leads to a large hydrogen loss correlated with a moderate deuterium enrichment of the solid residue. The entire data set can be described by a Rayleigh distillation. The calculated fractionation factor is consistent with a kinetically controlled fractionation during the loss of hydrogen. Furthermore, for a given ionizing condition, the deuteration of the silicate residues is much lower than the deuteration measured on irradiated organic macromolecules. These results provide firm evidence of the limitations of ionizing irradiation as a driving mechanism for D-enrichment of silicate materials. The isotopic composition of the silicate dust cannot rise from a protosolar to a chondritic signature during solar irradiations. More importantly, these results imply that irradiation of the disk naturally induces a strong decoupling of the isotopic signatures of coexisting organics and silicates. This decoupling is consistent with the systematic difference observed between the heavy organic matter and the lighter water typically associated with minerals in the matrix of most carbonaceous chondrites.

  16. 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

  17. Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

    Science.gov (United States)

    Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

    2009-06-01

    The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

  18. Carbon, Chlorine, and Hydrogen Isotope Fractionation in Transformation of TCE to Ethene by a Dehalococcoides Culture

    NARCIS (Netherlands)

    Kuder, T.; van Breukelen, B.M.; Vanderford, M.; Philip, P.

    2013-01-01

    Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc.

  19. 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

  20. Growth phase dependent hydrogen isotopic fractionation in alkenone-producing haptophytes

    Directory of Open Access Journals (Sweden)

    M. D. Wolhowe

    2009-08-01

    Full Text Available Recent works have investigated use of the hydrogen isotopic composition of C37 alkenones (δDK37s, lipid biomarkers of certain haptophyte microalgae, as an independent paleosalinity proxy. We discuss herein the factors impeding the success of such an application and identify the potential alternative use of δDK37s measurements as a proxy for non-thermal, physiological stress impacts on the U37K' paleotemperature index. Batch-culture experiments with the haptophyte Emiliania huxleyi (CCMP 1742 were conducted to determine the magnitude and variability of the isotopic contrasts between individual C37 alkenones. Further experiments were conducted with Emiliania huxleyi (CCMP 1742 andGephyrocapsa oceanica (PZ3-1 to determine whether, and to what extent, δDK37s varies between the physiological extremes of nutrient-replete exponential growth and nutrient-depleted senescence. Emiliania huxleyi was observed to exhibit an isotopic contrast between di- and tri-unsaturated C37 alkenones (αK37:3-K37:2≈0.97 that is nearly identical to that reported recently by others for environmental samples. Furthermore, this contrast appears to be constant with growth stage. The consistency of the offset across different growth stages suggests that a single, well-defined value for αK37:3-K37:2 may exist and that its use in an isotope mass-balance will allow accurate determination of δD values for individual alkenones without having to rely on time- and labor-intensive chemical separations. The isotopic fractionation between growth medium and C37 alkenones was observed to increase dramatically upon the onset of nutrient-depletion-induced senescence, suggesting that δDK37s may serve as an objective tool for recognizing and potentially correcting, at least semi-quantitatively, for the effects

  1. Carbon and Hydrogen Stable Isotope Fractionation during Aerobic Bacterial Degradation of Aromatic Hydrocarbons†

    Science.gov (United States)

    Morasch, Barbara; Richnow, Hans H.; Schink, Bernhard; Vieth, Andrea; Meckenstock, Rainer U.

    2002-01-01

    13C/12C and D/H stable isotope fractionation during aerobic degradation was determined for Pseudomonas putida strain mt-2, Pseudomonas putida strain F1, Ralstonia pickettii strain PKO1, and Pseudomonas putida strain NCIB 9816 grown with toluene, xylenes, and naphthalene. Different types of initial reactions used by the respective bacterial strains could be linked with certain extents of stable isotope fractionation during substrate degradation. PMID:12324375

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

    Directory of Open Access Journals (Sweden)

    G. M. Weiss

    2017-12-01

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

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

    Science.gov (United States)

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

    2017-12-01

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

  4. Ice-vapor equilibrium fractionation factor of hydrogen and oxygen isotopes

    DEFF Research Database (Denmark)

    Ellehøj, Mads Dam; Steen-Larsen, Hans Christian; Johnsen, Sigfus Johann

    2013-01-01

    RATIONALE: The equilibrium fractionation factors govern the relative change in the isotopic composition during phase transitions of water. The commonly used results, which were published more than 40 years ago, are limited to a minimum temperature of -33 degrees C. This limits the reliability...... values, with a temperature dependency in accordance with theory for equilibrium fractionation. We obtain the following expressions for the temperature dependency of the fractionation coefficients: ln(alpha(delta 2H)) = 0.2133 - 203.10/T + 48888/T-2 ln(alpha(delta 18O)) = 0.0831 - 49.192/T + 8312.5/T2...... Compared with previous experimental work, a significantly larger for H-2 is obtained while, for O-18, is larger for temperatures below -20 degrees C and slightly lower for temperatures above this. CONCLUSIONS: Using the new values for alpha, a Rayleigh distillation model shows significant changes in both...

  5. Deuterium isotope effects and fractionation factors of hydrogen-bonded A:T base pairs of DNA

    International Nuclear Information System (INIS)

    Vakonakis, Ioannis; Salazar, Miguel; Kang, Mijeong; Dunbar, Kim R.; Li Wang, Andy C.

    2003-01-01

    Deuterium isotope effects and fractionation factors of N1...H3-N3 hydrogen bonded Watson-Crick A:T base pairs of two DNA dodecamers are presented here. Specifically, two-bond deuterium isotope effects on the chemical shifts of 13 C2 and 13 C4, 2 Δ 13 C2 and 2 Δ 13 C4, and equilibrium deuterium/protium fractionation factors of H3, Φ, were measured and seen to correlate with the chemical shift of the corresponding imino proton, δ H3 . Downfield-shifted imino protons associated with larger values of 2 Δ 13 C2 and 2 Δ 13 C4 and smaller Φ values, which together suggested that the effective H3-N3 vibrational potentials were more anharmonic in the stronger hydrogen bonds of these DNA molecules. We anticipate that 2 Δ 13 C2, 2 Δ 13 C4 and Φ values can be useful gauges of hydrogen bond strength of A:T base pairs

  6. Intracellular Cadmium Isotope Fractionation

    Science.gov (United States)

    Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

    2011-12-01

    Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

  7. Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

    Science.gov (United States)

    Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

    2017-09-01

    Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  8. Minimal Influence of [NiFe] Hydrogenase on Hydrogen Isotope Fractionation in H2-Oxidizing Cupriavidus necator

    Directory of Open Access Journals (Sweden)

    Brian J. Campbell

    2017-10-01

    Full Text Available Fatty acids produced by H2-metabolizing bacteria are sometimes observed to be more D-depleted than those of photoautotrophic organisms, a trait that has been suggested as diagnostic for chemoautotrophic bacteria. The biochemical reasons for such a depletion are not known, but are often assumed to involve the strong D-depletion of H2. Here, we cultivated the bacterium Cupriavidus necator H16 (formerly Ralstonia eutropha H16 under aerobic, H2-consuming, chemoautotrophic conditions and measured the isotopic compositions of its fatty acids. In parallel with the wild type, two mutants of this strain, each lacking one of two key hydrogenase enzymes, were also grown and measured. In all three strains, fractionations between fatty acids and water ranged from -173‰ to -235‰, and averaged -217‰, -196‰, and -226‰, respectively, for the wild type, SH- mutant, and MBH- mutant. There was a modest increase in δD as a result of loss of the soluble hydrogenase enzyme. Fractionation curves for all three strains were constructed by growing parallel cultures in waters with δDwater values of approximately -25‰, 520‰, and 1100‰. These curves indicate that at least 90% of the hydrogen in fatty acids is derived from water, not H2. Published details of the biochemistry of the soluble and membrane-bound hydrogenases confirm that these enzymes transfer electrons rather than intact hydride (H- ions, providing no direct mechanism to connect the isotopic composition of H2 to that of lipids. Multiple lines of evidence thus agree that in this organism, and presumably others like it, environmental H2 plays little or no direct role in controlling lipid δD values. The observed fractionations must instead result from isotope effects in the reduction of NAD(PH by reductases with flavin prosthetic groups, which transfer two electrons and acquire H+ (or D+ from solution. Parallels to NADPH reduction in photosynthesis may explain why D/H fractionations in C. necator

  9. Fractionation of hydrogen, oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

    NARCIS (Netherlands)

    Brader, A.V.; Winden, J.F.; Bohncke, S.J.P.; Beets, C.J.; Reichart, G.-J.; De Leeuw, J.W.

    2010-01-01

    Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were

  10. Chromatographic hydrogen isotope separation

    International Nuclear Information System (INIS)

    Aldridge, F.T.

    1983-01-01

    Intermetallic compounds with the CaCu5 type of crystal structure, particularly LaNiCo and CaNi5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors

  11. Chromatographic hydrogen isotope separation

    International Nuclear Information System (INIS)

    Aldridge, F.T.

    1981-01-01

    Intermetallic compounds with the CaCu5 type of crystal structure , particularly LaNiCo and CaNi5, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation colum. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale mutli-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen can produce large quantities of heavy water at an effective cost for use in heavy water reactors

  12. Container for hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    1976-01-12

    A container is described for storage, shipping and and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same. The container is compact, safe against fracture or accident, and is reusable. It consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and is retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates.

  13. Container for hydrogen isotopes

    International Nuclear Information System (INIS)

    1976-01-01

    A container is described for storage, shipping and and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same. The container is compact, safe against fracture or accident, and is reusable. It consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and is retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates

  14. There is no temperature dependence of net biochemical fractionation of hydrogen and oxygen isotopes in tree-ring cellulose.

    Science.gov (United States)

    Roden, J S; Ehleringer, J R

    2000-01-01

    The isotopic composition of tree-ring cellulose was obtained over a two-year period from small diameter, riparian zone trees along an elevational transect in Big Cottonwood Canyon, Utah, USA to test for a possible temperature dependence of net biological fractionation during cellulose synthesis. The isotope ratios of stream water varied by only 3.6% and 0.2% in deltaD and delta18O, respectively, over an elevation change of 810m. The similarity in stream water and macroenvironment over the short (13km) transect produced nearly constant stem and leaf water deltaD and delta18O values. In addition, what few seasonal variations observed in the isotopic composition of source water and atmospheric water vapor or in leaf water evaporative enrichment were experienced equally by all sites along the elevational transect. The temperature at each site along the transect spanned a range of > or = 5 degrees C as calculated using the adiabatic lapse rate. Since the deltaD and delta18O values of stem and leaf water varied little for these trees over this elevation/temperature transect, any differences in tree-ring cellulose deltaD and delta18O values should have been associated with temperature effects on net biological fractionation. However, the slopes of the regressions of elevation versus the deltaD and delta18O values of tree-ring cellulose were not significantly different from zero indicating little or no temperature dependence of net biological fractionation. Therefore, cross-site climatic reconstruction studies using the isotope ratios of cellulose need not be concerned that temperatures during the growing season have influenced results.

  15. Hydrogen isotope technology

    International Nuclear Information System (INIS)

    Anon.

    1980-01-01

    Hydrogen pumping speeds on panels of molecular sieve types 5A and Na-Y were compared for a variety of sieve (and chevron) temperatures between 10 and 30 K. Although pumping speeds declined with time, probably because of the slow diffusion of hydrogen from the surface of the sieve crystals into the internal regions, the different sieve materials and operating conditions could be compared using time-averaged pump speeds. The (average) pumping speeds declined with increasing temperature. Under some conditions, the Na-Y sieve performed much better than the 5A sieve. Studies of the effect of small concentrations (approx. 4%) of hydrogen on helium pumping indicate that compound cryopumps in fusion reactors will not have to provide complete screening of hydrogen from helium panels. The concentrations of hydrogen did not lower effective helium pumping speeds or shorten the helium operating period between instabilities. Studies of tritium recovery from blankets of liquid lithium focused on design and construction of a flowing-lithium test system and on ultimate removal of tritium from yttrium sorbents. At 505 0 C, tritium release from yttrium behaves as a diffusion-controlled process, but the release rates are very low. Apparently, higher temperatures will be required for effective sorbent regeneration. An innovative technique for separating hydrogen isotopes by using bipolar electrolysis with permeable electrodes was analyzed to determine its potential usefulness in multistage separation

  16. Noncovalent Hydrogen Isotope Effects

    Science.gov (United States)

    Buchachenko, A. L.; Breslavskaya, N. N.

    2018-02-01

    Zero-point energies (ZPE) and isotope effects, induced by intermolecular, noncovalent vibrations, are computed and tested by experimental data. The ZPE differences of H- and D-complexes of water with hydrogen, methane, and water molecules are about 100-300 cal/mol; they result to isotope effects IE of 1.20-1.70. Semi-ionic bonds between metal ions and water ligands in M(H2O) 6 2+ complexes are much stronger; their ZPEs are about 12-14 kcal/mol per molecule and result to IE of 1.9-2.1 at 300 K. Protonated (deuterated) water and biwater exhibit the largest ZPE differences and isotope effects; the latter are 25-28 and 12-13 for water and biwater, respectively. Noncovalent IEs contribute markedly into the experimentally measured effects and explain many anomalous and even magic properties of the effects, such as the dependence of IE on the solvents and on the presence of the third substances, enormously large isotope effects at the mild conditions, the difference between IEs measured in the reactions of individual protiated and deuterated compounds and those measured in their mixture. Noncovalent IEs are not negligible and should be taken into account to make correct and substantiated conclusions on the reaction mechanisms. The kinetic equations are derived for the total isotope effects, which include noncovalent IEs as additive factors.

  17. Application of site-specific natural isotope fractionation (SNIF-NMR) of hydrogen to the characterization of European beers

    International Nuclear Information System (INIS)

    Martin, G.J.; Benbernou, M.; Lantier, F.

    1985-01-01

    More than one hundred samples of European beers have been investigated by the new SNIF-NMR method which is based on 2H NMR at the natural abundance level and enables site-specific natural isotope fractionation factors in ethanol to be determined. The relative (R) and absolute (D/H)sub(i) parameters are shown to be characteristic of the country where the beers are brewed and the observed variations are explained in terms of cereal composition, water resource, and manufacturing processing (fermentation, yeast, temperature cycle). These new parameters find analytical and mechanistic applications in the identification of a beer and in the investigation of a fermentation process. (author)

  18. Electrochemically controlled iron isotope fractionation

    Science.gov (United States)

    Black, Jay R.; Young, Edward D.; Kavner, Abby

    2010-02-01

    Variations in the stable isotope abundances of transition metals have been observed in the geologic record and trying to understand and reconstruct the physical/environmental conditions that produced these signatures is an area of active research. It is clear that changes in oxidation state lead to large fractionations of the stable isotopes of many transition metals such as iron, suggesting that transition metal stable isotope signatures could be used as a paleo-redox proxy. However, the factors contributing to these observed stable isotope variations are poorly understood. Here we investigate how the kinetics of iron redox electrochemistry generates isotope fractionation. Through a combination of electrodeposition experiments and modeling of electrochemical processes including mass-transport, we show that electron transfer reactions are the cause of a large isotope separation, while mass transport-limited supply of reactant to the electrode attenuates the observed isotopic fractionation. Furthermore, the stable isotope composition of electroplated transition metals can be tuned in the laboratory by controlling parameters such as solution chemistry, reaction overpotential, and solution convection. These methods are potentially useful for generating isotopically-marked metal surfaces for tracking and forensic purposes. In addition, our studies will help interpret stable isotope data in terms of identifying underlying electron transfer processes in laboratory and natural samples.

  19. Container for hydrogen isotopes

    International Nuclear Information System (INIS)

    Solomon, D.E.

    1977-01-01

    A container for the storage, shipping and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same which has compactness, which is safe against fracture or accident, and which is reusable is described. The container consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example, of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and will be retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates

  20. Melatonin labeled with hydrogen isotopes

    International Nuclear Information System (INIS)

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

    1989-01-01

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

  1. Melatonin labelled by hydrogen isotopes

    International Nuclear Information System (INIS)

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

    1988-01-01

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

  2. In-situ, high pressure and temperature experimental determination of hydrogen isotope fractionation between coexisting hydrous melt and silicate-saturated aqueous fluid

    Science.gov (United States)

    Mysen, B. O.

    2012-12-01

    Hydrogen isotope fractionation between water-saturated silicate melt and silicate-saturated aqueous fluid has been determined experimentally, in-situ with the samples in the 450-800C and 101-1567 MPa temperature and pressure range, respectively. The temperatures are, therefore higher than those where hydrogen bonding in fluids and melts is important [1]. The experiments were conducted with a hydrothermal diamond anvil cell (HDAC) as the high-temperature/-pressure tool and vibrational spectroscopy to determine D/H fractionation. Compositions were along the haploandesite join, Na2Si4O9 - Na2(NaAl)4O9 [Al/(Al+Si)=0-0.1], and a 50:50 (by volume) H2O:D2O fluid mixture as starting material. Platinum metal was used to enhance equilibration rate. Isotopic equilibrium was ascertained by using variable experimental duration at given temperature and pressure. In the Al-free Na-silicate system, the enthalpy change of the (D/H) equilibrium of fluid is 3.1±0.7 kJ/mol, whereas for coexisting melt, ΔH=0 kJ/mol within error. With Al/(Al+Si)=0.1, ΔH=5.2±0.9 kJ/mol for fluid and near 0 within error for coexisting melt melt. For the exchange equilibrium between melt and fluid, H2O(melt)+D2O(fluid)=H2O(fluid)+D2O(melt), the ΔH=4.6±0.7 and 6.5±0.7 kJ/mol for the two Al-free and Al-bearing compositions, respectively, respectively. The D/H equilibration within fluids and melts and, therefore, D/H partitioning between coexisting fluid and melt reflect the influence of dissolved H2O(D2O) in melts and dissolved silicate components in H2O(D2O) fluid on their structure. The positive temperature- and pressure-dependence of silicate solubility and on silicate structure in silicate-saturated aqueous fluid governs the D/H fractionation in the fluid because increasing silicate solute concentration in fluid results in silicate polymerization [2]. These structural effects may be analogous to observed solute-dependent oxygen isotope fractionation between brine and CO2 [3]. In the temperature

  3. Isotopic fractionation of tritium in biological systems.

    Science.gov (United States)

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

    2014-04-01

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

  4. Chain-Length Distribution and Hydrogen Isotopic Fraction of n-alkyl Lipids in Aquatic and Terrestrial Plants: Implications for Paleoclimate Reconstructions

    Science.gov (United States)

    Gao, L.; Littlejohn, S.; Hou, J.; Toney, J.; Huang, Y.

    2008-12-01

    Recent studies demonstrate that in lacustrine sediments, aquatic plant lipids (e.g., C22-fatty acid) record lake water D/H ratio variation, while long-chain fatty acids (C26-C32, major components of terrestrial plant leaf waxes), record D/H ratios of precipitation (especially in arid regions). However, there are insufficient literature data for the distribution and hydrogen isotopic fractionation of n-alkyl lipids in aquatic and terrestrial plants. In this study, we determined the chain-length distributions and D/H ratios of n-alkyl lipids from 17 aquatic plant species (9 emergent, 4 floating and 4 submerge species) and 13 terrestrial plant species (7 grasses and 6 trees) from Blood Pond, Massachusetts. Our results are consistent with previous studies and provide a solid basis for the paleoclimatic reconstruction using D/H ratios of aquatic and terrestrial plant biomarkers. In addition, systematic hydrogen isotopic analyses on leaf waxes, leaf, stem and soil waters from trees and grasses significantly advance our understanding of our previously observed large D/H ratio difference between tree and grass leaf waxes. Our data indicate that the observed difference is not due to differences in leaf water D/H ratios. In comparison with grasses, trees use greater proportion of D-enriched residual or stored carbohydrates (as opposed to current photosynthetic carbohydrates) for leaf wax biosynthesis, resulting in higher leaf wax D/H ratios. The residual carbohydrates are enriched in deuterium because of the preferential consumption of light-hydrogen substrates during plant metabolism.

  5. Natural fractionation of uranium isotopes

    International Nuclear Information System (INIS)

    Noordmann, Janine

    2015-01-01

    The topic of this thesis was the investigation of U (n( 238 U) / n( 235 U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n( 238 U) and n( 235 U), on Earth.

  6. Biogeochemistry of the stable hydrogen isotopes

    International Nuclear Information System (INIS)

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

    1980-01-01

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

  7. Biogeochemistry of the stable hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-08-01

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

  8. Determination of hydrogen isotope composition in organic compounds

    International Nuclear Information System (INIS)

    Ordzhonikidze, K.G.; Parulava, L.P.; Vakhaniya, G.V.; Tarielashvili, V.O.

    1989-01-01

    method for determination of hydrogen isotope composition just in organic compounds using mass-spectrometer of the second class is suggested. The method enables to determine atomic fraction of hydrogen without multiplet separation. The accuracy of determination of deuterium atomic fraction in acetone in 1-99% range was equal to 3-0.2% respectively

  9. Natural fractionation of uranium isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Noordmann, Janine

    2015-01-24

    The topic of this thesis was the investigation of U (n({sup 238}U) / n({sup 235}U)) isotope variations in nature with a focus on samples (1) that represent the continental crust and its weathering products (i.e. granites, shales and river water) (2) that represent products of hydrothermal alteration on mid-ocean ridges (i.e. altered basalts, carbonate veins and hydrothermal water) and (3) from restricted euxinic basins (i.e. from the water column and respective sediments). The overall goal was to explore the environmental conditions and unravel the mechanisms that fractionate the two most abundant U isotopes, n({sup 238}U) and n({sup 235}U), on Earth.

  10. Can a sponge fractionate isotopes?

    Science.gov (United States)

    Patel, B; Patel, S; Balani, M C

    1985-03-22

    activities can be modified is by fractionation on the basis of mass of isotope. In view of the remarkable concentration factors observed for stable and radioactive isotopes of the same element and the specific activities reached, it is desirable that species of sponges, especially from the coastal and estuarine environments, be monitored to detect levels of pollution due to anthropogenic substances.

  11. Mass fractionation processes of transition metal isotopes

    Science.gov (United States)

    Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

    2002-06-01

    Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

  12. 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

  13. 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)

  14. Isotopic fractionation of soil water during evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Leopoldo, P R [Faculdade de Ciencias Medicas e Biologicas de Botucatu (Brazil); Salati, E; Matsui, E [Centro de Energia Nuclear na Agricultura, Piracicaba (Brazil)

    1974-07-01

    The study of the variation of D/H relation in soil water during evaporation is studied. The isotopic fractionation of soil water has been observed in two soils of light and heavy texture. Soil columns were utilized. Soil water was extracted in a system operated under low pressure and the gaseous hydrogen was obtained by decomposition of the water and was analyzed in a GD-150 mass spectrometer for deuterium content. The variation of the delta sub(eta) /sup 0///sub 00/ value during evaporation showed that for water held at potentials below 15 atm, the deuterium content of soil water stays practically constant. For water held at potentials higher than 15 atm, corresponding to the third stage of evaporation, there is a strong tendency of a constant increase of delta sub(eta) /sup 0///sub 00/ of the remaining water.

  15. 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

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  17. Copper isotope fractionation by desert shrubs

    International Nuclear Information System (INIS)

    Navarrete, Jesica U.; Viveros, Marian; Ellzey, Joanne T.; Borrok, David M.

    2011-01-01

    Copper has two naturally occurring stable isotopes of masses 63 and 65 which can undergo mass dependent fractionation during various biotic and abiotic chemical reactions. These interactions and their resulting Cu isotope fractionations can be used to determine the mechanisms involved in the cycling of Cu in natural systems. In this study, Cu isotope changes were investigated at the organismal level in the metal-accumulating desert plant, Prosopis pubescens. Initial results suggest that the lighter Cu isotope was preferentially incorporated into the leaves of the plant, which may suggest that Cu was actively transported via intracellular proteins. The roots and stems show a smaller degree of Cu isotope fractionation and the direction and magnitude of the fractionations was dependent upon the levels of Cu exposure. Based on this and previous work with bacteria and yeast, a trend is emerging that suggests the lighter Cu isotope is preferentially incorporated into biological components, while the heavier Cu isotope tends to become enriched in aqueous solutions. In bacteria, plants and animals, intracellular Cu concentrations are strictly regulated via dozens of enzymes that can bind, transport, and store Cu. Many of these enzymes reduce Cu(II) to Cu(I). These initial results seem to fit into a broader picture of Cu isotope cycling in natural systems where oxidation/reduction reactions are fundamental in controlling the distributions of Cu isotopes.

  18. Hydrogen isotope effect through Pd in hydrogen transport pipe

    International Nuclear Information System (INIS)

    Tamaki, Masayoshi

    1992-01-01

    This investigation concerns hydrogen system with hydrogen transport pipes for transportation, purification, isotope separation and storage of hydrogen and its isotopes. A principle of the hydrogen transport pipe (heat pipe having hydrogen transport function) was proposed. It is comprised of the heat pipe and palladium alloy tubes as inlet, outlet, and the separation membrane of hydrogen. The operation was as follows: (1) gas was introduced into the heat pipe through the membrane in the evaporator; (2) the introduced gas was transported toward the condenser by the vapor flow; (3) the transported gas was swept and compressed to the end of the condenser by the vapor pressure; and (4) the compressed gas was exhausted from the heat pipe through the membrane in the condenser. The characteristics of the hydrogen transport pipe were examined for various working conditions. Basic performance concerning transportation, evacuation and compression was experimentally verified. Isotopic dihydrogen gases (H 2 and D 2 ) were used as feed gas for examining the intrinsic performance of the isotope separation by the hydrogen transport pipe. A simulated experiment for hydrogen isotope separation was carried out using a hydrogen-helium gas mixture. The hydrogen transport pipe has a potential for isotope separation and purification of hydrogen, deuterium and tritium in fusion reactor technology. (author)

  19. 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.

  20. Treatment and storage of hydrogen isotopes

    International Nuclear Information System (INIS)

    Jung, H. S.; Lee, H. S.; An, D. H.; Kim, K. R.; Lee, S. H.; Choi, H. J.; Back, S. W.; Kang, H. S.; Eom, K. Y.; Lee, M. S.

    2000-01-01

    Storage of gaseous hydrogen isotopes in a cylinder is a well-established technology. However, Immobilization in the solid form is preferred for long-term storage of radioactive isotope gas because of the concern for leakage of the gas. The experimental thermodynamic p-c-T data show that Ti and U soak up hydrogen isotope gas at a temperature of a few hundred .deg. C and modest pressures. It was found that more hydrogen is dissolved in the metal than deuterium at constant pressure. Thus, the lighter isotope tends to be enriched in the solid phase

  1. 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)

  2. Laser photochemical separation of hydrogen isotopes

    International Nuclear Information System (INIS)

    Fowler, M.C.

    1979-01-01

    A method of separating isotopes of hydrogen utilizing isotopically selective photodissociation of organic acid is disclosed. Specifically acetic or formic acid containing compounds of deuterated nd hydrogenated acid is irradiated by radiation having a wavelength in the infrared spectrum between 9.2 to 10.8 microns to produce deuterium hydroxide and deuterium hydride respectively. Maintaining the acid at an elevated temperature significantly improves the yield of isotope separation

  3. Geochemical importance of isotopic fractionation during respiration

    International Nuclear Information System (INIS)

    Schleser, G.; Foerstel, H.

    1975-01-01

    In 1935 it was found that atmospheric oxygen contained a relatively greater abundance of the 18 O isotope than did the oxygen bound in water (Dole effect). A major contribution to the fractionation of the stable oxygen isotopes should result from the respiration of microorganisms. In this respect our interest centers on the soil because nearly all organic material produced on land is decomposed within the soil. The oceans are less important because the primary productivity on land is twice the value for the oceans. In a first approach we measured the oxygen isotope fractionation during the respiration of E. coli K12 for different respiration rates. These results, accomplished with a chemostat, indicate that the fractionation factor α of the oxygen isotopes increases with the increasing respiratory activity, measured as Q/sub O 2 /. At low dilution rates or growth rates respectively of about 0.05 h -1 , the fractionation factor amounts to 1.006 increasing to 1.017 at dilution rates of about 1.0 h -1 . The results are interpreted as a kinetic mass fractionation due to the slightly different diffusion coefficients of 16 O 2 and 18 O 16 O. The respiration rates in conjunction with the corresponding fractionation data are compared with the respiration rates of typical soil microorganisms such as Azotobacter, in order to deduce fractionation data for these organisms. This is necessary to calculate a mean global fractionation factor. Understanding the Dole effect with these fractionation processes should finally give us the opportunity to calculate gas-exchange rates between the atmosphere and the oceans, on the basis of the behavior of the stable oxygen isotopes

  4. Boron-isotope fractionation in plants

    Energy Technology Data Exchange (ETDEWEB)

    Marentes, E [Univ. of Guelph, Dept. of Horticultural Science, Guelph, Ontario (Canada); Vanderpool, R A [USDA/ARS Grand Forks Human Nutrition Research Center, Grand Forks, North Dakota (United States); Shelp, B J [Univ. of Guelph, Dept. of Horticultural Science, Guelph, Ontario (Canada)

    1997-10-15

    Naturally-occurring variations in the abundance of stable isotopes of carbon, nitrogen, oxygen, and other elements in plants have been reported and are now used to understand various physiological processes in plants. Boron (B) isotopic variation in several plant species have been documented, but no determination as to whether plants fractionate the stable isotopes of boron, {sup 11}B and {sup 10}B, has been made. Here, we report that plants with differing B requirements (wheat, corn and broccoli) fractionated boron. The whole plant was enriched in {sup 11}B relative to the nutrient solution, and the leaves were enriched in {sup 10}B and the stem in {sup 11}B relative to the xylem sap. Although at present, a mechanistic role for boron in plants is uncertain, potential fractionating mechanisms are discussed. (author)

  5. Boron-isotope fractionation in plants

    International Nuclear Information System (INIS)

    Marentes, E.; Vanderpool, R.A.; Shelp, B.J.

    1997-01-01

    Naturally-occurring variations in the abundance of stable isotopes of carbon, nitrogen, oxygen, and other elements in plants have been reported and are now used to understand various physiological processes in plants. Boron (B) isotopic variation in several plant species have been documented, but no determination as to whether plants fractionate the stable isotopes of boron, 11 B and 10 B, has been made. Here, we report that plants with differing B requirements (wheat, corn and broccoli) fractionated boron. The whole plant was enriched in 11 B relative to the nutrient solution, and the leaves were enriched in 10 B and the stem in 11 B relative to the xylem sap. Although at present, a mechanistic role for boron in plants is uncertain, potential fractionating mechanisms are discussed. (author)

  6. Process chemistry related to hydrogen isotopes

    International Nuclear Information System (INIS)

    Iwasaki, Matae; Ogata, Yukio

    1991-01-01

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

  7. Iron isotopic fractionation during continental weathering

    Energy Technology Data Exchange (ETDEWEB)

    Fantle, Matthew S.; DePaolo, Donald J.

    2003-10-01

    The biological activity on continents and the oxygen content of the atmosphere determine the chemical pathways through which Fe is processed at the Earth's surface. Experiments have shown that the relevant chemical pathways fractionate Fe isotopes. Measurements of soils, streams, and deep-sea clay indicate that the {sup 56}Fe/{sup 54}Fe ratio ({delta}{sup 56}Fe relative to igneous rocks) varies from +1{per_thousand} for weathering residues like soils and clays, to -3{per_thousand} for dissolved Fe in streams. These measurements confirm that weathering processes produce substantial fractionation of Fe isotopes in the modern oxidizing Earth surface environment. The results imply that biologically-mediated processes, which preferentially mobilize light Fe isotopes, are critical to Fe chemistry in weathering environments, and that the {delta}{sup 56}Fe of marine dissolved Fe should be variable and negative. Diagenetic reduction of Fe in marine sediments may also be a significant component of the global Fe isotope cycle. Iron isotopes provide a tracer for the influence of biological activity and oxygen in weathering processes through Earth history. Iron isotopic fractionation during weathering may have been smaller or absent in an oxygen-poor environment such as that of the early Precambrian Earth.

  8. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    Science.gov (United States)

    Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

    1997-01-01

    Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

  9. Enhancing atom densities in solid hydrogen by isotopic substitution

    International Nuclear Information System (INIS)

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

    1991-01-01

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

  10. 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.

  11. 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

  12. Application of gas chromatography in hydrogen isotope separation

    International Nuclear Information System (INIS)

    Ye Xiaoqiu; Sang Ge; Peng Lixia; Xue Yan; Cao Wei

    2008-01-01

    The principle of gas chromatographic separation of hydrogen isotopes was briefly introduced. The main technology and their development of separating hydrogen isotopes, including elution chromatography, hydrogen-displacement chromatography, self-displacement chromatography and frontal chromatography were discussed in detail. The prospect of hydrogen isotope separation by gas chromatography was presented. (authors)

  13. Separation of hydrogen isotopes for tritium waste removal

    International Nuclear Information System (INIS)

    Wilkes, W.R.

    1975-01-01

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

  14. Hydrogen isotope separation by cryogenic distillation method

    International Nuclear Information System (INIS)

    Hayakawa, Nobuo; Mitsui, Jin

    1987-01-01

    Hydrogen isotope separation in fusion fuel cycle and tritium recovery from heavy water reactor are very important, and therefore the early establishment of these separation techniques are desired. The cryogenic distillation method in particular is promising for the separation of hydrogen isotope and the recovery of high concentrated tritium. The studies of hydrogen isotope separation by cryogenic distillation method have been carried out by using the experimental apparatus made for the first time in Japan. The separation of three components (H 2 -HD-D 2 ) under total reflux conditions was got by using the packing tower of 500 mm height. It was confirmed that the Height Equivalent Theoretical Plate (HETP) was 20 - 30 mm for the vapor's line velocity of 20 - 80 mm/s. (author)

  15. CARBON ISOTOPE FRACTIONATION IN PROTOPLANETARY DISKS

    International Nuclear Information System (INIS)

    Woods, Paul M.; Willacy, Karen

    2009-01-01

    We investigate the gas-phase and grain-surface chemistry in the inner 30 AU of a typical protoplanetary disk (PPD) using a new model which calculates the gas temperature by solving the gas heating and cooling balance and which has an improved treatment of the UV radiation field. We discuss inner-disk chemistry in general, obtaining excellent agreement with recent observations which have probed the material in the inner regions of PPDs. We also apply our model to study the isotopic fractionation of carbon. Results show that the fractionation ratio, 12 C/ 13 C, of the system varies with radius and height in the disk. Different behavior is seen in the fractionation of different species. We compare our results with 12 C/ 13 C ratios in the solar system comets, and find a stark contrast, indicative of reprocessing.

  16. Hydrogen-isotopic composition of some hydrous manganese minerals

    International Nuclear Information System (INIS)

    Hariya, Y.; Tsutsumi, M.

    1981-01-01

    Initial data on the hydrogen-isotopic compositions in hydrous Mn minerals from various occurrences fall in a wide range from -298 to -84per thousand, relative to SMOW. deltaD-values of todorokite and cryptomelane from Tertiary deposits show -89 and -150per thousand. 10 A-manganite and delta-MnO 2 from deep-sea nodules have relatively restricted deltaD-values ranging from -96 to -84per thousand. The deltaD-values for manganese bog ores from recent hot springs show almost -105per thousand. It is recognized that the isotopic values obtained for the deep-sea nodules and recent bog ores are slightly different ranged. Manganite and groutite are unique in their hydrogen-isotopic compositions, having the most depleted deltaD-values ranging from -298 to -236per thousand. MnO(OH) minerals are more deuterium-depleted hydrous minerals than any other hydrothermal minerals from various ore deposits. Hydrogen-isotope fractionation factors between manganite and water were experimentally determined to be 0.7894, 0.7958 and 0.8078 at 150 0 , 200 0 and 250 0 C respectively. The present experimental results indicate that if manganites were formed at temperatures below 250 0 C, under isotopic equilibrium conditions most of the manganite mineralization in the Tertiary manganese deposits must have precipitated from meteoric hydrothermal solutions. (Auth.)

  17. Ca isotopic fractionation patterns in forest ecosystems

    Science.gov (United States)

    Kurtz, A. C.; Takagi, K.

    2012-12-01

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

  18. Copper isotope fractionation in acid mine drainage

    Science.gov (United States)

    Kimball, B.E.; Mathur, R.; Dohnalkova, A.C.; Wall, A.J.; Runkel, R.L.; Brantley, S.L.

    2009-01-01

    We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The ??65Cu values (based on 65Cu/63Cu) of enargite (??65Cu = -0.01 ?? 0.10???; 2??) and chalcopyrite (??65Cu = 0.16 ?? 0.10???) are within the range of reported values for terrestrial primary Cu sulfides (-1??? waters (1.38??? ??? ??65Cu ??? 1.69???). The average isotopic fractionation (??aq-min = ??65Cuaq - ??65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ?? 0.14??? and 1.60 ?? 0.14??? for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ?? 0.14???) and enargite (0.98 ?? 0.14???) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (??aq-mino = - 0.57 ?? 0.14 ???, where mino refers to the starting mineral) and no apparent fractionation for enargite (??aq-mino = 0.14 ?? 0.14 ???). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of ??65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage

  19. Electrochemical hydrogen isotope sensor based on solid electrolytes

    International Nuclear Information System (INIS)

    Matsumoto, Hiroshige; Hayashi, Hiroyuki; Iwahara, Hiroyasu

    2002-01-01

    An electrochemical sensor of hydrogen isotopes based on solid electrolytes for determining the hydrogen isotope ratios and/or total hydrogen pressures in gases has been developed. This paper describes the methodology of the hydrogen isotope sensing together with experimental results. When hydrogen isotope gases are introduced to an electrochemical cell using a proton-conducting electrolyte (hydrogen isotope cell), the electromotive force (EMF) of the cell agrees with that theoretically estimated. The EMF signals can be used for the determination of the hydrogen isotope ratio in gases if the total hydrogen pressure is predetermined. By supplementary use of an oxide ion conductor cell, both the ratio and total pressure of the hydrogen isotopes can be simultaneously determined. (author)

  20. Hydrogen isotope permeation in elastomeric materials

    International Nuclear Information System (INIS)

    Steinmeyer, R.H.; Braun, J.D.

    1976-01-01

    The permeabilities of elastomeric and polymeric materials to hydrogen isotopes were measured at room temperature. The technique for measuring permeation rates is based on the following constant-volume method: a fixed pressure of gas is applied to one side of the specimen to be studied and the permeability constant is determined from the observed rate of pressure increase in an initially evacuated volume on the other side of the specimen. Permeability constants for hydrogen, deuterium, and tritium were measured for Mylar, Teflon, Kapton, Saran, Buna-N, and latex rubber. Results were compared with literature values for hydrogen and deuterium where available and showed excellent agreement

  1. Thermomagnetic torque in hydrogen isotopes

    International Nuclear Information System (INIS)

    Cramer, J.A.

    1975-01-01

    The thermomagnetic torque has been measured in parahydrogen and ortho and normal deuterium for pressures from 0.10 to 2.0 torr and temperatures from 100 to 370 K. Since the torque depends on the precession of the molecular rotational magnetic moment around the field direction, coupling of the molecular nuclear spin to the rotational moment can affect the torque. Evidence of spin coupling effects is found for the torque in both deuterium modifications. In para hydrogen the torque at all temperatures and pressures exhibits behavior expected of a gas of zero nuclear spin molecules. Additionally, earlier data for hydrogen deuteride and for normal hydrogen from 105 to 374 K are evaluated and discussed. The high pressure limiting values of torque peak heights and positions for all these gases are compared with theory

  2. Method of eliminating gaseous hydrogen isotopes

    International Nuclear Information System (INIS)

    Nagakura, Masaaki; Imaizumi, Hideki; Suemori, Nobuo; Aizawa, Takashi; Naito, Taisei.

    1983-01-01

    Purpose: To prevent external diffusion of gaseous hydrogen isotopes such as tritium or the like upon occurrence of tritium leakage accident in a thermonuclear reactor by recovering to eliminate the isotopes rapidly and with safety. Method: Gases at the region of a reactor container where hydrogen isotopes might leak are sucked by a recycing pump, dehumidified in a dehumidifier and then recycled from a preheater through a catalytic oxidation reactor to a water absorption tower. In this structure, the dehumidifier is disposed at the upstream of the catalytic oxidation reactor to reduce the water content of the gases to be processed, whereby the eliminating efficiency for the gases to be processed can be maintained well even when the oxidation reactor is operated at a low temperature condition near the ambient temperature. This method is based on the fact that the oxidating reactivity of the catalyst can be improved significantly by eliminating the water content in the gases to be processed. (Yoshino, Y.)

  3. Measuring hydrogen-isotope distribution profiles

    International Nuclear Information System (INIS)

    Poppe, C.H.

    1977-01-01

    A new nondestructive technique was developed for measuring the depth distribution of hydrogen isotopes absorbed or implanted near the surface of any material. The method allows real-time study of the inventory and diffusion of hydrogen, deuterium, and tritium. Briefly, the technique involves bombarding the surface with a monoenergetic beam of ions chosen for their ability to react with the hydrogen isotope in question and produce fast neutrons. The energy distribution of the neutrons is a sensitive indicator of the energy of the bombarding particles at the instant of reaction, and hence of the depth of the reaction sites below he surface of the material. A sensitivity of one part per million was obtained for tritium in copper. The technique is applicable to several energy-related materials problems. 5 figures

  4. Revised models of interstellar nitrogen isotopic fractionation

    Science.gov (United States)

    Wirström, E. S.; Charnley, S. B.

    2018-03-01

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

  5. The study of the deuterium isotopic fractionation through the cell membrane of the plant

    International Nuclear Information System (INIS)

    Berdea, P.; Cuna, Stela; Deliu, C.

    2002-01-01

    The purpose of this study is to prove that there is a water deuterium isotope fractionation when the water passes through the cell membrane. The carrots (Daucus carota) were grown in vitro in a Murashige and Skoog mineral-salt medium and have been exposed to a water solution with a uniform isotopic content. After seven days the cell culture was filtered and the cell water was vacuum extracted. The water from aqueous solution and the cell water were analyzed for hydrogen by isotope ratio mass spectrometry. The procedure was repeated for 14 and 21 day old cell cultures. The measurements have revealed a water deuterium isotopic fractionation between extra-cellular water and cellular water. The deuterium content was found to be higher within the cells by 10 o / oo for non-embryonic cells and 13 o / oo for the embryonic cells. This fractionation is a non-evaporative fractionation between intracellular and extra-cellular water and it represents a new step in the overall fractionation of deuterium water in the plants. The existence of such isotopic fractionation through the cell membrane implies that the relationship between the deuterium content of cellulose nitrate in plant and meteoric water should be revised. Also, this finding is of interest for understanding the balance and dynamics of the hydrogen isotopes in the environment. (authors)

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

    Energy Technology Data Exchange (ETDEWEB)

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

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

  7. Hydrogen isotope analysis by quadrupole mass spectrometry

    International Nuclear Information System (INIS)

    Ellefson, R.E.; Moddeman, W.E.; Dylla, H.F.

    1981-03-01

    The analysis of isotopes of hydrogen (H, D, T) and helium ( 3 He, 4 He) and selected impurities using a quadrupole mass spectrometer (QMS) has been investigated as a method of measuring the purity of tritium gas for injection into the Tokamak Fusion Test Reactor (TFTR). A QMS was used at low resolution, m/Δm 3 He, and 4 He in HT/D 2

  8. Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry

    Science.gov (United States)

    Coplen, Tyler B.; Qi, Haiping

    2010-01-01

    An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) δ2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

  9. Experimental study of relationship between average isotopic fractionation factor and evaporation rate

    Directory of Open Access Journals (Sweden)

    Tao Wang

    2010-12-01

    Full Text Available Isotopic fractionation is the basis of tracing the water cycle using hydrogen and oxygen isotopes. Isotopic fractionation factors in water evaporating from free water bodies are mainly affected by temperature and relative humidity, and vary significantly with these atmospheric factors over the course of a day. The evaporation rate (E can reveal the effects of atmospheric factors. Therefore, there should be a certain functional relationship between isotopic fractionation factors and E. An average isotopic fractionation factor (α* was defined to describe isotopic differences between vapor and liquid phases in evaporation with time intervals of days. The relationship between α* and E based on the isotopic mass balance was investigated through an evaporation pan experiment with no inflow. The experimental results showed that the isotopic compositions of residual water were more enriched with time; α* was affected by air temperature, relative humidity, and other atmospheric factors, and had a strong functional relation with E. The values of α* can be easily calculated with the known values of E, the initial volume of water in the pan, and isotopic compositions of residual water.

  10. Intracrystalline site preference of hydrogen isotopes in borax

    International Nuclear Information System (INIS)

    Pradhananga, T.M.; Matsuo, S.

    1985-01-01

    The total hydrogen involved in borax synthesized at 25 0 C in aqueous solution is enriched in deuterium by 5.3% compared with the mother liquor. There is no change in the value of the D/H fractionation factor between the hydrogen in borax and those in the mother liquor with changes in the degree of supersaturation. The fractionation factor changes slightly with a change in the crystallization temperature of borax in the range from 5 to 25 0 C. The D/H ratio in the different sites of borax was estimated by a fractional dehydration technique. The results show that hydrogen atoms of the polyanionic group [B 4 O 5 (OH) 4 ] are much more enriched in deuterium than those of the cationic group [Na 2 x 8H 2 O]. The delta D values, referred to the mother liquor from which the borax was crystallized, for the cationic group (site A) and the polyanionic group (site B) are -35 +/- 3 and 167 +/- 13%, respectively based on the fractional dehydration results obtained at -21 0 C. At -21 0 C, isotopic exchange between different sites during dehydration is assumed not to occur. The mechanism for dehydration of borax is discussed. 48 references, 8 figures, 3 tables

  11. The hydrogen isotopic composition of kaolin minerals in Japan

    International Nuclear Information System (INIS)

    Marumo, Katsumi; Nagasawa, Keinosuke; Kuroda, Yoshimasu.

    1979-01-01

    Hydrogen isotopic composition (D/H ratio) was determined for kaolin minerals from geothermal areas and sedimentary and hydrothermal kaolin deposits in Japan. On the Ohnuma, Matsukawa, and Ohtake geothermal areas, the hydrogen isotopic fractionation factor between kaolin minerals and water was calculated to fall between 0.97 and 0.99 for the temperature range of 50 to 200 0 C, a fact which shows that the temperature of formation has no important effect on the D/H ratio of kaolin minerals. D/H ratio of kaolinites and dickites from many kaolin deposits shows local variation, and seems to correlate with isotopic variation of the present-day meteoric surface water. Exceptions are seen in some kaolin deposits such as Shokozan, Hiroshima Prefecture, where kaolinite and dickite have considerably high values of D/H ratio, and seem to have reacted with water rich in deuterium. D/H ratio of halloysite is not correlated with that of the present-day meteoric surface water. As Lawrence and Taylor (1971) pointed out, the original D/H ratio of constitutional water of halloysite is not preserved because of the isotopic exchange between the interlayer water and the constitutional water. (author)

  12. Hydrogen isotope separation for fusion power applications

    Energy Technology Data Exchange (ETDEWEB)

    Smith, R., E-mail: robert.smith@ccfe.ac.uk [EURATOM/CCFE Fusion Association, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); JET-EFDA, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); Whittaker, D.A.J.; Butler, B.; Hollingsworth, A.; Lawless, R.E.; Lefebvre, X.; Medley, S.A.; Parracho, A.I.; Wakeling, B. [EURATOM/CCFE Fusion Association, Culham Science Centre, Abingdon OX14 3DB (United Kingdom); JET-EFDA, Culham Science Centre, Abingdon OX14 3DB (United Kingdom)

    2015-10-05

    Highlights: • Summary of the tritium plant, the Active Gas Handling System (AGHS), at JET. • Review of the Water Detritiation System (WDS) under construction. • Design of the new Material Detritiation Facility (MDF). • Review of problems in fusion related to metal/hydrogen system. - Abstract: The invited talk given at MH2014 in Salford ranged over many issues associated with hydrogen isotope separation, fusion machines and the hydrogen/metal systems found in the Joint European Torus (JET) machine located near Oxford. As this sort of talk does not lend itself well to a paper below I have attempted to highlight some of the more pertinent information. After a description of the Active Gas Handling System (AGHS) a brief summary of isotope separation systems is described followed by descriptions of three major projects currently being undertaken by the Tritium Engineering and Science Group (TESG), the upgrade to the Analytical Systems (AN-GC) at the AGH, the construction of a Water Detritiation System (WDS) and a Material Detritiation Facility (MDF). Finally, a review of some of the challenges facing fusion with respect to metal/hydrogen systems is presented.

  13. A Hydrogen and He Isotope Nanoprobe

    Energy Technology Data Exchange (ETDEWEB)

    Doyle, Barney L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Van Deusen, Stuart B. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-09-01

    Materials that incorporate hydrogen and helium isotopes are of great interest at Sandia and throughout the NNSA and DOE. The Ion Beam Lab at SNL-NM has invented techniques using micron to mm-size MeV ion beams to recoil these light isotopes (Elastic Recoil Detection or ERD) that can very accurately make such measurements. However, there are many measurements that would benefit NW and DOE that require much better resolution, such as the distribution of H isotopes (and 3He) in individual grains of materials relevant to TPBARs, H and He-embrittlement of weapon components important to Tritium Sustainment Programs, issues with GTSs, batteries… Higher resolution would also benefit the field of materials science in general. To address these and many other issues, nm-scale lateral resolution is required. This LDRD demonstrated that neutral H atoms could be recoiled through a thin film by 70 keV electrons and detected with a Channeltron electron multiplier (CEM). The electrons were steered away from the CEM by strong permanent magnets. This proved the feasibility that the high energy electrons from a transmissionelectron- microscope-TEM can potentially be used to recoil and subsequently detect (e-ERD), quantify and map the concentration of H and He isotopes with nm resolution. This discovery could lead to a TEM-based H/He-isotope nanoprobe with 1000x higher resolution than currently available.

  14. Effects of trace element concentration on enzyme controlled stable isotope fractionation during aerobic biodegradation of toluene.

    Science.gov (United States)

    Mancini, Silvia A; Hirschorn, Sarah K; Elsner, Martin; Lacrampe-Couloume, Georges; Sleep, Brent E; Edwards, Elizabeth A; Lollar, Barbara Sherwood

    2006-12-15

    The effects of iron concentration on carbon and hydrogen isotopic fractionation during aerobic biodegradation of toluene by Pseudomonas putida mt-2 were investigated using a low iron medium and two different high iron media. Mean carbon enrichment factors (epsilonc) determined using a Rayleigh isotopic model were smaller in culture grown under high iron conditions (epsilonc = -1.7+/-0.1%) compared to low iron conditions (epsilonc = -2.5+/-0.3%). Mean hydrogen enrichment factors (epsilonH) were also significantly smaller for culture grown under high iron conditions (epsilonH = -77 +/-4%) versus low iron conditions (EpsilonH = -159+/-11%). A mechanistic model for enzyme kinetics was used to relate differences in the magnitude of isotopic fractionation for low iron versus high iron cultures to the efficiency of the enzymatic transformation. The increase of carbon and hydrogen enrichment factors at low iron concentrations suggests a slower enzyme-catalyzed substrate conversion step (k2) relative to the enzyme-substrate binding step (k-l) at low iron concentration. While the observed differences were subtle and, hence, do not significantly impact the ability to use stable isotope analysis in the field, these results demonstrated that resolvable differences in carbon and hydrogen isotopic fractionation were related to low and high iron conditions. This novel result highlights the need to further investigate the effects of other trace elements known to be key components of biodegradative enzymes.

  15. Molybdenum isotope fractionation in the mantle

    Science.gov (United States)

    Liang, Yu-Hsuan; Halliday, Alex N.; Siebert, Chris; Fitton, J. Godfrey; Burton, Kevin W.; Wang, Kuo-Lung; Harvey, Jason

    2017-02-01

    We report double-spike molybdenum (Mo) isotope data for forty-two mafic and fifteen ultramafic rocks from diverse locations and compare these with results for five chondrites. The δ98/95Mo values (normalized to NIST SRM 3134) range from -0.59 ± 0.04 to +0.10 ± 0.08‰. The compositions of one carbonaceous (CI) and four ordinary chondrites are relatively uniform (-0.14 ± 0.01‰, 95% ci (confidence interval)) in excellent agreement with previous data. These values are just resolvable from the mean of 10 mid-ocean ridge basalts (MORBs) (0.00 ± 0.02‰, 95% ci). The compositions of 13 mantle-derived ultramafic xenoliths from Kilbourne Hole, Tariat and Vitim are more diverse (-0.39 to -0.07‰) with a mean of -0.22 ± 0.06‰ (95% ci). On this basis, the isotopic composition of the bulk silicate Earth (BSE or Primitive Mantle) is within error identical to chondrites. The mean Mo concentration of the ultramafic xenoliths (0.19 ± 0.07 ppm, 95% ci) is similar in magnitude to that of MORB (0.48 ± 0.13 ppm, 95% ci), providing evidence, either for a more compatible behaviour than previously thought or for selective Mo enrichment of the subcontinental lithospheric mantle. Intraplate and ocean island basalts (OIBs) display significant isotopic variability within a single locality from MORB-like to strongly negative (-0.59 ± 0.04‰). The most extreme values measured are for nephelinites from the Cameroon Line and Trinidade, which also have anomalously high Ce/Pb and low Mo/Ce relative to normal oceanic basalts. δ98/95Mo correlates negatively with Ce/Pb and U/Pb, and positively with Mo/Ce, explicable if a phase such as an oxide or a sulphide liquid selectively retains isotopically heavy Mo in the mantle and fractionates its isotopic composition in low degree partial melts. If residual phases retain Mo during partial melting, it is possible that the [Mo] for the BSE may be misrepresented by values estimated from basalts. This would be consistent with the high Mo

  16. Kinetics of the excited muonic hydrogen in the mixtures of hydrogen isotopes in helium

    International Nuclear Information System (INIS)

    Bystritskij, V.M.; Kravtsov, A.V.; Popov, N.P.

    1989-01-01

    De-excitation of the excited muonic hydrogen in the mixture of hydrogen isotopes and helium is considered. The method is proposed which allows one to determine the rates of the muon transfer from the excited muonic hydrogen to helium nuclei, as well as the probability of the direct muon atomic capture by nuclei of hydrogen isotopes. 20 refs.; 4 figs

  17. 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

  18. Xenon Fractionation and Archean Hydrogen Escape

    Science.gov (United States)

    Zahnle, K. J.

    2015-01-01

    Xenon is the heaviest gas found in significant quantities in natural planetary atmospheres. It would seem the least likely to escape. Yet there is more evidence for xenon escape from Earth than for any element other than helium and perhaps neon. The most straightforward evidence is that most of the radiogenic Xe from the decay of (129)I (half-life 15.7 Myr) and (244)Pu (half-life 81 Myr) that is Earth's birthright is missing. The missing xenon is often attributed to the impact erosion of early atmospheres of Earth and its ancestors. It is obvious that if most of the radiogenic xenon were driven off by impacts, most of the rest of the atmophiles fared the same fate. The other line of evidence is in the nonradiogenic isotopes of xenon and its silent partner, krypton. Atmospheric xenon is strongly mass fractionated (at about 4% per amu) compared to any known solar system source (Figure 1). This is in stark contrast to krypton, which may not be fractionated at all: atmospheric Kr is slightly heavier than solar Kr (at about 0.5% per amu), but it is the same as in carbonaceous chondrites. Nonradiogenic xenon is also under abundant relative to krypton (the so-called "missing xenon" problem). Together these observations imply that xenon has been subject to fractionating escape and krypton not.

  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. 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

  1. Hydrogen isotope ratios of mouse tissues are influenced by a variety of factors other than diet

    International Nuclear Information System (INIS)

    DeNiro, M.J.; Epstein, S.

    1981-01-01

    Hydrogen isotopes are fractionated during biochemical reactions in a variety of organisms. A number of experiments have shown that the D/H ratios of animals and their tissues are not controlled solely by the D/H ratios of their food. The authors performed a simple experiment which indicated that the D/H ratios of a significant fraction of the organically bonded hydrogen in animal tissues must be determined by the isotopic composition of water that the samples encounter. Aliquots of dried mouse brain and liver and mouse food were exposed to water vapors of different D/H ratios prior to isotopic analysis. The results of the experiment showed that at least 16 percent of the hydrogen in mouse brain is exchangeable with the hydrogen of water; the corresponding values for mouse liver and mouse food were 25 to 29 percent

  2. 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)

  3. Impact analysis of a hydrogen isotopes container

    International Nuclear Information System (INIS)

    Lee, M. S.; Hwang, C. S.; Jeong, H. S.

    2003-01-01

    The container used for the radioactive materials, containing hydrogen isotopes is evaluated in a view of hypothetical accident. The computational analysis is a cost effective tool to minimize testing and streamline the regulatory procedures, and supports experimental programs to qualify the container for the safe transport of radioactive materials. The numerical analysis of 9m free-drop onto a flat unyielding, horizontal surface has been performed using the explicit finite element computer program ABAQUS. Especially free-drop simulations for 30 .deg. C tilted condition are precisely estimated

  4. Dynamic simulation of hydrogen isotope distillation unit

    International Nuclear Information System (INIS)

    Le Lann, J.M.; Latge, C.; Joulia, X.; Sere-Peyrigain, P.

    1995-01-01

    Dynamic simulation of hydrogen isotope distillation unit involved in the complex environment of a fusion power plant can be a powerful technique in view to analyze the tritium hazard potential. In this paper, issues related to the development of such a dynamic simulator with model formulation and the numerical treatment of the resulting Differential-Algebraic equation (DAE) system are properly adressed. The typical dynamic characteristics of such columns are quantitatively and qualitatively enlighted on case study with very large disturbances. The developed system has proven to be beneficial for understanding the dynamic behaviour and further for developing control schemes. (orig.)

  5. Dynamic simulation of hydrogen isotope distillation unit

    International Nuclear Information System (INIS)

    Le Lann, J.M.; Joulia, X.; Sere-Peyrigain, P.

    1994-01-01

    Dynamic simulation of hydrogen isotope distillation unit involved in the complex environment of a fusion power plant can be a powerful technique in view to analyze the tritium hazard potential. Issues related to the development of such a dynamic simulator with model formulation and the numerical treatment of the resulting Differential-Algebraic equation (DAE) system are properly addressed. The typical dynamic characteristics of such columns are quantitatively and qualitatively enlightened on case study with very large disturbances. The developed system has proven to be beneficial for understanding the dynamic behaviour and further for developing control schemes. (author) 12 refs.; 4 figs

  6. Short-term measurement of carbon isotope fractionation in plants

    International Nuclear Information System (INIS)

    O'Leary, M.H.; Treichel, I.; Rooney, M.

    1986-01-01

    Combustion-based studies of the carbon-13 content of plants give only an integrated, long-term value for the isotope fractionation associated with photosynthesis. A method is described here which permits determination of this isotope fractionation in 2 to 3 hours. To accomplish this, the plant is enclosed in a glass chamber, and the quantity and isotopic content of the CO 2 remaining in the atmosphere are monitored during photosynthesis. Isotope fractionation studies by this method give results consistent with what is expected from combustion studies of C 3 , C 4 , and Crassulacean acid metabolism plants. This method will make possible a variety of new studies of environmental and species effects in carbon isotope fractionation

  7. Adsorption methods for hydrogen isotope storage on zeolite sieves

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  8. Relationship between microbial sulfate reduction rates and sulfur isotopic fractionation

    Science.gov (United States)

    Matsu'Ura, F.

    2009-12-01

    Sulfate reduction is one of the common processes to obtain energy for certain types of microorganisms.They use hydrogen gas or organic substrates as electron donor and sulfates as electron acceptor, and reduce sulfates to sulfides. Sulfate reducing microbes extend across domains Archea and Bacteria, and are believed to be one of the earliest forms of terrestrial life (Shen 2004). The origin of 34S-depleted (light) sulfide sulfur, especially δ34S vials, which contain 40ml of liquid culture media slightly modified from DSMZ #63 medium.Excess amount of Fe (II) is added to the DSMZ#63 medium to precipitate sulfide as iron sulfide. The vials were incubated at 25°C, 30°C, and 37°C, respectively. 21 vials were used for one temperature and sulfide and sulfate was collected from each three glass vials at every 12 hours from 72 hours to 144 hours after start of incubation. The sulfide was precipitated as iron sulfide and the sulfate was precipitated as barite. Sulfur isotope compositions of sulfate and sulfide were measured by standard method using Delta Plus mass-spectrometer. [Results and Discussion] The fractionation between sulfide and sulfate ranged from 2.7 to 11.0. The fractionation values varied among the different incubation temperature and growth phase of D. desulfuricans. The maximum fractionation values of three incubation temperatures were 9.9, 11.0, and 9.7, for 25 °C, 30°C, and 37°C, respectively. These results were different from standard model and Canfield et al. (2006). I could not find the clear correlation between ∂34S values and incubation temperatures in this experiment. The measured fractionation values during the incubation varied with incubation stage. The fractionation values clearly increased with incubation time at every temperature, and at 25°C ∂34S value was 3.6 at the 72h and it increased to 7.9 at 144 hours. This indicated the difference of sulfate reduction rate due to the growth phase of SRB. In the early logarithmic growth phase

  9. 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

  10. Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

    Science.gov (United States)

    Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

    2014-01-01

    Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

  11. Monitoring biodegradation of hydrocarbons by stable isotope fractionation

    Science.gov (United States)

    Dorer, Conrad; Fischer, Anko; Herrmann, Steffi; Richnow, Hans-Hermann; Vogt, Carsten

    2010-05-01

    In the last decade, several studies have demonstrated that stable isotope tools are highly applicable for monitoring anaerobic biodegradation processes. An important methodological approach is to characterize distinct degradation pathways with respect to the specific mechanism of C-H-bond cleavage and to quantify the extent of biodegradation by compound specific isotope analysis (CSIA). Here, enrichment factors (ɛbulk) needed for a CSIA field site approach must be determined in laboratory reference experiments. Recent research results from different laboratories have shown that single ɛbulk values for similar degradation pathways can be highly variable; thus, the use of two-dimensional compound specific isotope analysis (2D-CSIA) has been encouraged for characterizing biodegradation pathways more precisely. 2D-CSIA for hydrocarbons can be expressed by the slope of the linear regression for hydrogen versus carbon discrimination known as lambda ≈ ɛHbulk/ɛCbulk. We determined the carbon and hydrogen isotope fractionation for the biodegradation of benzene, toluene and xylenes by various reference cultures. Specific enzymatic reactions initiating different biodegradation pathways could be distinguished by 2D-CSIA. For the aerobic di- and monohydroxylation of the benzene ring, lambda values always lower than 9 were observed. Enrichment cultures degrading benzene anaerobically produced significant different values: lambda values between 8-19 were oberved for nitrate-reducing consortia, whereas sulfate-reducing and methanogenic consortia showed always lambda values greater than 20 [1,2]. The observed variations suggest that (i) aerobic benzene biodegradation can be distinguished from anaerobic biodegradation, and (ii) that more than a single mechanism seems to exist for the activation of benzene under anoxic conditions. lambda values for anaerobic toluene degradation initiated by the enzyme benzylsuccinate synthase (BSS) ranged from 4 to 41, tested with strains using

  12. Kinetic isotopic fractionation during diffusion of ionic species in water

    Science.gov (United States)

    Richter, Frank M.; Mendybaev, Ruslan A.; Christensen, John N.; Hutcheon, Ian D.; Williams, Ross W.; Sturchio, Neil C.; Beloso, Abelardo D.

    2006-01-01

    Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine DLi/DK,D/D,D/D,D/D,andD/D. The measured ratio of the diffusion coefficients for Li and K in water (D Li/D K = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D/D=0.99772±0.00026). This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D/D=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D/D=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.

  13. Fractionation of boron isotopes in Icelandic hydrothermal systems

    International Nuclear Information System (INIS)

    Aggarwal, J.K.

    1995-01-01

    Boron isotope ratios have been determined in a variety of different geothermal waters from hydrothermal systems across Iceland. Isotope ratios from the high temperature meteoric water recharged systems reflect the isotope ratio of the host rocks without any apparent fractionation. Seawater recharged geothermal systems exhibit more positive δ 1 1B values than the meteoric water recharged geothermal systems. Water/rock ratios can be assessed from boron isotope ratios in the saline hydrothermal systems. Low temperature hydrothermal systems also exhibit more positive δ 1 1B than the high temperature systems, indicating fractionation of boron due to absorption of the lighter isotope onto secondary minerals. Fractionation of boron in carbonate deposits may indicate the level of equilibrium attained within the systems. (author). 14 refs., 2 figs

  14. 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

  15. 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

  16. Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

    Science.gov (United States)

    Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

    2016-04-01

    Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

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

    Science.gov (United States)

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

    2016-12-01

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

  18. Temperature dependence of carbon isotope fractionation in CAM plants

    International Nuclear Information System (INIS)

    Deleens, E.; Treichel, I.; O'Leary, M.H.

    1985-01-01

    The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoë daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17 degrees C nights, 23 degrees C days), the isotope fractionation for both plants is -4 per thousand (that is, malate is enriched in (13)C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0 per thousand at 27 degrees C/33 degrees C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process

  19. Temperature dependence of carbon isotope fractionation in CAM plants

    Energy Technology Data Exchange (ETDEWEB)

    Deleens, E.; Treichel, I.; O' Leary, M.H.

    1985-09-01

    The carbon isotope fractionation associated with nocturnal malic acid synthesis in Kalanchoe daigremontiana and Bryophyllum tubiflorum was calculated from the isotopic composition of carbon-4 of malic acid, after appropriate corrections. In the lowest temperature treatment (17/sup 0/C nights, 23/sup 0/C days), the isotope fractionation for both plants is -4% per thousand (that is, malate is enriched in /sup 13/C relative to the atmosphere). For K. daigremontiana, the isotope fractionation decreases with increasing temperature, becoming approximately 0% per thousand at 27/sup 0/C/33/sup 0/C. Detailed analysis of temperature effects on the isotope fractionation indicates that stomatal aperture decreases with increasing temperature and carboxylation capacity increases. For B. tubiflorum, the temperature dependence of the isotope fractionation is smaller and is principally attributed to the normal temperature dependences of the rates of diffusion and carboxylation steps. The small change in the isotopic composition of remaining malic acid in both species which is observed during deacidification indicates that malate release, rather than decarboxylation, is rate limiting in the deacidification process. 28 references, 1 figure, 4 tables.

  20. Diversity of sulfur isotope fractionations by sulfate-reducing prokaryotes

    DEFF Research Database (Denmark)

    Detmers, Jan; Brüchert, Volker; Habicht, K S

    2001-01-01

    Batch culture experiments were performed with 32 different sulfate-reducing prokaryotes to explore the diversity in sulfur isotope fractionation during dissimilatory sulfate reduction by pure cultures. The selected strains reflect the phylogenetic and physiologic diversity of presently known...... sulfate reducers and cover a broad range of natural marine and freshwater habitats. Experimental conditions were designed to achieve optimum growth conditions with respect to electron donors, salinity, temperature, and pH. Under these optimized conditions, experimental fractionation factors ranged from 2.......0 to 42.0 per thousand. Salinity, incubation temperature, pH, and phylogeny had no systematic effect on the sulfur isotope fractionation. There was no correlation between isotope fractionation and sulfate reduction rate. The type of dissimilatory bisulfite reductase also had no effect on fractionation...

  1. Molybdenum isotope fractionation during adsorption to organic matter

    Science.gov (United States)

    King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

    2018-01-01

    Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

  2. Hydrogen isotope separation experience at the Savannah River Site

    International Nuclear Information System (INIS)

    Lee, M.W.

    1993-01-01

    Savannah River Site (SRS) is a sole producer of tritium for US Weapons Program. SRS has built Facilities, developed the tritium handling processes, and operated safely for the last forty years. Tritium is extracted from the irradiated reactor target, purified, mixed with deuterium, and loaded to the booster gas bottle in the weapon system for limited lifetime. Tritium is recovered from the retired bottle and recycled. Newly produced tritium is branded into the recycled tritium. One of the key process is the hydrogen isotope separation that tritium is separated from deuterium and protium. Several processes have been used for the hydrogen isotope separation at SRS: Thermal Diffusion Column (TD), Batch Cryogenic Still (CS), and Batch Chromatography called Fractional Sorption (FS). TD and CS requires straight vertical columns. The overall system separation factor depends on the length of the column. These are three story building high and difficult to put in glove box. FS is a batch process and slow operation. An improved continuous chromatographic process called Thermal Cycling Absorption Process (TCAP) has been developed. It is small enough to be about to put in a glove box yet high capacity comparable to CS. The SRS tritium purification processes can be directly applicable to the Fusion Fuel Cycle System of the fusion reactor

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

    International Nuclear Information System (INIS)

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

    1990-01-01

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

  4. 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

  5. Pressure dependent isotopic fractionation in the photolysis of formaldehyde-d2

    DEFF Research Database (Denmark)

    Nilsson, E.J.K.; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

    2014-01-01

    role in the observed pressure dependent photolytic fractionation of deuterium. The model shows that part of the fractionation is a result of competition between the isotopologue dependent rates of unimolecular dissociation and collisional relaxation. We suggest that the remaining fractionation is due......The isotope effects in formaldehyde photolysis are the key link between the δD of methane emissions and the δD of atmospheric in situ hydrogen production. A few recent studies have suggested that a pressure dependence in the isotopic fractionation can partly explain enrichment of deuterium...... with altitude in the atmosphere. The mechanism and the extent of this pressure dependency is, however, not adequately described. In the present work D2CO and H2CO were photolyzed in a static reaction chamber at bath gas pressures of 50, 200, 400, 600 and 1000 mbar; these experiments compliment and extend our...

  6. Development of a new method for hydrogen isotope analysis of trace hydrocarbons in natural gas samples

    Directory of Open Access Journals (Sweden)

    Xibin Wang

    2016-12-01

    Full Text Available A new method had been developed for the analysis of hydrogen isotopic composition of trace hydrocarbons in natural gas samples by using solid phase microextraction (SPME combined with gas chromatography-isotope ratio mass spectrometry (GC/IRMS. In this study, the SPME technique had been initially introduced to achieve the enrichment of trace content of hydrocarbons with low abundance and coupled to GC/IRMS for hydrogen isotopic analysis. The main parameters, including the equilibration time, extraction temperature, and the fiber type, were systematically optimized. The results not only demonstrated that high extraction yield was true but also shows that the hydrogen isotopic fractionation was not observed during the extraction process, when the SPME device fitted with polydimethylsiloxane/divinylbenzene/carbon molecular sieve (PDMS/DVB/CAR fiber. The applications of SPME-GC/IRMS method were evaluated by using natural gas samples collected from different sedimentary basins; the standard deviation (SD was better than 4‰ for reproducible measurements; and also, the hydrogen isotope values from C1 to C9 can be obtained with satisfying repeatability. The SPME-GC/IRMS method fitted with PDMS/DVB/CAR fiber is well suited for the preconcentration of trace hydrocarbons, and provides a reliable hydrogen isotopic analysis for trace hydrocarbons in natural gas samples.

  7. Fractionation of Stable Isotopes in Atmospheric Aerosol Reactions

    DEFF Research Database (Denmark)

    Meusinger, Carl

    -independent) fractionation processes of stable isotopes of C, N, O and S in order to investigate three different systems related to aerosols: 1. Post-depositional processes of nitrate in snow that obscure nitrate ice core records 2. Formation and aging of secondary organic aerosol generated by ozonolysis of X...... reactions and undergo complex chemical and physical changes during their lifetimes. In order to assess processes that form and alter aerosols, information provided by stable isotopes can be used to help constrain estimates on the strength of aerosol sources and sinks. This thesis studies (mass...... as required. The kndings provide important results for the studies' respective felds, including a description of the isotopic fractionation and quantum yield of nitrate photolysis in snow, equilibrium fractionation in secondary organic aerosol and fractionation constants of different oxidation pathways of SO2....

  8. Intracrystalline site preference of hydrogen isotopes in the water of crystallization of copper sulfate pentahydrate

    International Nuclear Information System (INIS)

    Kita, I.; Matsuo, S.

    1981-01-01

    Difference in the isotopic partition at different sites of the water of crystallization of CuSO 4 .5H 2 O (the site preference) was estimated for the hydrogen isotopes. Fractional dehydration of CuSO 4 .5H 2 O under vacuum at 0 and 25 0 C was used to determine the isotopic ratio, the amount of dehydrated water, and the rate process of dehydration. The following results were obtained. (1) Two maxima occur in the isotopic ratio in the dehydration range, F < 0.8. (2) The dehydration occurs by the three sequential zeroth-order rate processes which have different rate constants for dehydration. The three different rate constants may be explained by the combination of the rate constants of dehydration of the water molecules dehydrated. The estimation of the difference in hydrogen isotope distribution for different sites, i.e., four of the five water molecules in the coordination sphere of copper ion (site A) and one bonded to the sulfate ion through hydrogen bonding (site B) was made. The site preference of hydrogen isotopes (delta D,%) was concluded to be -3.20 +- 0.52 for site A and +2.26 +- 2.09 for site B, where the delta D value was referred to the isotopic ratio of the mother liquor from which the crystal was formed

  9. Intracrystalline site preference of hydrogen isotopes in the water of crystallization of copper sulfate pentahydrate

    Energy Technology Data Exchange (ETDEWEB)

    Kita, I.; Matsuo, S.

    1981-04-02

    Difference in the isotopic partition at different sites of the water of crystallization of CuSO/sub 4/.5H/sub 2/O (the site preference) was estimated for the hydrogen isotopes. Fractional dehydration of CuSO/sub 4/.5H/sub 2/O under vacuum at 0 and 25/sup 0/C was used to determine the isotopic ratio, the amount of dehydrated water, and the rate process of dehydration. The following results were obtained. (1) Two maxima occur in the isotopic ratio in the dehydration range, F < 0.8. (2) The dehydration occurs by the three sequential zeroth-order rate processes which have different rate constants for dehydration. The three different rate constants may be explained by the combination of the rate constants of dehydration of the water molecules dehydrated. The estimation of the difference in hydrogen isotope distribution for different sites, i.e., four of the five water molecules in the coordination sphere of copper ion (site A) and one bonded to the sulfate ion through hydrogen bonding (site B) was made. The site preference of hydrogen isotopes (delta D,%) was concluded to be -3.20 +- 0.52 for site A and +2.26 +- 2.09 for site B, where the delta D value was referred to the isotopic ratio of the mother liquor from which the crystal was formed.

  10. 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

  11. Device to remove hydrogen isotopes from a gas phase

    International Nuclear Information System (INIS)

    Morlock, G.; Wiesemes, J.; Bachner, D.

    1977-01-01

    The device described here guarantees the selective removal of hydrogen isotopes from gas phases in order to prevent the occurence of explosive H 2 gas mixtures, or to separate off radioactive tritium in nuclear plants from the gas phase. It consists of a closed container whose walls are selectively penetrable by hydrogen isotopes. It is simultaneously filled compactly and presssure-resistant with a metal bulk (e.g. powder, sponges or the like of titanium or other hydrogen isotope binding metal). Walling and bulk are maintained at suitable working temperatures by means of a system according to the Peltier effect. The whole thing is safeguarded by protective walling. (RB) [de

  12. Gallium isotope fractionation during Ga adsorption on calcite and goethite

    Science.gov (United States)

    Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

    2018-02-01

    Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its

  13. Calcium Isotope Geochemistry: Research Horizons and Nanoscale Fractionation Processes

    Science.gov (United States)

    Watkins, J. M.; Depaolo, D. J.; Richter, F. M.; Fantle, M. S.; Simon, J. I.; Ryerson, F. J.; Ewing, S. A.; Turchyn, A. V.; Yang, W.; Owens, T. L.

    2008-12-01

    Interest in studies of calcium isotope variations in nature continues to increase. Investigations span human biology, plants and soils, oceanography and paleoclimate, early solar system processes, aqueous geochemistry, and silicate liquid structure. Variations in the 44Ca/40Ca ratio are generally small, about 5 ‰, but gradual small improvements in analytical capability now yield 0.05 to 0.1 ‰ resolution. The field is still plagued by a lack of universal standards for isotope ratios and data representation, but these are secondary issues. Traditional isotopic systems have been based in equilibrium thermodynamics, which can explain the magnitude and sign of observed mass-dependent fractionation behavior. For Ca isotopes this is not the case. There is still no reliable way to estimate the equilibrium free energy associated with isotopic exchange between most phases of interest. Experiments are difficult to interpret because it is almost impossible to precipitate minerals from aqueous solution at equilibrium at low temperature. Some studies suggest that, for example, there is no equilibrium isotopic fractionation between calcite and dissolved aqueous Ca. There is good evidence that most Ca isotopic fractionation is caused by kinetic effects. The details of the controlling processes are still missing, and without this mechanistic understanding it is difficult to fully understand the implications of natural isotopic variations. Recent work on dissolved Ca, calcite, and sulfates in both laboratory and natural settings is shedding light on where the fractionation may arise. There is emerging evidence for mass dependent fractionation associated with aqueous diffusion, but probably the primary source of the effects is in the details of precipitation of minerals from solution. This makes the fractionation potentially dependent on a number of factors, including solution composition and mineral growth rate. The next challenge is to develop appropriate experimental tests and

  14. The lack of potassium-isotopic fractionation in Bishunpur chondrules

    Science.gov (United States)

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

    2000-01-01

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

  15. Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

    Science.gov (United States)

    Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

    2018-06-01

    As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during

  16. Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

    Science.gov (United States)

    Ellis, A.; Johnson, T. M.; Bullen, T. D.

    2001-12-01

    Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no

  17. Tritium isotope fractionation in biological systems and in analytical procedures

    International Nuclear Information System (INIS)

    Kim, M.A.; Baumgaertner, Franz

    1989-01-01

    The organically bound tritium (OBT) is evaluated in biological systems by determining the tritium distribution ratio (R-value), i.e. tritium concentrations in organic substance to cell water. The determination of the R-value always involves isotope fractionation is applied analytical procedures and hence the evaluation of the true OBT -value in a given biological system appears more complicated than hitherto known in the literature. The present work concentrates on the tritium isotope fractionation in the cell water separation and on the resulting effects on the R-value. The analytical procedures examined are vacuum freeze drying under equilibrium and non-equilibrium conditions and azeotropic distillation. The vaporization isotope effects are determined separately in the phase transition of solid or liquid to gas in pure tritium water systems as well as in real biological systems, e.g. corn plant. The results are systematically analyzed and the influence of isotope effects on the R-value is rigorously quantified

  18. Gas-chromatographic separation of hydrogen isotopic mixtures

    International Nuclear Information System (INIS)

    Preda, Anisoara; Bidica, Nicolae

    2005-01-01

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

  19. 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

  20. Isotopic fractionation and profile evolution of a melting snowcover

    Institute of Scientific and Technical Information of China (English)

    周石硚; 中尾正义; 桥本重将; 坂井亚规子; 成田英器; 石川信敬

    2001-01-01

    Successive snow pits were dug intensively in a melting snowcover. Water was successfully separated from snow grains in the field for the first time. By measuring δ18O values of water and snow grain samples as well as comparing isotopic profiles, it is found that meltwater percolating down in snow develops quick and clear isotopic fractionation with snow grains, but exerts no clear impact on the δ18O profile of the snowcover through which the meltwater percolates.

  1. New mass spectrometers for hydrogen isotope analyses

    International Nuclear Information System (INIS)

    Chastagner, P.; Daves, H.L.; Hess, W.B.

    1981-01-01

    Two advanced mass spectrometers for the accurate analysis of mixtures of the hydrogen isotopes are being evaluated by Du Pont personnel at the Savannah River Laboratory. One is a large double-focusing instrument with a resolution of 2000 at mass 4, an abundance sensitivity of > 100,000 for the HT-D 2 doublet, and a sophisticated electronic control and data collection system. The second is a smaller, simpler, stigmatic-focusing instrument in which exceptionally high ion intensities (> 1 x 10 -9 A) result in high signal to noise ratios. A containment facility with sample inlet systems and a standard distribution system was built to permit testing with tritium mixtures. The characteristics of the mass spectrometers under a variety of operating conditions will be presented. Factors to be discussed include: sample equilibration and its elimination; linearity; trimer formation; gas interference; stability; signal to noise ratio; mass discrimination; and anticipated precision and accu sublimed molybdenum collector of Converter No. 262; and (3) demonstration of tungsten CVD onto molybdenum flange using a reuseable graphite mandrel

  2. Chromium isotope fractionation during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

    The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during the Ar...... et al., 2007, Water Air Soil Poll. 179, 381-390. [2] Sánchez-Pastor et al., 2011, Cryst. Growth Des. 11, 3081-3089.......The chromium (Cr) isotopic composition of carbonates can potentially be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenvironmental changes, for example related to the rise of oxygen during...... the Archaean and Protoerozoic, needs careful assessment of the signal robustness and necessitates a thorough understanding of the Cr cycle in Earth system processes. We conducted experiments testing the incorporation and isotopic fractionation of chromate into the calcite lattice. Our experiments indicate...

  3. Separation of hydrogen isotopes via single column pressure swing adsorption

    International Nuclear Information System (INIS)

    Wong, Y.W.; Hill, F.B.

    1981-01-01

    Separation of hydrogen isotopes based on kinetic isotope effects was studied. The mixture separated was hydrogen containing a trace of tritium as HT and the hydride was vanadium monohydride. The separation was achieved using the single-column pressure swing process. Stage separation factors are larger and product cuts smaller than for a two-column pressure swing process operated in the same monohydride phase

  4. Diffusive Fractionation of Lithium Isotopes in Olivine Grain Boundaries

    Science.gov (United States)

    Homolova, V.; Watson, E. B.

    2012-12-01

    Diffusive fractionation of isotopes has been documented in silicate melts, aqueous fluids, and single crystals. In polycrystalline rocks, the meeting place of two grains, or grain boundaries, may also be a site of diffusive fractionation of isotopes. We have undertaken an experimental and modeling approach to investigate diffusive fractionation of lithium (Li) isotopes by grain boundary diffusion. The experimental procedure consists of packing a Ni metal capsule with predominantly ground San Carlos olivine and subjecting the capsule to 1100C and 1GPa for two days in a piston cylinder apparatus to create a nominally dry, 'dunite rock'. After this synthesis step, the capsule is sectioned and polished. One of the polished faces of the 'dunite rock' is then juxtaposed to a source material of spodumene and this diffusion couple is subject to the same experimental conditions as the synthesis step. Li abundances and isotopic profiles (ratios of count rates) were analyzed using LA-ICP-MS. Li concentrations linearly decrease away from the source from 550ppm to the average concentration of the starting olivine (2.5ppm). As a function of distance from the source, the 7Li/6Li ratio decreases to a minimum before increasing to the background ratio of the 'dunite rock'. The 7Li/6Li ratio minimum coincides with the lowest Li concentrations above average 'dunite rock' abundances. The initial decrease in the 7Li/6Li ratio is similar to that seen in other studies of diffusive fractionation of isotopes and is thought to be caused by the higher diffusivity (D) of the lighter isotope relative to the heavier isotope. The relationship between D and mass (m) is given by (D1/D2) =(m2/m1)^β, where β is an empirical fractionation factor; 1 and 2 denote the lighter and heavier isotope, respectively. A fit to the Li isotopic data reveals an effective DLi of ~1.2x10^-12 m/s^2 and a β of 0.1. Numerical modelling was utilized to elucidate the relationship between diffusive fractionation

  5. Isotope Fractionation of Water During Evaporation Without Condensation

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  6. Hydrogen isotope recovering and reutilizing method and its device

    International Nuclear Information System (INIS)

    Ide, Takahiro.

    1988-01-01

    Purpose: To enable safety and convenient recovery and reutilization of gaseous tritium and other hydrogen isotopes. Constitution: Two kinds of metal hydrides different from each other in the dissociation pressure at an identical temperature are combined, in which a metal hydride of higher dissociation pressure is used for recovery and reutilization for most portion of gaseous hydrogen isotope gases, while the metal hydride of lower dissociation pressure is used for the recovery and reutilization of the remaining gaseous hydrogen isotopes. This enables to extremely lower the concentration of the remaining gaseous hydrogen isotopes, that is, the concentration of tritium in the recoverying system. In addition, since the heating temperature required for releasing the gaseous hydrogen isotopes absorbed in both of the metal hydrides is within such a range as causing no problem for the permeation of the gaseous hydrogen isotopes, there is no requirement for the countermeasure to tritium permeation or the facility for recovering permeated tritium and there is no problem for the material degradation due to the heating at high temperature. (Kawakami, Y.)

  7. Isotope mixtures of hydrogen in vanadium

    International Nuclear Information System (INIS)

    Mecking-Schloetensack, P.

    1982-03-01

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

  8. Soil tension mediates isotope fractionation during soil water evaporation

    Science.gov (United States)

    Gaj, Marcel; McDonnell, Jeffrey

    2017-04-01

    Isotope tracing of the water cycle is increasing in its use and usefulness. Many new studies are extracting soil waters and relating these to streamflow, groundwater recharge and plant transpiration. Nevertheless, unlike isotope fractionation factors from open water bodies, soil water fractionation factors are poorly understood and until now, only empirically derived. In contrast to open water evaporation where temperature, humidity and vapor pressure gradient define fractionation (as codified in the well-known Craig and Gordon model), soil water evaporation includes additionally, fractionation by matrix effects. There is yet no physical explanation of kinetic and equilibrium fraction from soil water within the soil profile. Here we present a simple laboratory experiment with four admixtures of soil grain size (from sand to silt to clay). Oven-dried samples were spiked with water of known isotopic composition at different soil water contents. Soils were then stored in sealed bags and the headspace filled with dry air and allowed to equilibrate for 24hours. Isotopic analysis of the headspace vapor was done with a Los Gatos Inc. water vapor isotope analyzer. Soil water potential of subsamples were measured with a water potential meter. We show for the first time that soil tension controls isotope fractionation in the resident soil water. Below a Pf 3.5 the δ-values of 18O and 2H of the headspace vapor is more positive and increases with increasing soil water potential. Surprisingly, we find that the relationship between soil tension and equilibrium fractionation is independent of soil type. However, δ-values of each soil type plot along a distinct evaporation line. These results indicate that equilibrium fractionation is affected by soil tension in addition to temperature. Therefore, at high soil water tension (under dry conditions) equilibrium fractionation is not consistent with current empirical formulations that ignore these effects. These findings may have

  9. On the noble gas isotopic fractionation in naturally occurring gases

    International Nuclear Information System (INIS)

    Marty, B.

    1984-01-01

    The isotopic composition of neon in the mantle is an important geochemical constraint on the formation of the earth and subsequent degassing. Some deviation of neon isotopic composition in natural gas and rock samples from the atmospheric value which can not be accounted for by the known nuclear process has been reported, and Nagao et al. interpreted the deviation as the result of mass fractionation in natural gas in Japan. The possible cause of such fractionation was investigated. Gaseous diffusion, such as (a) free-molecule diffusion, (b) mutual diffusion and (c) thermal diffusion, is able to cause isotopic fractionation. After the detailed consideration on these three diffusion processes, conclusion that free-molecule diffusion occurs only in very particular condition, and it is questionable that thermal diffusion occurs in nature, were obtained. (b) which means the interaction of two or more gases, is supposed to occur in nature, and is able to confirm experimentally. In mutual diffusion only, gas transfer is concerned, but other form of fractionation should not be neglected. In solid diffusion, gas is trapped by fine grained sedimentary rocks, and may be fractionated by adsorption and communication to exterior through minute channels. Underground water also works as noble gas reservoir. For example, when gas stream is in contact with water, continuous exchange is possible to take place at the interface of gas and liquid, which contributes to the fractionation. (Ishimitsu, A.)

  10. Boron isotope fractionation in column chromatography with glucamine type fibers

    International Nuclear Information System (INIS)

    Sonoda, Akinari; Makita, Yoji; Hirotsu, Takahiro

    2008-01-01

    Glucamine type polymers have specific affinity toward boric acid and borate ion. Among them, Chelest Fiber GRY-L showed larger fractionation for boron isotopes than other polymers in our previous study. For this study, we used Chelest Fibers with different fiber lengths (1.0 mm, 0.5 mm, and 0.3 mm) as column packing materials to perform chromatographic separation of boron isotopes. The shorter fiber has larger packing density when packed into the column using a dry method. The 0.3-mm-long fiber has a larger backpressure than fibers of other lengths. Boron adsorption capacities were measured using the breakthrough operation. At this time, the 0.5-mm-long fiber showed the highest capacity. When we measured the isotope ratio profile for fibers of different length using column chromatography, 0.5-mm-long fibers displayed the highest boron isotope fractionation. The 0.5-mm-long fiber is promising as a packing material of column chromatography for boron isotope separation. We also changed operation methods. The lower eluent concentration and the slower flow rate are suitable for boron isotope separation. (author)

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

    Science.gov (United States)

    Mizota, Chitoshi; Yamanaka, Toshiro

    2011-12-01

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

  12. Interaction of hydrogen and its isotopes with irradiated beryllium

    International Nuclear Information System (INIS)

    Tazhibaeva, I.L.; Shestakov, V.P.; Klepikov, A.Kh.; Pomanenko, O.G.; Chikhraj, E.V.; Kenzhin, E.A.; Zverev, V.V.; Kolbanenkov, A.N.

    2000-01-01

    In the article the results of experiments on hydrogen and its isotopes accumulation and gas-release from irradiated beryllium are presented. The irradiation was conducted at different media and temperatures in the RA and IVG.1M reactors. The measurements were carried out by thermal desorption method. Hydrogen release from beryllium samples saturated at different conditions were calculated. Dependence of hydrogen confinement character in beryllium from grain orientation in the sample, temperature and irradiation rate was revealed

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

    Science.gov (United States)

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

    2015-03-01

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

  14. Interactions of hydrogen isotopes and oxides with metal tubes

    International Nuclear Information System (INIS)

    Longhurst, G. R.; Cleaver, J.

    2008-01-01

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)

  15. Interactions of hydrogen isotopes and oxides with metal tubes

    Energy Technology Data Exchange (ETDEWEB)

    Longhurst, G. R. [Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415-3860 (United States); Cleaver, J. [Idaho State Univ., 921 South 8th Avenue, Pocatello, ID 83201 (United States)

    2008-07-15

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results. (authors)

  16. Interactions of Hydrogen Isotopes and Oxides with Metal Tubes

    International Nuclear Information System (INIS)

    Longhurst, Glen R.

    2008-01-01

    Understanding and accounting for interaction of hydrogen isotopes and their oxides with metal surfaces is important for persons working with tritium systems. Reported data from several investigators have shown that the processes of oxidation, adsorption, absorption, and permeation are all coupled and interactive. A computer model has been developed for predicting the interaction of hydrogen isotopes and their corresponding oxides in a flowing carrier gas stream with the walls of a metallic tube, particularly at low hydrogen concentrations. An experiment has been constructed to validate the predictive model. Predictions from modeling lead to unexpected experiment results

  17. [Carbon isotope fractionation in plants]: Annual technical progress report

    International Nuclear Information System (INIS)

    O'Leary, M.H.

    1988-01-01

    Plants fractionate carbon isotopes during photosynthesis in ways which reflect photosynthetic pathway and environment. The fractionation is product of contributions from diffusion, carboxylation and other factors which can be understood using models which have been developed in our work. The object of our work is to use this fractionation to learn about the factors which control the efficiency of photosynthesis. Unlike previous studies, we do not rely principally on combustion methods, but instead develop more specific methods with substantially higher resolving power. We have recently developed a new short-term method for studying carbon isotope fractionation which promises to provide a level of detail about temperature, species, and light intensity effects on photosynthesis which has not been available until now. We are studying the isotopic compositions of metabolites (particularly aspartic acid) in C 3 plants in order to determine the role of phosphoenolpyruvate carboxylase in C 3 photosynthesis. We are studying the relative roles of diffusion and carboxylation in nocturnal CO 2 fixation in CAM plants. We are studying the use of isotopic content as an index of water-use efficiency in C 3 plants. We are developing new methods for studying carbon metabolism in plants. 3 refs

  18. Room temperature Sieving of Hydrogen Isotopes Using 2-D Materials

    Energy Technology Data Exchange (ETDEWEB)

    Hitchcock, D. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Colon-Mercado, H. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Krentz, T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Serkiz, S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Velten, J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Xiao, S. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-09-28

    Hydrogen isotope separation is critical to the DOE’s mission in environmental remediation and nuclear nonproliferation. Isotope separation is also a critical technology for the NNSA, and the ability to perform the separations at room temperature with a relatively small amount of power and space would be a major advancement for their respective missions. Recent work has shown that 2-D materials such as graphene and hexagonal boron nitride can act as an isotopic sieve at room temperature; efficiently separating hydrogen isotopes in water with reported separation ratios of 10:1 for hydrogen: deuterium separation for a single pass. The work performed here suggests that this technique has merit, and furthermore, we are investigating optimization and scale up of the required 2-D material based membranes.

  19. Hydrogen isotope analysis of amino acids and whole cells reflects biosynthetic processing of nutrient- and water-derived hydrogen

    Science.gov (United States)

    Griffin, P.; Newsome, S.; Steele, A.; Fogel, M. L.

    2011-12-01

    Hydrogen (H) isotopes serve as sensitive tracers of biochemical processes that can be exploited to answer critical questions in biogeochemistry, ecology, and microbiology. Despite this apparent utility, relatively little is known about the specific mechanisms of H isotope fractionation involved in biosynthesis. In order to understand how organisms incorporate hydrogen from their chemical milieu into biomass, we have cultured the model bacterium E. coli MG1655 in a variety of media composed of deuterium-labeled nutrients and waters. Isotopic analysis of bulk cell mass reveals that the H fractionation between media water and cell material varies as a function of the nutrient source, with commonly used organic food sources (glucose and tryptone) leading to far smaller fractionation signals than non-standard ones (such as formamide, adenine, and urea). In addition, we have completed compound specific isotope analysis of amino acids using combined GC-IRMS. Amino acids harvested from E. coli cultured on glucose in water of varied D/H composition posses an extraordinary range of isotopic compositions (400-600 %). Furthermore, these amino acids follow a systematic distribution of D/H where proline is always heaviest and glycine is always lightest. However, when the short-chain peptide tryptone is used in place of glucose, only the non-essential amino acids reflect media water D/H values, suggesting the direct incorporation of some media-borne amino acids into cellular protein. These observations provide a foundation for understanding the cellular routing of hydrogen obtained from food and water sources and indicate that D/H analysis can serve as a powerful probe of biological function.

  20. Transport hysteresis and hydrogen isotope effect on confinement

    Science.gov (United States)

    Itoh, S.-I.; Itoh, K.

    2018-03-01

    A Gedankenexperiment on hydrogen isotope effect is developed, using the transport model with transport hysteresis. The transport model with hysteresis is applied to case where the modulational electron cyclotron heating is imposed near the mid-radius of the toroidal plasmas. The perturbation propagates either outward or inward, being associated with the clockwise (CW) hysteresis or counter-clockwise (CCW) hysteresis, respectively. The hydrogen isotope effects on the CW and CCW hysteresis are investigated. The local component of turbulence-driven transport is assumed to be the gyro-Bohm diffusion. While the effect of hydrogen mass number is screened in the response of CW hysteresis, it is amplified in CCW hysteresis. This result motivates the experimental studies to compare CW and CCW cases in order to obtain further insight into the physics of hydrogen isotope effects.

  1. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

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

    Science.gov (United States)

    Piper, Thomas; Thevis, Mario

    2017-01-01

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

  3. Hot vacuum extraction-isotopic dilution mass spectrometry for determination of hydrogen isotopes in zircaloys

    International Nuclear Information System (INIS)

    Shi, Y.; Leeson, P.K.; Wilkin, D.; Britton, A.; Macleod, R.

    2016-01-01

    A hot vacuum extraction-isotope dilution mass spectrometry (HVE-IDMS) was studied for determination of hydrogen isotopes in zirconium metal and alloys as nuclear reactor materials. A theoretical assessment of the completeness of the extraction of hydrogen isotopes under the chosen condition was carried out based on the hydrogen and deuterium solubility data for zirconium. The optimal isotopic spiking condition for conventional IDMS was further explored for the special case IDMS where the isotope abundance of the samples is varied and non-natural. Applying the optimal conditions, the accurate IDMS determination was realized. The agreement between the measured values and the certified or prepared values of standard reference materials and homemade standard materials validate the method developed. (author)

  4. Chromium stable isotope fractionation in modern biogeochemical cycling

    DEFF Research Database (Denmark)

    Paulukat, Cora Stefanie

    oxygen in the Earth’s atmosphere. Oxidative rock weathering on land induces oxidation of immobile Cr(III) to mobile Cr(VI). Isotopically relatively heavy Cr(VI) is released to runoff, and transported by rivers to the oceans, where it is incorporated into chemical sediments and carbonate shells...... laterite soils from India, formed on ultramafic rocks, indicates extensive leaching of isotopically heavy Cr(VI). Transferring this knowledge to ancient weathering profiles, negatively fractionated Cr is clear evidence for the presence of free oxygen in the atmosphere. The second part demonstrates...

  5. 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

  6. 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...

  7. 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...

  8. 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

  9. 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

  10. Retention of hydrogen isotopes and helium in nickel

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-01

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

  11. Permeability of hydrogen isotopes through Pd-Ag membrane

    International Nuclear Information System (INIS)

    Yoshida, Hiroshi

    1981-01-01

    This paper represents the permeabilities, diffusion coefficients and isotope effects for hydrogen and deuterium through Pd-25 wt.% Ag alloy tubes The feed gas H 2 or D 2 flowing into the permeation cell was preheated before it reached to the outer surface of the permeation tube made of palladium-silver alloy. Permeation time lag method could be successfully carried out with the present apparatus to measure both permeability and diffusion coefficient. The square-root pressure dependence for the permeation of hydrogen isotopes was observed. The observed systematic temperature dependence indicates that the approximation of the Arrhenius' relation was effective within this experimental conditions. Some tendency of permeation fluxes in relation to the reciprocal temperature, 1/T, was seen. The permeability ratio was larger than the square root of isotopic mass ratio, and it decreased with temperature rise. On the contrary, the diffusion coefficient ratio was much smaller than the square root of isotopic mass ratio. (Kato, T.)

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

    Science.gov (United States)

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

    2017-01-01

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

  13. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

    OpenAIRE

    Frédéric Moynier; Toshiyuki Fujii

    2017-01-01

    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000?ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000?...

  14. H/D Isotope Effects in Hydrogen Bonded Systems

    Directory of Open Access Journals (Sweden)

    Aleksander Filarowski

    2013-04-01

    Full Text Available An extremely strong H/D isotope effect observed in hydrogen bonded A-H…B systems is connected with a reach diversity of the potential shape for the proton/deuteron motion. It is connected with the anharmonicity of the proton/deuteron vibrations and of the tunneling effect, particularly in cases of short bridges with low barrier for protonic and deuteronic jumping. Six extreme shapes of the proton motion are presented starting from the state without possibility of the proton transfer up to the state with a full ionization. The manifestations of the H/D isotope effect are best reflected in the infra-red absorption spectra. A most characteristic is the run of the relationship between the isotopic ratio nH/nD and position of the absorption band shown by using the example of NHN hydrogen bonds. One can distinguish a critical range of correlation when the isotopic ratio reaches the value of ca. 1 and then increases up to unusual values higher than . The critical range of the isotope effect is also visible in NQR and NMR spectra. In the critical region one observes a stepwise change of the NQR frequency reaching 1.1 MHz. In the case of NMR, the maximal isotope effect is reflected on the curve presenting the dependence of Δd (1H,2H on d (1H. This effect corresponds to the range of maximum on the correlation curve between dH and ΔpKa that is observed in various systems. There is a lack in the literature of quantitative information about the influence of isotopic substitution on the dielectric properties of hydrogen bond except the isotope effect on the ferroelectric phase transition in some hydrogen bonded crystals.

  15. Cadmium isotope fractionation of materials derived from various industrial processes

    Energy Technology Data Exchange (ETDEWEB)

    Martinková, Eva, E-mail: eva.cadkova@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Chrastný, Vladislav, E-mail: chrastny@fzp.czu.cz [Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcká 129, 165 21 Prague 6 (Czech Republic); Francová, Michaela, E-mail: michaela.francova@fzp.czu.cz [Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcká 129, 165 21 Prague 6 (Czech Republic); Šípková, Adéla, E-mail: adela.sipkova@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Čuřík, Jan, E-mail: jan.curik@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Myška, Oldřich, E-mail: oldrich.myska@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic); Mižič, Lukáš, E-mail: lukas.mizic@geology.cz [Czech Geological Survey, Geologická 6, 152 00 Prague 5 (Czech Republic)

    2016-01-25

    Highlights: • All studied industrial processes were accompanied by Cd isotope fractionation. • ϵ{sup 114/110} Cd values of the waste materials were discernible from primary sources. • Technology in use plays an important role in Cd isotope fractionation. - Abstract: Our study represents ϵ{sup 114/110} Cd {sub NIST3108} values of materials resulting from anthropogenic activities such as coal burning, smelting, refining, metal coating, and the glass industry. Additionally, primary sources (ore samples, pigment, coal) processed in the industrial premises were studied. Two sphalerites, galena, coal and pigment samples exhibited ϵ{sup 114/110} Cd{sub NIST3108} values of 1.0 ± 0.2, 0.2 ± 0.2, 1.3 ± 0.1, −2.3 ± 0.2 and −0.1 ± 0.3, respectively. In general, all studied industrial processes were accompanied by Cd isotope fractionation. Most of the industrial materials studied were clearly distinguishable from the samples used as a primary source based on ϵ{sup 114/110} Cd {sub NIST3108} values. The heaviest ϵ{sup 114/110} Cd{sub NIST3108} value of 58.6 ± 0.9 was found for slag resulting from coal combustion, and the lightest ϵ{sup 114/110} Cd{sub NIST3108} value of −23 ± 2.5 was observed for waste material after Pb refinement. It is evident that ϵ{sup 114/110} Cd {sub NIST3108} values depend on technological processes, and in case of incomplete Cd transfer from source to final waste material, every industrial activity creates differences in Cd isotope composition. Our results show that Cd isotope analysis is a promising tool to track the origins of industrial waste products.

  16. Isotopic Fractionation of Mercury in Great Lakes Precipitation

    Science.gov (United States)

    Gratz, L. E.; Keeler, G. J.; Blum, J. D.; Sherman, L. S.

    2009-12-01

    Mercury (Hg) is a hazardous bioaccumulative neurotoxin, and atmospheric deposition is a primary way in which mercury enters terrestrial and aquatic ecosystems. However, the chemical processes and transport regimes that mercury undergoes from emission to deposition are not well understood. Thus the use of mercury isotopes to characterize the biogeochemical cycling of mercury is a rapidly growing area of study. Precipitation samples were collected in Chicago, IL, Holland, MI, and Dexter, MI from April 2007 - October 2007 to begin examining the isotopic fractionation of atmospheric mercury in the Great Lakes region. Results show that mass-dependent fractionation relative to NIST-3133 (MDF - δ202Hg) ranged from -0.8‰ to 0.2‰ (±0.2‰) in precipitation samples, while mass-independent fractionation (MIF - Δ199Hg) varied from 0.1‰ to 0.6‰ (±0.1‰). Although clear urban-rural differences were not observed, this may be due to the weekly collection of precipitation samples rather than collection of individual events, making it difficult to truly characterize the meteorology and source influences associated with each sample and suggesting that event-based collection is necessary during future sampling campaigns. Additionally, total vapor phase mercury samples were collected in Dexter, MI in 2009 to examine isotopic fractionation of mercury in ambient air. In ambient samples δ202Hg ranged from 0.3‰ to 0.5‰ (±0.1‰), however Δ199Hg was not significant. Because mercury in precipitation is predominantly Hg2+, while ambient vapor phase mercury is primarily Hg0, these results may suggest the occurrence of MIF during the oxidation of Hg0 to Hg2+ prior to deposition. Furthermore, although it has not been previously reported or predicted, MIF of 200Hg was also detected. Δ200Hg ranged from 0.0‰ to 0.2‰ in precipitation and from -0.1‰ to 0.0‰ in ambient samples. This work resulted in methodological developments in the collection and processing of

  17. Development of Separation Materials Containing Palladium for Hydrogen Isotopes Separation

    International Nuclear Information System (INIS)

    Deng Xiaojun; Luo Deli; Qian Xiaojing

    2010-01-01

    Displacement chromatography (DC) is a ascendant technique for hydrogen isotopes separation. The performance of separation materials is a key factor to determine the separation effect of DC. At present,kinds of materials are researched, including palladium materials and non-palladium materials. It is hardly replaceable because of its excellent separation performance, although palladium is expensive. The theory of hydrogen isotopes separation using DC was introduced at a brief manner, while several palladium separation materials were expatiated in detail(Pd/K, Pd-Al 2 O 3 , Pd-Pt alloy). Development direction of separation materials for DC was forecasted elementarily. (authors)

  18. Quantitative mass-spectrometric analysis of hydrogen helium isotope mixtures

    International Nuclear Information System (INIS)

    Langer, U.

    1998-12-01

    This work deals with the mass-spectrometric method for the quantitative analysis of hydrogen-helium-isotope mixtures, with special attention to fusion plasma diagnostics. The aim was to use the low-resolution mass spectrometry, a standard measuring method which is well established in science and industry. This task is solved by means of the vector mass spectrometry, where a mass spectrum is repeatedly measured, but with stepwise variation of the parameter settings of a quadruple mass spectrometer. In this way, interfering mass spectra can be decomposed and, moreover, it is possible to analyze underestimated mass spectra of complex hydrogen-helium-isotope mixtures. In this work experimental investigations are presented which show that there are different parameters which are suitable for the UMS-method. With an optimal choice of the parameter settings hydrogen-helium-isotope mixtures can be analyzed with an accuracy of 1-3 %. In practice, a low sensitivity for small helium concentration has to be noted. To cope with this task, a method for selective hydrogen pressure reduction has been developed. Experimental investigations and calculations show that small helium amounts (about 1 %) in a hydrogen atmosphere can be analyzed with an accuracy of 3 - 10 %. Finally, this work deals with the effects of the measuring and calibration error on the resulting error in spectrum decomposition. This aspect has been investigated both in general mass-spectrometric gas analysis and in the analysis of hydrogen-helium-mixtures by means of the vector mass spectrometry. (author)

  19. Chromatographic enrichment of isotopes in hydrogen and water samples on palladium

    International Nuclear Information System (INIS)

    Andreev, B.M.; Polevoi, A.S.; Perevezentsev, A.N.

    1987-01-01

    Data on the isotopic enrichment of hydrogen and water samples by chromatography on palladium have been analyzed. Experimental data on the effect of temperature, hydrogen flow, volume of the enriched fraction, and length of the chromatographic column on the degree of separation attainable in the column have been obtained. It has been shown that the maximum separation achievable (regardless of the type of the isotope mixture) at 273 K falls with increase of hydrogen flow and volume of the enriched gas fraction recoverable from the column. A separation degree of ∼ 1040 has been achieved for a mixture of protium and deuterium in a 10-mm wide and 0.6-m long chromatographic column packed with palladium black with a grain size of 0.2-0.5 mm at 273 K and a specific hydrogen flow of 1.22 mole/m 2 x sec. For a protium-tritium mixture a separation degree of ∼ 90 has been reached in a similar column at 273 K and a specific hydrogen flow of 0.4 mole/m 2 x sec

  20. Laser separation of isotopes of hydrogen

    International Nuclear Information System (INIS)

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

    1980-01-01

    Laser isotope separation technique is explained and various methods based on the technique are discussed in detail. Requirements of any laser isotope separation method to be acceptable for the production of heavy water are mentioned and economic viability of this process for heavy water production is examined. Investigations carried out to use this technique for deuterium separation using methanol, formaldehyde, propynal, 2,2,-dichloro-1-1-1,-trifluoroethane (Freon 123), polyvinyl chloride and fluoroform-d are reviewed. (M.G.B.)

  1. Isotope fractionation associated with the direct photolysis of 4-chloroaniline.

    Science.gov (United States)

    Ratti, Marco; Canonica, Silvio; McNeill, Kristopher; Erickson, Paul R; Bolotin, Jakov; Hofstetter, Thomas B

    2015-04-07

    Compound-specific isotope analysis is a useful approach to track transformations of many organic soil and water pollutants. Applications of CSIA to characterize photochemical processes, however, have hardly been explored. In this work, we systematically studied C and N isotope fractionation associated with the direct photolysis of 4-Cl-aniline used as a model compound for organic micropollutants that are known to degrade via photochemical processes. Laboratory experiments were carried out at an irradiation wavelength of 254 nm over the pH range 2.0 to 9.0 as well as in the presence of Cs(+) as a quencher of excited singlet 4-Cl-aniline at pH 7.0 and 9.0. We observed considerable variation of C and N isotope enrichment factors, ϵC and ϵN, between -1.2 ± 0.2‰ to -2.7 ± 0.2‰ for C and -0.6 ± 0.2‰ to -9.1 ± 1.6‰ for N, respectively, which could not be explained by the speciation of 4-Cl-aniline alone. In the presence of 1 M Cs(+), we found a marked increase of apparent (13)C-kinetic isotope effects ((13)C-AKIE) and decrease of 4-Cl-aniline fluorescence lifetimes. Our data suggest that variations of C and N isotope fractionation originate from heterolytic dechlorination of excited triplet and singlet states of 4-Cl-aniline. Linear correlations of (13)C-AKIE vs (15)N-AKIE were distinctly different for these two reaction pathways and may be explored further for the identification of photolytic aromatic dechlorination reactions.

  2. Controllable isotope fractionation with thermal ionisation mass-spectrometers

    International Nuclear Information System (INIS)

    Hebeda, E.H.

    1980-01-01

    Isotopic ratios measured with thermal ionisation mass-spectrometers are biased by fractionation effects. A sample must therefore be analyzed according to the same procedures as applied for the analysis of the standard reference material. A comparison of the behaviour of the sample with that of the standard can then be used as a criterion whether the analytical results are acceptable or not. In this way it is possible to obtain reproducibilities similar to those for elements acceptable or not. In this way it is possible to obtain reproducibilities similar to those for elements where the fractionation can be determined by an internal standard. This procedure of controlled fractionation is demonstrated by means of the 88 Sr/ 86 Sr ratios measured on geological samples and the SRM 987 standard. (orig.)

  3. Hydrogen isotopes identification with the electromagnetic calorimeter TAPS

    International Nuclear Information System (INIS)

    Matulewicz, T.; Aphecetche, L.; Charbonnier, Y.; Delagrange, H.; Martinez, G.; Schutz, Y.; Marques, F.M.; Diaz, J.; and others.

    1996-01-01

    A new method has been developed to identify protons and more generally charged massive particles, like charged pions, hydrogen isotopes and heavier particles reaching the TAPS detector. The method was tested on events from the reaction Ar+Ca at 180 A.MeV. (K.A.)

  4. Cascades for hydrogen isotope separation using metal hydrides

    International Nuclear Information System (INIS)

    Hill, F.B.; Grzetic, V.

    1982-01-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes

  5. Cascades for hydrogen isotope separation using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B; Grzetic, V [Brookhaven National Lab., Upton, NY (USA)

    1983-02-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes.

  6. Quantum mechanical calculation of diffusion of hydrogen isotopes in vanadium

    International Nuclear Information System (INIS)

    Yoshinari, Osamu

    2013-01-01

    Highlights: • Diffusion of H isotopes in V was investigated with a quantum mechanical calculation. • Calculated diffusion coefficients quantitatively agreed with the experimental data. • H in V jumps via quantum mechanical tunneling between the two tetrahedral sites. • H tunneling between ground states is dominant at low temperatures. • H tunneling between exited states becomes important at higher temperatures. -- Abstract: Diffusion of hydrogen isotopes in vanadium was investigated by a quantum mechanical calculation. Wave functions and the corresponding eigen energies (E) for hydrogen isotopes were obtained as a function of hydrogen position along the diffusion path (ξ) by solving the three dimensional Schrödinger equation. Hydrogen potential was calculated by using a first principles method with a nudged elastic band technique. By analyzing the E–ξ curves, the tunneling matrix elements were obtained for the coincidence states between two neighboring tetrahedral sites. It was clarified that the tunneling between ground states was dominant at low temperatures, whereas the contribution of that between the first exited states becomes larger at higher temperatures. The transition temperature of the dominant tunneling decreases with the isotope mass. The calculated temperature dependence of the diffusion for the V–H system quantitatively agreed with the experimental data in the literature, although those for the V–D and –T systems were somewhat underestimated

  7. 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.).

  8. Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

    Science.gov (United States)

    Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

    2017-12-01

    Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

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

    Science.gov (United States)

    Coplen, Tyler B.; Qi, Haiping

    2016-01-01

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

  10. Study on atmospheric hydrogen enrichment by cryopump method and isotope separation by gas chromatography

    International Nuclear Information System (INIS)

    Taniyama, Yuki; Momoshima, Noriyuki

    2001-01-01

    To obtain the information of source of atmospheric hydrogen tritium an analysis of tritium isotopes is thought to be effective. So an atmospheric hydrogen enrichment apparatus and a cryogenic gas chromatographic column were made. Experiments were carried out to study the performance of cryopump to enrich atmospheric hydrogen and the column to separate hydrogen isotopes that obtained by cryopump method. The cryopump was able to process about 1000 1 atmosphere and the column was able to separate hydrogen isotopes with good resolution. (author)

  11. Large sulfur isotope fractionations in Martian sediments at Gale crater

    Science.gov (United States)

    Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

    2017-09-01

    Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

  12. Adsorption methods for hydrogen isotope storage on zeolitic sieves

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  13. Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

    Energy Technology Data Exchange (ETDEWEB)

    Richter, Frank [Univ. of Chicago, IL (United States)

    2016-11-09

    The overall objective of the DOE-funded research by grant DE-FG02-01ER15254 was document and quantify kinetic isotope fractionations during chemical and thermal (i.e., Soret) diffusion in liquids (silicate melts and water) and in the later years to include alloys and major minerals such as olivine and pyroxene. The research involved both laboratory experiments and applications to natural settings. The key idea is that major element zoning on natural geologic materials is common and can arise for either changes in melt composition during cooling and crystallization or from diffusion. The isotope effects associated with diffusion that we have documented are the key for determining whether or not the zoning observed in a natural system was the result of diffusion. Only in those cases were the zoning is demonstrably due to diffusion can use independently measured rates of diffusion to constrain the thermal evolution of the system.

  14. Isotope Fractionation Studies in Prestellar Cores: The Case of Nitrogen

    Science.gov (United States)

    Milam, Stefanie N.; Charnley, Steven B.

    2011-01-01

    Isotopically fractionated material is found in many solar system objects, including meteorites and comets. It is considered, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing, thus preserving the fractionation. In interstellar molecular clouds, ion-molecule chemistry continually cycles nitrogen between the two main reservoirs - N and N2 - leading to only minor N-15 enrichments. Charnley and Rodgers showed that depletion of CO removes oxygen from the gas and weakens this cycle such that significant N-15 fractionation can occur for N2 and other N-bearing species in such cores. Observations are being conducted at millimeter and submillimeter wavelengths employing various facilities in order to both spatially and spectrally, resolve emission from these cores. A preliminary study to obtain the N-14/N-15 ratio in nitriles (HCN and HNC) was conducted at the Arizona Radio Observatory's 12m telescope on Kitt Peak, AZ. Spectra were obtained at high resolution (0.08 km/s) in order to resolve dynamic properties of each source as well as to resolve hyperfine structure present in certain isotopologues. This study included four dark cloud cores, observed to have varying levels of molecular depletion: L1521E, L1498, L1544, and L1521F. Previous studies of the N-14/N-15 ratio towards LI544 were obtained with N2H+ and NIH3, yielding ratios of 446 and >700, respectively. The discrepancy observed in these two measurements suggests a strong chemical dependence on the fractionation of nitrogen. Ratios (C,N, and D) obtained from isotopologues for a particular molecule are likely tracing the same chemical heritage and are directly comparable within a given source. Results and comparisons between the protostellar evolutionary state and isomer isotope fractionation as well as between other N-bearing species will be presented.

  15. 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)

  16. Calcium isotope fractionation in a silicate dominated Cenozoic aquifer system

    Science.gov (United States)

    Li, Junxia; DePaolo, Donald J.; Wang, Yanxin; Xie, Xianjun

    2018-04-01

    To understand the characteristics of Ca isotope composition and fractionation in silicate-dominated Quaternary aquifer system, hydrochemical and isotope studies (87Sr/86Sr, 13CDIC and 44/40Ca) were conducted on groundwater, sediment and rock samples from the Datong basin, China. Along the groundwater flow path from the basin margin to the center, groundwater hydrochemical type evolves from Ca-HCO3 to Na-HCO3/Na-Cl type, which results from aluminosilicate hydrolysis, vertical mixing, cation exchange between CaX2 and NaX, and calcite/dolomite precipitation. These processes cause the decrease in groundwater Ca concentration and the associated modest fractionation of groundwater Ca isotopes along the flowpath. The groundwater δ44/40Ca value varies from -0.11 to 0.49‰. The elevated δ44/40Ca ratios in shallow groundwater are attributed to vertical mixing involving addition of irrigation water, which had the average δ44/40Ca ratio of 0.595‰. Chemical weathering of silicate minerals and carbonate generates depleted δ44/40Ca signatures in groundwater from Heng Mountain (east area) and Huanghua Uplift (west area), respectively. Along the groundwater flow path from Heng Mountain to central area of east area, cation exchange between CaX2 and NaX on clay mineral results in the enrichment of heavier Ca isotope in groundwater. All groundwater samples are oversaturated with respect to calcite and dolomite. The groundwater environment rich in organic matter promotes the precipitation of carbonate minerals via the biodegradation of organic carbon, thereby further promoting the elevation of groundwater δ44/40Ca ratios.

  17. Molecular dynamics simulation of hydrogen isotope injection into graphene

    International Nuclear Information System (INIS)

    Nakamura, Hiroaki; Takayama, Arimichi; Ito, Atsushi

    2007-07-01

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

  18. 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)

  19. Magnesium isotope fractionation in bacterial mediated carbonate precipitation experiments

    Science.gov (United States)

    Parkinson, I. J.; Pearce, C. R.; Polacskek, T.; Cockell, C.; Hammond, S. J.

    2012-12-01

    Magnesium is an essential component of life, with pivotal roles in the generation of cellular energy as well as in plant chlorophyll [1]. The bio-geochemical cycling of Mg is associated with mass dependant fractionation (MDF) of the three stable Mg isotopes [1]. The largest MDF of Mg isotopes has been recorded in carbonates, with foraminiferal tests having δ26Mg compositions up to 5 ‰ lighter than modern seawater [2]. Magnesium isotopes may also be fractionated during bacterially mediated carbonate precipitation and such carbonates are known to have formed in both modern and ancient Earth surface environments [3, 4], with cyanobacteria having a dominant role in carbonate formation during the Archean. In this study, we aim to better constrain the extent to which Mg isotope fractionation occurs during cellular processes, and to identify when, and how, this signal is transferred to carbonates. To this end we have undertaken biologically-mediated carbonate precipitation experiments that were performed in artificial seawater, but with the molar Mg/Ca ratio set to 0.6 and with the solution spiked with 0.4% yeast extract. The bacterial strain used was marine isolate Halomonas sp. (gram-negative). Experiments were run in the dark at 21 degree C for two to three months and produced carbonate spheres of various sizes up to 300 μm in diameter, but with the majority have diameters of ~100 μm. Control experiments run in sterile controls (`empty` medium without bacteria) yielded no precipitates, indicating a bacterial control on the precipitation. The carbonate spheres are produced are amenable to SEM, EMP and Mg isotopic analysis by MC-ICP-MS. Our new data will shed light on tracing bacterial signals in carbonates from the geological record. [1] Young & Galy (2004). Rev. Min. Geochem. 55, p197-230. [2] Pogge von Strandmann (2008). Geochem. Geophys. Geosys. 9 DOI:10.1029/2008GC002209. [3] Castanier, et al. (1999). Sed. Geol. 126, 9-23. [4] Cacchio, et al. (2003

  20. Chlorine isotope fractionation during supergene enrichment of copper

    Science.gov (United States)

    Reich, M.; Barnes, J.; Barra, F.; Milojevic, C.; Drew, D.

    2017-12-01

    Supergene enrichment of Cu deposits in the Atacama Desert has played a critical role in making this the prime Cu-producing province of the world. The Cu-hydroxychloride atacamite is a major component of supergene zones in this region whereas in similar deposits elsewhere it is rare. Atacamite requires saline water to form and dissolves rapidly when exposed to fresh, meteoric water. Previous chlorine stable isotope data [1] for atacamite mineralization at the Radomiro Tomic, Chuquicamata and Mina Sur Cu deposits show δ37Cl values that range from -0.1 to +0.2‰, indicating a similar nonmagmatic source for the introduction of chloride. However, distal atacamite mineralization on the periphery of these orebodies show more fractionated and lighter δ37Cl values (-3.2 to -0.1‰). Although little disagreement currently exists about the involvement of saline groundwater during the formation of atacamite [2], no δ37Cl data are currently available for atacamite within a single deposit and/or supergene enrichment profile that allow explaining the aforementioned differences in the observed δ37Cl values. Furthermore, no experimental data for chlorine isotope fractionation between Cu-hydroxychloride minerals and water exist that help evaluate possible mechanisms of fractionation along the groundwater flow path. Here we present a new database that combines detailed mineralogical observations with δ37Cl data of atacamite along a thick ( 100 m) supergene enrichment profile at the Barreal Seco IOCG deposit in the Atacama Desert of northern Chile. Chlorine stable isotope data of atacamite vary between -0.62 and +2.1 ‰ and show a well-defined trend where δ37Cl values progressively decrease (become lighter) with depth. These data, when combined with new experimental determinations of chlorine isotope fractionation between atacamite and water, point to changes triggered by the progressive deepening of groundwater tables during Andean uplift and the extreme desiccation of

  1. Iron isotope fractionation during hydrothermal ore deposition and alteration

    Science.gov (United States)

    Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

    2006-06-01

    Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

  2. Proposed configuration for ITER hydrogen isotope separation system (ISS)

    International Nuclear Information System (INIS)

    Lazar, A.; Brad, S.; Sofalca, N.; Vijulie, M.; Cristescu, I.; Doer, L; Wurster, W.

    2008-01-01

    Full text: The isotope separation system utilizes cryogenic distillation and catalytic reaction for isotope exchange to separate elemental hydrogen isotope gas mixtures. The ISS shall separate hydrogen isotope mixtures from two sources to produce up to five different products. These are: protium, effluent for discharge to the atmosphere, deuterium for fuelling, deuterium for NB injector (NBI) source gas, 50 % and 90% T fuelling streams. The concept of equipment 3D layout for the ISS main components were developed using the Part Design, Assembly Design, Piping Design, Equipment Arrangement and Plant Layout application from CATIA V5. The 3D conceptual layouts for ISS system were created having as reference the DDD -32-B report, the drawings 0028.0001.2D. 0100. R 'Process Flow Diagram'; 0029.0001.2D. 0200.R 'Process Instrumentation Diagram -1' (in the cold box); 0030.0001.2D. 0100. R 'Process Instrumentation Diagram -2' (in the hard shell confinement) and imputes from TLK team. The main components designed for ISS are: ISS cold box system (CB) with cryogenic distillation columns (CD) and recovery heat exchangers (HX), ISS hard shell containment (HSC) system with metals bellow pumps (MB) and chemical equilibrators (RC), valve box system, instrumentation box system, vacuum system and hydrogen expansion vessels. Work related to these topics belongs to the contract FU06-CT-2006-00508 (EFDA 06-1511) from the EFDA Technology Workprogramm 2006 and was done in collaboration with FZK Association team during the period January 2007 - September 2008. (authors)

  3. 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

  4. Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

    Science.gov (United States)

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

    2012-01-01

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

  5. 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.)

  6. A catalyst for hydrogenating medium-distilled petroleum fractions

    Energy Technology Data Exchange (ETDEWEB)

    Mordanov, M A; Gasanova, Zh I; Isaev, A Ia; Khavkin, V A; Kurganov, V M; Musaeva, S K

    1982-01-01

    The catalyst for hydrogenating medium-distilled petroleum fractions, which contain Cr/sub 2/O/sub 3/ and Ni-concentrate components in the gamma-A1/sub 2/O/sub 3/ transfer agent, also contains, as a Ni-concentrate component, NiO and Re in the following component ratios (by percentage): Cr/sub 2/O/sub 3/ 25-44, NiO 4-25, Re 1-2 and the transfer agent the remainder, in order to improve catalytic resistance to catalyst toxins--nitrous and sulfurous compounds. The resistance of the proposed catalyst to toxins makes it possible to hydrogenate in less stringent conditions (280 degrees, 30 atmospheres) without first hydropurifying the raw material. Here, the catalyst's selectivity reaches 100 percent (aromatic hydrocarbons are absent); the yield of the target fraction is 99 percent.

  7. Hydrogen isotopic substitution experiments in nanostructured porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Palacios, W.D. [Facultad de Ciencias Exactas y Naturales y Agrimensura - (UNNE), Avenida Libertad 5500, 3400 Corrientes (Argentina); Koropecki, R.R. [INTEC (CONICET-UNL), Gueemes 3450, 3000 Santa Fe (Argentina)], E-mail: rkoro@intec.ceride.gov.ar; Arce, R.D. [INTEC (CONICET-UNL), Gueemes 3450, 3000 Santa Fe (Argentina); Busso, A. [Facultad de Ciencias Exactas y Naturales y Agrimensura - (UNNE), Avenida Libertad 5500, 3400 Corrientes (Argentina)

    2008-04-30

    Nanostructured porous silicon is usually prepared by electrochemical anodization of monocrystalline silicon using a fluorine-rich electrolyte. As a result of this process, the silicon atoms conserve their original crystalline location, and many of the dangling bonds appearing on the surface of the nanostructure are saturated by hydrogen coming from the electrolyte. This work presents an IR study of the effects produced by partial substitution of water in the electrolytic solution by deuterium oxide. The isotopic effects on the IR spectra are analyzed for the as-prepared samples and for the samples subjected to partial thermal effusion of hydrogen and deuterium. We demonstrate that, although deuterium is chemically indistinguishable from hydrogen, it presents a singular behaviour when used in porous silicon preparation. We found that deuterium preferentially bonds forming Si-DH groups. A possible explanation of the phenomenon is presented, based on the different diffusivities of hydrogen and deuterium.

  8. Hydrogen isotopic substitution experiments in nanostructured porous silicon

    International Nuclear Information System (INIS)

    Palacios, W.D.; Koropecki, R.R.; Arce, R.D.; Busso, A.

    2008-01-01

    Nanostructured porous silicon is usually prepared by electrochemical anodization of monocrystalline silicon using a fluorine-rich electrolyte. As a result of this process, the silicon atoms conserve their original crystalline location, and many of the dangling bonds appearing on the surface of the nanostructure are saturated by hydrogen coming from the electrolyte. This work presents an IR study of the effects produced by partial substitution of water in the electrolytic solution by deuterium oxide. The isotopic effects on the IR spectra are analyzed for the as-prepared samples and for the samples subjected to partial thermal effusion of hydrogen and deuterium. We demonstrate that, although deuterium is chemically indistinguishable from hydrogen, it presents a singular behaviour when used in porous silicon preparation. We found that deuterium preferentially bonds forming Si-DH groups. A possible explanation of the phenomenon is presented, based on the different diffusivities of hydrogen and deuterium

  9. 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

  10. Separation of tritium from other hydrogen isotopes

    International Nuclear Information System (INIS)

    Roth, E.

    1988-01-01

    The paper describes a plant that has been operated at Marcoule for tritium production and used thermal diffusion enrichment, a facility that was built in Saclay to enrich hydrogen in tritium for low level measurements, and the Laue Langevin Institute tritium extraction plant. Details are given on the project under construction for the tritium separation facility at JET using Gas Chromatography, and on proposals for circuits for NET. Studies on catalysers for liquid phase catalytic exchange, on electrolysers, or different gas chromatography arrangements, are described. Systems designed for reprocessing plants, for detritiation of heavy water by distillation are briefly accounted for

  11. 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.

  12. 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

  13. Strontium isotope fractionation in soils and pedogenic processes

    Energy Technology Data Exchange (ETDEWEB)

    Shalev, Netta [Institute of Earth Sciences, The Hebrew University of Jerusalem, 91904 Jerusalem (Israel); Geological Survey of Israel, 30 Malkhe Israel Street, 95501 Jerusalem (Israel); Lazar, Boaz [Institute of Earth Sciences, The Hebrew University of Jerusalem, 91904 Jerusalem (Israel); Halicz, Ludwik; Stein, Mordechai; Gavrieli, Ittai; Sandler, Amir; Segal, Irena [Geological Survey of Israel, 30 Malkhe Israel Street, 95501 Jerusalem (Israel)

    2013-07-01

    The stable isotope composition of strontium (the ratio {sup 88}Sr/{sup 86}Sr expressed as δ{sup 88/86}Sr) showed significant fractionation in mountain soils of the Judea Highland. In order to understand this phenomenon, we studied the elemental composition and the stable and radiogenic Sr isotopic composition in soil transects conducted from semi-arid (desert fringe) to wetter (Mediterranean) climate zones. These transects were selected because the degree of soil leaching depends on the amount of precipitation and the permeability of the underlying bedrock. These soils are the pedogenic products of leaching of the accumulated desert dust and the underlying carbonate bed-rocks resulting in, among others, enrichment of the residual soils in Al-clays. A clear negative correlation was found between the δ{sup 88/86}Sr and Al{sub 2}O{sub 3} (Al-clay content) values of the soils, the high δ{sup 88/86}Sr-low Al{sub 2}O{sub 3} being the dust end-member. This preliminary study demonstrates the feasibility of using stable {sup 88}Sr-{sup 86}Sr isotopes as tracers of terrestrial weathering processes. (authors)

  14. Hydrogen isotope storage in zircaloy scrap

    Energy Technology Data Exchange (ETDEWEB)

    Lee, H. S.; Kuk, I. H.; Chung, H.; Paek, S. W.; Kang, H. S

    1999-08-01

    8 MCi of tritium a year will be produced after wolsong TRF is in operation. The metal hydride form is one of useful tritium storage. The metals in use for metal hydride are uranium, titanium, etc., however uranium is limited to use by regulation, and titanium is relatively costly. Both metals are not produced in country but whole amount is imported. On the other hand 2,000kg of zircaloy scrap is produced by CANDU nuclear fuel fabrication process, which is also useful for hydrogen storage. The purpose of this study is to evaluation of hydrogen absorption capacity for zircaloy scrap that is produced as waste by CANDU nuclear fuel fabrication process. The sample evacuated for an hour at 1000 deg C. The strip showed higher capacity : 0.7 at 25 deg C, 2.0 at 200 deg C, 2.0 at 200 deg C, 2.0 at 400 deg C, respectively. The H/M values for commercial zircaloy sponge were 2.0 at 25 deg C and 2.0 at 400 deg C.

  15. 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)

  16. Hydrogen isotope storage in zircaloy scrap

    International Nuclear Information System (INIS)

    Lee, H. S.; Kuk, I. H.; Chung, H.; Paek, S. W.; Kang, H. S.

    1999-08-01

    8 MCi of tritium a year will be produced after wolsong TRF is in operation. The metal hydride form is one of useful tritium storage. The metals in use for metal hydride are uranium, titanium, etc., however uranium is limited to use by regulation, and titanium is relatively costly. Both metals are not produced in country but whole amount is imported. On the other hand 2,000kg of zircaloy scrap is produced by CANDU nuclear fuel fabrication process, which is also useful for hydrogen storage. The purpose of this study is to evaluation of hydrogen absorption capacity for zircaloy scrap that is produced as waste by CANDU nuclear fuel fabrication process. The sample evacuated for an hour at 1000 deg C. The strip showed higher capacity : 0.7 at 25 deg C, 2.0 at 200 deg C, 2.0 at 200 deg C, 2.0 at 400 deg C, respectively. The H/M values for commercial zircaloy sponge were 2.0 at 25 deg C and 2.0 at 400 deg C

  17. 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

  18. Solubility of hydrogen isotopes in liquid LiPb

    International Nuclear Information System (INIS)

    Konishi, S.; Yamamoto, Y.; Noborio, K.; Calderoni, P.; Merrill, B.

    2014-01-01

    This research was performed mainly in the first half of the task 1-2 of TITAN project to investigate the interaction between hydrogen isotopes and liquid LiPb. Solubility of hydrogen in liquid LiPb was measured under a static condition. Kyoto University provided the first experimental apparatus shipped to Idaho, and Kyushu University succeeded the experiment and further improved. Obtained solubility generally agreed with some previous reports, but varied orders of magnitudes suggesting influence of impurity or other chemical processes. (author)

  19. Diatom-induced silicon isotopic fractionation in Antarctic sea ice

    Science.gov (United States)

    Francois, F.; Damien, C.; Jean-Louis, T.; Anthony, W.; Luc, A.

    2006-12-01

    We measured silicon-isotopic composition of dissolved silicon and biogenic silica collected by sequential melting from spring 2003 Antarctic pack ice (Australian sector). Sea ice is a key ecosystem in the Southern Ocean and its melting in spring has been often thought to have a seeding effect for the surface waters, triggering blooms in the mixed layer. This work is the first investigation of the silicon isotopes' proxy in sea ice and allows to estimate the activity of sea-ice diatoms in the different brine structures and the influence of sea- ice diatoms on the spring ice edge blooms. The relative use of the dissolved silicon pool by sea-ice diatoms is usually assessed by calculating nutrient:salinity ratios in the brines. However such an approach is biased by difficulties in evaluating the initial nutrient concentrations in the different brines structures, and by the impossibility to account for late sporadic nutrient replenishments. The silicon-isotopic composition of biogenic silica is a convenient alternative since it integrates an average Si utilization on all generations of diatoms. Measurements were performed on a MC-ICP-MS, in dry plasma mode using external Mg doping. Results are expressed as delta29Si relative to the NBS28 standard. From three sea ice cores with contrasted physico-chemical characteristics, we report significant isotopic fractionations linked to the diatoms activity, with distinct silicon biogeochemical dynamics between different brine structure. The diatoms in snow ice and in brine pockets of frazil or congelation ice have the most positive silicon-isotopic composition (+0.53 to +0.86 p.mil), indicating that they grow in a closed system and use a significant part of the small dissolved silicon pool. In the brine channels and skeletal layer, diatoms display a relatively less positive Si-isotopic composition (+0.41 to +0.70 p.mil), although it is still heavier compared to equilibrium fractionation (+0.38 p.mil). This suggests that they have

  20. The fractioning factor and the number of theorical plates in isotopic enrichment columns determined simultaneously

    International Nuclear Information System (INIS)

    Ducatti, Carlos

    1997-01-01

    Using an analytical approach and an analytical graphical method, it was determined simultaneously the fractioning factor and the number of theoretical plates in isotopic enrichment columns during the conditions of dinamical isotopic equilibrium. (author). 5 refs., 2 figs., 2 tabs

  1. Deuterium isotope separation factor between hydrogen and liquid water

    International Nuclear Information System (INIS)

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

    1976-01-01

    The overall deuterium isotope separation factor between hydrogen and liquid water, α, has been measured directly for the first time between 280 and 370 0 K. The data are in good agreement with values of α calculated from literature data on the equilibrium constant for isotopic exchange between hydrogen and water vapor, K 1 , and the liquid-vapor separation factor, α/sub V/. The temperature dependence of α over the range 273-473 0 K based upon these new experimental results and existing literature data is given by the equation ln α = -0.2143 + (368.9/T) + (27,870/T 2 ). Measurements on α/sub V/ given in the literature have been surveyed and the results are summarized over the same temperature range by the equation ln α/sub V/ = 0.0592 - (80.3/T) +

  2. Co-deposition of palladium with hydrogen isotopes

    International Nuclear Information System (INIS)

    Dash, J.; Ambadkar, A.

    2006-01-01

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

  3. Hydrogen isotopes transport parameters in fusion reactor materials

    International Nuclear Information System (INIS)

    Serra, E.; Ogorodnikova, O.V.

    1998-01-01

    This work presents a review of hydrogen isotopes-materials interactions in various materials of interest for fusion reactors. The relevant parameters cover mainly diffusivity, solubility, trap concentration and energy difference between trap and solution sites. The list of materials includes the martensitic steels (MANET, Batman and F82H-mod.), beryllium, aluminium, beryllium oxide, aluminium oxide, copper, tungsten and molybdenum. Some experimental work on the parameters that describe the surface effects is also mentioned. (orig.)

  4. Experimental study of hydrogen isotopes storage on titanium bed

    International Nuclear Information System (INIS)

    Vasut, Felicia; Zamfirache, Marius; Bornea, Anisia; Pearsica, Claudia; Bidica, Nicolae

    2002-01-01

    As known, the Nuclear Power Plant Cernavoda equipped with a Canadian reactor, of CANDU type, is the most powerful tritium source from Europe. On long term, due to a 6·10 16 Bq/year, Cernavoda area will be contaminated due to the increasing tritium quantity. Also, the continuous contamination of heavy water from the reactor, induces a reduction of moderation's capacity. Therefore, one considers that it is improperly to use heavy water if its activity level is higher than 40 Ci/kg in the moderator and 2 Ci/kg in the cooling fluid. For these reasons, we have developed a detritiation technology, based on catalytic isotopic exchange and cryogenic distillation. Tritium will be removed from the tritiated heavy water, so it appears the necessity of storage of tritium in a special vessel that can provide a high level of protection and safety of environment and personal. There several metals were tested as storage beds for hydrogen isotopes. One of the reference materials used for storage of hydrogen isotopes is uranium, a material with a great storage capacity, but unfortunately it is a radioactive metal and also can react with the impurities from the stored gas. Other metals and alloys as ZrCo, Ti, FeTi are also adequate as storage beds at normal temperature. The paper presents studies about the reaction between hydrogen and titanium used as storage bed for the hydrogen isotopes resulted after the detritiation of tritiated heavy water. The experiments that were carried out used protium and mixture of deuterium and protium at different storage parameters as process gas. (authors)

  5. Low temperature isotope effects of hydrogen diffusion in metallic glasses

    International Nuclear Information System (INIS)

    Hofmann, A.; Kronmueller, H.

    1989-01-01

    Snoek-like relaxation peaks of Hydrogen and Deuterium in amorphous Fe 80 B 20 , Fe 40 Ni 40 P 14 B 6 and Fe 91 Zr 9 are detected. At low H, D concentrations the peaks are near 200 K and show small isotope effects of the average activation energies (anti Q H ≅ 0.6 eV, anti Q D - anti Q H ≤ 10 meV). For higher H, D-contents the peaks shift to lower temperatures around to 120 K and show distinct isotope effects in the activation energies (anti Q H ≅ 0.3 eV, anti Q D - anti Q H ≅ 30 meV) and in the amplitude of the low temperature tails of the relaxation peaks. This points to isotope mass dependent deviations from the Arrhenius law due to nonthermal tunneling processes. (orig.)

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

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  7. Membrane pumping technology, helium and hydrogen isotopes separation in the fusion hydrogen

    International Nuclear Information System (INIS)

    Pigarov, A.Yu.; Pistunovich, V.I.; Busnyuk, A.O.

    1994-01-01

    A gas pumping system for the ITER, improved by implementation of superpermeable membranes for selective hydrogen isotope exhaust, is considered. The study of the pumping capability of a niobium membrane for a hydrogen-helium mixture has been fulfilled. The membrane superpermeability can be only realized for atomic hydrogen. Helium does not pass through the membrane, and its presence does not affect the hydrogen pumping. A detailed Monte Carlo simulation of gas behavior for the experimental facility has been done. The probability of permeation for a hydrogen atom for one collision with the membrane is ∼0.1; the same probability of molecule permeation is ∼10 -5 . The probability for atomization, i.e. re-emission of an atomizer is ∼0.2; the probability of recombination of an atom is ∼0.2

  8. Thermal desorption spectroscopy for investigating hydrogen isotope behavior in materials

    International Nuclear Information System (INIS)

    Xia Tirui; Yang Hongguang; Zhan Qin; Han Zhibo; He Changshui

    2012-01-01

    The behavior of hydrogen isotope generated in fusion reactor materials is the key issue for safety and economic operation of fusion reactors and becomes an interesting field. In order to investigate the mechanism of hydrogen isotope such as diffusion, release and retention, a high-sensitivity thermal desorption spectroscopy (TDS) in combination with a quadruple mass spectrometer (QMS) was developed. A major technical breakthrough in ultrahigh vacuum (UHV), low hydrogen background, linear heating and sensitivity calibration of TDS system was made. UHV of l × 10 -7 Pa and low hydrogen background of l × 10 -9 Pa were obtained by combining turbo molecule pump and sputter ion pump. Specimens can be linearly heated up to 1173 K at the rate of 1 to 50 K/min under the MCGS PID software. Sensitivity calibration of the TDS system was accomplished using a special deuterium leak in the detector mode of QMS second electron multiplier. The desorption sensitivity coefficient and the minimum detection limit of deuterium desorption rate are 6.22 × l0 24 s -l · and l.24 × l0 -10 s -1 , respectively. The measurement was also routinely conducted on a specimen of standard, deuterium-containing Zr-4 alloy maintained in the laboratory, so as to validate the TDS method. (authors)

  9. Effect of experimentally observed hydrogenic fractionation on inertial confinement fusion ignition target performance

    International Nuclear Information System (INIS)

    McKenty, P. W.; Wittman, M. D.; Harding, D. R.

    2006-01-01

    The need of cryogenic hydrogenic fuels in inertial confinement fusion (ICF) ignition targets has been long been established. Efficient implosion of such targets has mandated keeping the adiabat of the main fuel layer at low levels to ensure drive energies are kept at reasonable minima. The use of cryogenic fuels helps meet this requirement and has therefore become the standard in most ICF ignition designs. To date most theoretical ICF ignition target designs have assumed a homogeneous layer of deuterium-tritium (DT) fuel kept slightly below the triple point. However, recent work has indicated that, as cryogenic fuel layers are formed inside an ICF capsule, isotopic dissociation of the tritium (T), deuterium (D), and DT takes place leading to a 'fractionation' of the final ice layer. This paper will numerically investigate the effects that various scenarios of fractionation have on hot-spot formation, ignition, and burn in ICF ignition target designs

  10. Diamond and Diamond-Like Materials as Hydrogen Isotope Barriers

    International Nuclear Information System (INIS)

    Foreman, L.R.; Barbero, R.S.; Carroll, D.W.; Archuleta, T.; Baker, J.; Devlin, D.; Duke, J.; Loemier, D.; Trukla, M.

    1999-01-01

    This is the final report of a two-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The purpose of this project was to develop diamond and diamond-like thin-films as hydrogen isotope permeation barriers. Hydrogen embrittlement limits the life of boost systems which otherwise might be increased to 25 years with a successful non-reactive barrier. Applications in tritium processing such as bottle filling processes, tritium recovery processes, and target filling processes could benefit from an effective barrier. Diamond-like films used for low permeability shells for ICF and HEDP targets were also investigated. Unacceptable high permeabilities for hydrogen were obtained for plasma-CVD diamond-like-carbon films

  11. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    Science.gov (United States)

    Summers, David P.

    2003-01-01

    mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

  12. 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.

  13. Boron isotope fractionation in magma via crustal carbonate dissolution.

    Science.gov (United States)

    Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

    2016-08-04

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

  14. Boron isotope fractionation in magma via crustal carbonate dissolution

    Science.gov (United States)

    Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

    2016-08-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to -41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

  15. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki

    2017-03-01

    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca2+ and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements.

  16. 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.)

  17. Interplay of community dynamics, temperature, and productivity on the hydrogen isotope signatures of lipid biomarkers

    Directory of Open Access Journals (Sweden)

    S. N. Ladd

    2017-09-01

    Full Text Available The hydrogen isotopic composition (δ2H of lipid biomarkers has diverse applications in the fields of paleoclimatology, biogeochemistry, and microbial community dynamics. Large changes in hydrogen isotope fractionation have been observed among microbes with differing core metabolisms, while environmental factors including temperature and nutrient availability can affect isotope fractionation by photoautotrophs. Much effort has gone into studying these effects under laboratory conditions with single species cultures. Moving beyond controlled environments and quantifying the natural extent of these changes in freshwater lacustrine settings and identifying their causes is essential for robust application of δ2H values of common short-chain fatty acids as a proxy of net community metabolism and of phytoplankton-specific biomarkers as a paleohydrologic proxy. This work targets the effect of community dynamics, temperature, and productivity on 2H∕1H fractionation in lipid biomarkers through a comparative time series in two central Swiss lakes: eutrophic Lake Greifen and oligotrophic Lake Lucerne. Particulate organic matter was collected from surface waters at six time points throughout the spring and summer of 2015, and δ2H values of short-chain fatty acids, as well as chlorophyll-derived phytol and the diatom biomarker brassicasterol, were measured. We paired these measurements with in situ incubations conducted with NaH13CO3, which were used to calculate the production rates of individual lipids in lake surface water. As algal productivity increased from April to June, net discrimination against 2H in Lake Greifen increased by as much as 148 ‰ for individual fatty acids. During the same time period in Lake Lucerne, net discrimination against 2H increased by as much as 58 ‰ for individual fatty acids. A large portion of this signal is likely due to a greater proportion of heterotrophically derived fatty acids in the winter and early

  18. Transient competitive complexation in biological kinetic isotope fractionation explains nonsteady isotopic effects: Theory and application to denitrification in soils

    Science.gov (United States)

    Maggi, Federico; Riley, William J.

    2009-12-01

    The theoretical formulation of biological kinetic isotope fractionation often assumes first-order or Michaelis-Menten kinetics, the latter solved under the quasi-steady state assumption. Both formulations lead to a constant isotope fractionation factor, therefore they may return incorrect estimations of isotopic effects and misleading interpretations of isotopic signatures when fractionation is not a steady process. We have analyzed the isotopic signature of denitrification in biogeochemical soil systems by Menyailo and Hungate (2006) in which high and variable 15N-N2O enrichment during N2O production and inverse isotope fractionation during N2O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with Michaelis-Menten kinetics. When Michaelis-Menten kinetics were coupled to Monod kinetics to describe biomass and enzyme dynamics, and the quasi-steady state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observed concentrations, and variable and inverse isotope fractionations. These results imply a substantial revision in modeling isotopic effects, suggesting that steady state kinetics such as first-order, Rayleigh, and classic Michaelis-Menten kinetics should be superseded by transient kinetics in conjunction with biomass and enzyme dynamics.

  19. What Drives Carbon Isotope Fractionation by the Terrestrial Biosphere?

    Science.gov (United States)

    Still, Christopher; Rastogi, Bharat

    2017-11-01

    During photosynthesis, terrestrial plants preferentially assimilate the lighter and much more abundant form of carbon, 12C, which accounts for roughly 99% of naturally occurring forms of this element. This photosynthetic preference for lighter carbon is driven principally by differences in molecular diffusion of carbon dioxide with differing 13C/12C across stomatal pores on leaves, followed by differences in carboxylation rates by the Rubisco enzyme that is central to the process of photosynthesis. As a result of these slight preferences, which work out to about a 2% difference in the fixation rates of 12CO2 versus 13CO2 by C3 vegetation, plant tissues are depleted in the heavier form of carbon (13C) relative to atmospheric CO2. This difference has been exploited in a wide range of scientific applications, as the photosynthetic isotope signature is passed to ecosystem carbon pools and through ecological food webs. What is less appreciated is the signature that terrestrial carbon exchanges leave on atmospheric CO2, as the net uptake of carbon by land plants during their growing season not only draws down the local CO2 concentration, it also leaves behind relatively more CO2 molecules containing 13C. The converse happens outside the growing season, when autotrophic and heterotrophic respiration predominate. During these periods, atmospheric CO2 concentration increases and its corresponding carbon isotope composition becomes relatively depleted in 13C as the products of photosynthesis are respired, along with some small isotope fractionation that happen downstream of the initial photosynthetic assimilation. Similar phenomena were first observed at shorter time scales by the eminent carbon cycle scientist, Charles (Dave) Keeling. Keeling collected samples of air in glass flasks from sites along the Big Sur coast that he later measured for CO2 concentration and carbon isotope composition (δ13C) in his lab (Keeling, 1998). From these samples, Keeling observed increasing

  20. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kuehnel, Matthias

    2014-02-15

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  1. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    International Nuclear Information System (INIS)

    Kuehnel, Matthias

    2014-02-01

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  2. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kuehnel, Matthias

    2014-02-15

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  3. 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

  4. The Laboratory for Laser Energetics’ Hydrogen Isotope Separation System

    Energy Technology Data Exchange (ETDEWEB)

    Shmayda, W.T., E-mail: wshm@lle.rochester.edu; Wittman, M.D.; Earley, R.F.; Reid, J.L.; Redden, N.P.

    2016-11-01

    The University of Rochester’s Laboratory for Laser Energetics has commissioned a hydrogen Isotope Separation System (ISS). The ISS uses two columns—palladium on kieselguhr and molecular sieve—that act in a complementary manner to separate the hydrogen species by mass. The 4-sL per day throughput system is compact and has no moving parts. The columns and the attendant gas storage and handling subsystems are housed in a 0.8 -m{sup 3} glovebox. The glovebox uses a helium cover gas that is continuously processed to extract oxygen and water vapor that permeates through the glovebox gloves and any tritium that is released while attaching or detaching vessels to add feedstock to or drawing product from the system. The isotopic separation process is automated and does not require manual intervention. A total of 315 TBq of tritium was extracted from 23.6 sL of hydrogen with tritium purities reaching 99.5%. Deuterium was the sole residual component in the processed gas. Raffinate contained 0.2 TBq of activity was captured for reprocessing. The total emission from the system to the environment was 0.4 GBq over three weeks.

  5. 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)

  6. 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

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

    Science.gov (United States)

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

    2011-01-01

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

  8. Copper isotope fractionation between aqueous compounds relevant to low temperature geochemistry and biology

    Science.gov (United States)

    Fujii, Toshiyuki; Moynier, Frédéric; Abe, Minori; Nemoto, Keisuke; Albarède, Francis

    2013-06-01

    Isotope fractionation between the common Cu species present in solution (Cu+, Cu2+, hydroxide, chloride, sulfide, carbonate, oxalate, and ascorbate) has been investigated using both ab initio methods and experimental solvent extraction techniques. In order to establish unambiguously the existence of equilibrium isotope fractionation (as opposed to kinetic isotope fractionation), we first performed laboratory-scale liquid-liquid distribution experiments. Upon exchange between HCl medium and a macrocyclic complex, the 65Cu/63Cu ratio fractionated by -1.06‰ to -0.39‰. The acidity dependence of the fractionation was appropriately explained by ligand exchange reactions between hydrated H2O and Cl- via intramolecular vibrations. The magnitude of the Cu isotope fractionation among important Cu ligands was also estimated by ab initio methods. The magnitude of the nuclear field shift effect to the Cu isotope fractionation represents only ˜3% of the mass-dependent fractionation. The theoretical estimation was expanded to chlorides, hydroxides, sulfides, sulfates, and carbonates under different conditions of pH. Copper isotope fractionation of up to 2‰ is expected for different forms of Cu present in seawater and for different sediments (carbonates, hydroxides, and sulfides). We found that Cu in dissolved carbonates and sulfates is isotopically much heavier (+0.6‰) than free Cu. Isotope fractionation of Cu in hydroxide is minimal. The relevance of these new results to the understanding of metabolic processes was also discussed. Copper is an essential element used by a large number of proteins for electron transfer. Further theoretical estimates of δ65Cu in hydrated Cu(I) and Cu(II) ions, Cu(II) ascorbates, and Cu(II) oxalate predict Cu isotope fractionation during the breakdown of ascorbate into oxalate and account for the isotopically heavy Cu found in animal kidneys.

  9. Fractionation of carbon isotopes by thermophilic methanogenic bacteria

    International Nuclear Information System (INIS)

    Ivanov, M.V.; Belyaev, S.S.; Zyakun, A.M.; Bondar, V.A.; Shipin, O.P.; Laurinavichus, K.S.

    1985-01-01

    The authors investigated the pattern of fractionation of stable carbon isotopes by the thermophilic methane-forming bacteria under different growth conditions and at various rates of formation of methane. A pure culture of Methanobacterium thermoautotrophicum was used in the experiments under the following growth conditions: temperature 65-70 0 C; pH 7.2-7.6; NaCl content 0-0.9 g/liter. The methanogenic bacteria were cultivated in 0.15 liter flasks in mineral medium. A mixture of CO 2 and H 2 in a 1:4 ratio by volume served as the sole carbon and energy source. In all experiments, not more than 5% of the initial CO 2 level was utilized. The rate of methane generation was altered by adjusting the physicochemical growth parameters (temperature from 45-70 0 C, salinity from 0.9 to 40 g/liter NaCl, pH from 6.3 to 7.2). Methane in the samples was quantitatively determined in a chromatograph which had a flame-ionization detector and a column containing Porapak Q sorbent at T = 120 0 C. The carrier gas was CO 2 . The average specific rate of methane formation was calculated as ml CH 4 per mg dry biomass of bacteria per h. Soluble mineral carbon was isolated form the acidified culture liquid in the form of CO 2 and was quantitatively determined in a Chrom-4 chromatography provided with a katharometer and a column containing activated charcoal at T = 150 0 . The gas carrier was helium. The isotopic composition of carbon was determined in a CH-7 mass-spectrometer and was expressed in 13 C values (per thousand) with respect to the international PDB standard

  10. Simulation of startup period of hydrogen isotope separation distillation column

    International Nuclear Information System (INIS)

    Sazonov, A.B.; Kagramanov, Z.G.; Magomedbekov, Eh.P.

    2003-01-01

    Kinetic procedure for the mathematical simulation of start-up regime of rectification columns for molecular hydrogen isotope separation was developed. Nonstationary state (start-up period) of separating column for rectification of multi-component mixture was calculated. Full information on equilibrium and kinetic physicochemical properties of components in separating mixtures was used for the calculations. Profile of concentration of components by height of column in task moment of time was calculated by means of differential equilibriums of nonstationary mass transfer. Calculated results of nonstationary state of column by the 2 m height, 30 mm diameter during separation of the mixture: 5 % protium, 70 % deuterium, 25 % tritium were illustrated [ru

  11. Silicon Isotope Fractionation During Acid Water-Igneous Rock Interaction

    Science.gov (United States)

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

    2007-12-01

    Silica enrichment by metasomatic/hydrothermal alteration is a widespread phenomenon in crustal environments where acid fluids interact with silicate rocks. High-sulfidation epithermal ore deposits and acid-leached residues at hot-spring settings are among the best known examples. Acid alteration acting on basalts has also been invoked to explain the relatively high silica contents of the surface of Mars. We have analyzed basaltic-andesitic lavas from the Kawah Ijen volcanic complex (East Java, Indonesia) that were altered by interaction with highly acid (pH~1) sulfate-chloride water of its crater lake and seepage stream. Quantitative removal of major elements during this interaction has led to relative increase in SiO2 contents. Our silicon isotope data, obtained by HR-MC-ICPMS and reported relative to the NIST RM8546 (=NBS28) standard, show a systematic increase in &δ&&30Si from -0.2‰ (±0.3, 2sd) for unaltered andesites and basalts to +1.5‰ (±0.3, 2sd) for the most altered/silicified rocks. These results demonstrate that silicification induced by pervasive acid alteration is accompanied by significant Si isotope fractionation, so that alterered products become isotopically heavier than the precursor rocks. Despite the observed enrichment in SiO2, the rocks have experienced an overall net loss of silicon upon alteration, if Nb is considered as perfectly immobile. The observed &δ&&30Si values of the alteration products appeared to correlate well with the inferred amounts of silicon loss. These findings would suggest that &28Si is preferentially leached during water-rock interaction, implying that dissolved silica in the ambient lake and stream water is isotopically light. However, layered opaline lake sediments, that are believed to represent precipitates from the silica-saturated water show a conspicuous &30Si-enrichment (+1.2 ± 0.2‰). Because anorganic precipitation is known to discriminate against the heavy isotope (e.g. Basile- Doelsch et al., 2006

  12. C isotope fractionation during heterotrophic activity driven carbonate precipitation

    Science.gov (United States)

    Balci, Nurgul; Demirel, Cansu

    2016-04-01

    Stable carbon isotopic fractionation during carbonate precipitation induced by environmentally enriched heterotrophic halophilic microorganims was experimentally investigated under various salinity (% 4.5, %8, %15) conditions at 30 °C. Halophilic heterotrophic microorganims were enriched from a hypersaline Lake Acigöl located in SW Turkey (Balci et al.,2015) and later used for the precipitation experiments (solid and liquid medium). The carbonate precipitates had relatively high δ13C values (-4.3 to -16.9 ‰) compared to the δ13C values of the organic compounds that ranged from -27.5 to -25.4 ‰. At salinity of 4.5 % δ13C values of carbonate ranged from -4.9 ‰ to -10.9 ‰ with a 13C-enrichment factor of +20 to +16 ‰ higher than the δ13C values of the associated DOC (-27.5) . At salinity 8 % δ13C values of carbonate ranged from -16.3 ‰ to -11.7 ‰ with a 13C-enrichment factor of+11.3 to+15.9 ‰ higher than the δ13C values of the associated DOC. The respected values for 15 % salinity ranged from -12.3 ‰ to -9.7 ‰ with a 13C-enrichment factor of +15.2 to+16.8 ‰ higher than the δ13C values of the associated DOC. The carbonate precipitates produced in the solid medium are more enriched in 13C relative to liquid culture experiments. These results suggest that the carbon in the solid was derived from both the bacterial oxidation of organic compounds in the medium and from the atmospheric CO2. A solid medium used in the experiments may have suppressed convective and advective mass transport favouring diffusion-controlled system. This determination suggests that the rate and equilibration of CO2 exchange with the atmosphere is the major control on C isotope composition of carbonate minerals precipitated in the experiments. Key words: Lake Acıgöl, halophilic bacteria, carbonate biomineralization, C isotopes References Nurgul Balci, Meryem Menekşe, Nevin Gül Karagüler, M. Şeref Sönmez,Patrick Meister 2015.Reproducing authigenic carbonate

  13. Fractionation behavior of chromium isotopes during coprecipitation with calcium carbonate

    DEFF Research Database (Denmark)

    Rodler, Alexandra; Sánchez-Pastor, Nuria; Fernández-Díaz, Lurdes

    2015-01-01

    Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track paleoenviro......Interest in chromium (Cr) isotope incorporation into carbonates arises from the observation that Cr isotopic composition of carbonates could be used as a paleoclimate proxy to elucidate past fluctuations of oxygen contents in atmosphere and hydrosphere. The use of Cr isotopes to track...

  14. 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)

  15. Light hydrogen isotopes in the single - walled carbon nano tube

    International Nuclear Information System (INIS)

    Khugaev, A.V.; Sultanov, R.A.; Guster, D.

    2007-01-01

    Full text: Progress of our understanding of the molecular hydrogen behavior in the nano tube interior open an intriguing possibility for the applications of these knowledge's to the solution of the hydrogen storage problem and light isotopes gas selectivity. That can strongly change the situation at the energy production in the world and completely change our civil life. These investigations underline the influence of the quantum effects on the properties of molecular hydrogen in the nano tube interior and it leads to the pure quantum-mechanical reformulation of the problem for the hydrogen behavior inside carbon nano tube as a problem of molecular quantum system behavior in the external field induced by the regular nano tube surface. In the present paper the molecular hydrogen behavior in the carbon nano tube was considered in the simple quantum mechanical manner. The main attention was paid to the investigation of the quantum sieving selectivity in the dependence of nano tube composition, radius and symmetry properties. For the interaction potential between hydrogen and nano tube surface was taken some phenomenological LJ(12,6) - (Lennard - Jones) potential and the external field induced by the nano tube in its interior is considered as a simple sum over the all nano tube carbon atoms. Influence of the structure of rotation (vibration) spectrum of the energy levels of diatomic molecules, such as H 2 , HD and D 2 on the final results and finite size of the nano tube along the axis of symmetry, its boundary effects is discussed in details. Thermal oscillations of nano tube surface were considered separately in the dependence of the temperature gradient along of the axis of symmetry

  16. Laser-induced separation of hydrogen isotopes in the liquid phase

    International Nuclear Information System (INIS)

    Beattie, W.; Freund, S.; Holland, R.; Maier, W.

    1980-01-01

    A process for separating hydrogen isotopes which comprises (A) forming a liquid phase of hydrogen-bearing feedstock compound at a temperature at which the spectral features of the feedstock compound are narrow enough or the absorption edges sharp enough to permit spectral features corresponding to the different hydrogen isotopes to be separated to be distinguished, (B) irradiating the liquid phase at said temperature with monochromatic radiation of a first wavelength which selectively or at least preferentially excites those molecules of said feedstock compound containing a first hydrogen isotope, and (C) subjecting the excited molecules to physical or chemical processes or a combination thereof whereby said first hydrogen isotope contained in said excited molecules is separated from other hydrogen isotopes contained in the unexcited molecules in said liquid phase

  17. Short-term carbon isotopic fractionation in plants

    International Nuclear Information System (INIS)

    Rooney, M.A.

    1988-01-01

    A system was developed for measuring carbon isotopic fractionation in plants over a time interval of 1-3 hours, in contrast to leaf combustion studies which give long-term, integrated discrimination measurements. The system was used to study environmental effects on soybean (Glycine max) and corn (Zea mays) discrimination. Changes in leaf temperature, photon flux density (PFD), O 2 concentration, and CO 2 concentration produced little or no change in measured discrimination (Δ). For soybean, Δ increased with decreasing PFD. For corn, Δ decreased with decreasing O 2 concentration. For both soybean and corn, Δ increased with increasing CO 2 concentration. These changes in Δ were interpreted as environmental effects on stomatal conductance and photosynthetic capacity, which indirectly affect Δ by altering C i /C a . Respiratory discrimination in the dark and light was also investigated. Respired CO 2 was 5 per-thousand and 0-1 per-thousand more positive than leaf carbon for soybean and corn, respectively. Photorespiratory discrimination was 6-7 per-thousand for soybean, supporting the contention that glycine decarboxylase may be the source of discrimination in the photorespiratory pathway

  18. Chemical equilibria relating the isotopic hydrogens at low temperatures

    International Nuclear Information System (INIS)

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

    1976-01-01

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

  19. 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

  20. 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.

  1. Reliability of stable Pb isotopes to identify Pb sources and verifying biological fractionation of Pb isotopes in goats and chickens

    International Nuclear Information System (INIS)

    Nakata, Hokuto; Nakayama, Shouta M.M.; Yabe, John; Liazambi, Allan; Mizukawa, Hazuki; Darwish, Wageh Sobhy; Ikenaka, Yoshinori; Ishizuka, Mayumi

    2016-01-01

    Stable Pb isotope ratios (Pb-IRs) have been recognized as an efficient tool for identifying sources. This study carried out at Kabwe mining area, Zambia, to elucidate the presence or absence of Pb isotope fractionation in goat and chicken, to evaluate the reliability of identifying Pb pollution sources via analysis of Pb-IRs, and to assess whether a threshold for blood Pb levels (Pb-B) for biological fractionation was present. The variation of Pb-IRs in goat decreased with an increase in Pb-B and were fixed at certain values close to those of the dominant source of Pb exposure at Pb-B > 5 μg/dL. However, chickens did not show a clear relationship for Pb-IRs against Pb-B, or a fractionation threshold. Given these, the biological fractionation of Pb isotopes should not occur in chickens but in goats, and the threshold for triggering biological fractionation is at around 5 μg/dL of Pb-B in goats. - Highlights: • Presence of Pb isotope fractionation in goat and chicken was studied. • The variation of Pb-IRs in goat decreased with an increase in Pb-B. • Chickens did not show a clear relationship for Pb-IRs against Pb-B. • The biological fractionation of Pb isotopes should not occur in chickens but in goats. • Threshold for triggering biological fractionation is at 5 μg/dL of Pb-B in goats. - Biological fractionation and its threshold for stable Pb isotope ratio in goats and chickens were examined.

  2. Vapour pressure isotope effects in liquid hydrogen chloride

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, J.N.C.; Calado, J.C.G. (Instituto Superior Tecnico, Lisbon (Portugal)); Jancso, Gabor (Hungarian Academy of Sciences, Budapest (Hungary). Central Research Inst. for Physics)

    1992-08-10

    The difference between the vapour pressures of HCl and DCl has been measured over the temperature range 170-203 K by a differential manometric technique in a precision cryostat. In this range the vapour pressure of HCl is higher than that of DCl by 3.2% at 170 K, decreasing to 0.9% at 200 K. The reduced partition function ratios f[sub l]/f[sub g] derived from the vapour pressure data can be described by the equation ln(f[sub l]/f[sub g]) = (3914.57[+-]10)/T[sup 2] - (17.730[+-]0.055)/T. The experimentally observed H-D vapour pressure isotope effect, together with the values on the [sup 35]Cl-[sup 37]Cl isotope effect available in the literature, is interpreted in the light of the statistical theory of isotope effects in condensed systems by using spectroscopic data of the vapour and liquid phases. The results indicate that the rotation in liquid hydrogen chloride is hindered. Temperature-dependent force constants for the hindered translational and rotational motions were invoked in order to obtain better agreement between the model calculation and experiment. (author).

  3. Potential application of gas chromatography to the analysis of hydrogen isotopes

    International Nuclear Information System (INIS)

    Warner, D.K.; Sprague, R.E.; Bohl, D.R.

    1976-01-01

    Gas chromatography is used at Mound Laboratory for the analysis of hydrogen isotopic impurities in gas mixtures. This instrumentation was used to study the applicability of the gas chromatography technique to the determination of the major components of hydrogen isotopic gas mixtures. The results of this study, including chromatograms and precision data, are presented

  4. Insights into Wilson's Warbler migration from analyses of hydrogen stable-isotope ratios

    Science.gov (United States)

    Jeffrey F. Kelly; Viorel Atudorei; Zachary D. Sharp; Deborah M. Finch

    2002-01-01

    Our ability to link the breeding locations of individual passerines to migration stopover sites and wintering locations is limited. Stable isotopes of hydrogen contained in bird feathers have recently shown potential in this regard. We measured hydrogen stable-isotope ratios (deltaD) of feathers from breeding, migrating, and wintering Wilson's Warblers. Analyses...

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

    International Nuclear Information System (INIS)

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

    1981-01-01

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

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

  7. Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates

    Science.gov (United States)

    Skulan, Joseph; DePaolo, Donald J.

    1999-01-01

    Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the 44Ca/40Ca isotopic ratio, the total range of variation observed is 5.5‰, and as much as 4‰ variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers. PMID:10570137

  8. Determination of the interchangeable heavy-metal fraction in soils by isotope dilution mass spectrometry

    International Nuclear Information System (INIS)

    Gaebler, H.E.; Bahr, A.; Mieke, B.

    1999-01-01

    An isotope dilution technique using enriched stable isotopes is applied to determine the interchangeable heavy-metal fraction in soils. Metals in two soil samples are extracted at constant pH, with water, NH 4 NO 3 , and EDTA. A spike of enriched stable isotopes is added to the suspension of sample and eluant at the beginning of the extraction. The heavy-metal fraction which exchanges with the added spike during the extraction is called the interchangeable fraction. The extractable heavy-metal fractions are obtained from the heavy-metal concentrations in the eluates. Isotope ratios and concentrations are determined by HR-ICP-MS. The isotope dilution technique described enables both the extractable and the interchangeable heavy-metal fractions to be determined in the same experiment. The combination of both results gives additional information on elemental availability under different conditions that cannot be obtained by analyzing the extractable heavy-metal fractions alone. It is demonstrated that in some cases different eluants just shift the distribution of the interchangeable fraction of an element between the solid and liquid phases (e.g., Pb and Cd in a topsoil sample) while the amount of the interchangeable fraction itself remains constant. For other elements, as Ni, Zn, and Cr, the use of different eluants (different pH, complexing agents) sometimes enlarges the interchangeable fraction. (orig.)

  9. Isotopic fractionation during the uptake and elimination of inorganic mercury by a marine fish

    International Nuclear Information System (INIS)

    Xu, Xiaoyu; Wang, Wen-Xiong

    2015-01-01

    This study investigated the mass dependent (MDF) and independent fractionation (MIF) of stable mercury isotopes in fish during the uptake and elimination of inorganic species. Mercury accumulation during the exposure led to re-equilibration of organ isotopic compositions with the external sources, and elimination terminated the equilibrating with isotope ratios moving back to the original values. Generally, the isotopic behaviors corresponded to the changes of Hg accumulation in the muscle and liver, causing by the internal transportation, organ redistribution, and mixing of different sources. A small degree of MDF caused by biotransformation of Hg in the liver was documented during the elimination, whereas MIF was not observed. The absence of MIF during geochemical and metabolic processes suggested that mercury isotopes can be used as source tracers. Additionally, fish liver is a more responsive organ than muscle to track Hg source when it is mainly composed of inorganic species. - Highlights: • Isotopic behavior of Hg(II) during the uptake and elimination by a marine fish was studied. • Hg isotopic fractionation in the organ corresponded to the changes of Hg bioaccumulation. • Internal transportation, redistribution and mixing of different sources explained the isotopic changes. • Mass dependent fractionation in the liver was found during Hg elimination. • Liver is more responsive than muscle to track Hg sources using Hg stable isotopes. - Fish liver is a more responsive organ than muscle when mercury stable isotopes are applied to track sources that are mainly composed of inorganic species.

  10. Modeling of hydrogen isotopes separation in a metal hydride bed

    International Nuclear Information System (INIS)

    Charton, S.; Corriou, J.P.; Schweich, D.

    1999-01-01

    A predictive model for hydrogen isotopes separation in a non-isothermal bed of unsupported palladium hydride particles is derived. It accounts for the non-linear adsorption-dissociation equilibrium, hydrodynamic dispersion, pressure drop, mass transfer kinetics, heat of sorption and heat losses at the bed wall. Using parameters from the literature or estimated with classical correlations, the model gives simulated curves in agreement with previously published experiments without any parameter fit. The non-isothermal behavior is shown to be responsible for drastic changes of the mass transfer rate which is controlled by diffusion in the solid-phase lattice. For a feed at 300 K and atmospheric pressure, the endothermic hydride-to-deuteride exchange is kinetically controlled, whereas the reverse exothermic exchange is nearly at equilibrium. Finally, a simple and efficient thermodynamic model for the dissociative equilibrium between a metal and a diatomic gas is proposed. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  11. Wetting phenomena in films of molecular hydrogen isotopes

    International Nuclear Information System (INIS)

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

    1996-01-01

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

  12. Next-generation TCAP hydrogen isotope separation process

    International Nuclear Information System (INIS)

    Heung, L. K.; Sessions, H. T.; Poore, A. S.; Jacobs, W. D.; Williams, C. S.

    2008-01-01

    A thermal cycling absorption process (TCAP) for hydrogen isotope separation has been in operation at Savannah River Site since 1994. The process uses a hot/cold nitrogen system to cycle the temperature of the separation column. The hot/cold nitrogen system requires the use of large compressors, heat exchanges, valves and piping that is bulky and maintenance intensive. A new compact thermal cycling (CTC) design has recently been developed. This new design uses liquid nitrogen tubes and electric heaters to heat and cool the column directly so that the bulky hot/cold nitrogen system can be eliminated. This CTC design is simple and is easy to implement, and will be the next generation TCAP system at SRS. A twelve-meter column has been fabricated and installed in the laboratory to demonstrate its performance. The design of the system and its test results to date is discussed. (authors)

  13. 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)

  14. Large scale gas chromatographic demonstration system for hydrogen isotope separation

    International Nuclear Information System (INIS)

    Cheh, C.H.

    1988-01-01

    A large scale demonstration system was designed for a throughput of 3 mol/day equimolar mixture of H,D, and T. The demonstration system was assembled and an experimental program carried out. This project was funded by Kernforschungszentrum Karlsruhe, Canadian Fusion Fuel Technology Projects and Ontario Hydro Research Division. Several major design innovations were successfully implemented in the demonstration system and are discussed in detail. Many experiments were carried out in the demonstration system to study the performance of the system to separate hydrogen isotopes at high throughput. Various temperature programming schemes were tested, heart-cutting operation was evaluated, and very large (up to 138 NL/injection) samples were separated in the system. The results of the experiments showed that the specially designed column performed well as a chromatographic column and good separation could be achieved even when a 138 NL sample was injected

  15. Chromium isotope fractionation during oxidative weathering of a modern basaltic weathering profile

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary; Døssing, Lasse Nørbye; Frei, Robert

    Chromium can be used as a tracer of redox sensitive environmental processes. In soils Cr (III) is inert, immobile and resides predominantly in minerals, clays and oxides. Cr (VI) is toxic, soluble and mobile and is usually lost from the soil to local run off. Chromium isotopes have been shown...... to fractionate under both reducing and oxidizing conditions [1, 2]. Recent studies on d53Cr isotopes in laterite soils show that oxidative weathering of Cr-bearing rocks is accompanied by an isotopic fractionation, where by the lighter isotopes are retained in the residual soil and the heavier isotope...... is enriched in local runoff [1]. This study aims to quantify the stable Cr isotope composition of two modern basaltic weathering profiles, to help better understand the processes that oxidize inert Cr (III) to toxic Cr (VI). We sampled basaltic weathering profiles and associated river waters from areas of two...

  16. Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

    Science.gov (United States)

    Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

    2017-12-01

    The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

  17. Hydrogen/deuterium fractionation factors of the aqueous ligand of cobalt in Co(H2O)62+ and Co(II)-substituted carbonic anhydrase

    International Nuclear Information System (INIS)

    Kassebaum, J.W.

    1988-01-01

    The author has measured the hydrogen/deuterium fractionation factor for the rapidly exchanging aqueous ligands of cobalt in Co(H 2 O) 6 2+ and in three Co(II)-substituted isozymes of carbonic anhydrase. The fractionation factor was determined from NMR relaxation rates at 300 MHz of the protons of water in mixed solutions of H 2 O and D 2 O containing these complexes. In each case, the paramagnetic contribution to 1/T 2 was greater than to 1/T 1 , consistent with a chemical shift mechanism affecting 1/T 2 . The fractionation factors obtained from T 2 were 0.73 ± 0.02 for Co(H 2 O) 6 2+ , 0.72 ± 0.02 for Co(II)-substituted carbonic anhydrase I, 0.77 ± 0.01 for Co(II)-substituted carbonic anhydrase II, and 1.00 ± 0.07 for Co(Il)-substituted carbonic anhydrase III. He concluded that fractionation factors in these cases determined from T 1 and T 2 measured isotope preferences for different populations of ligand sites. Since T 2 has a large contribution from a chemical shift mechanism, the fractionation factor determined from T 2 has a large contribution of the fractionation of inner shell ligands. The fractionation factor of Co(H 2 O) 6 2+ was used to interpret the solvent hydrogen isotope effects on the formation of complexes of cobalt with the bidentate ligands glycine, N,N-dimethylglycine, and acetylacetone. The contribution of the fractionation factor of the inner water shell in Co(H 2 O) 6 2+ did not account completely for the measured isotope effect, and that the hydrogen/deuterium fractionation of outer shell water makes a large contribution to the isotope effect on the formation of these complexes

  18. 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

  19. Stable carbon isotope fractionation in the search for life on early Mars

    Science.gov (United States)

    Rothschild, L. J.; Desmarais, D.

    1989-01-01

    The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

  20. Weathering and vegetation controls on nickel isotope fractionation in surface ultramafic environments (Albania)

    Science.gov (United States)

    Estrade, Nicolas; Cloquet, Christophe; Echevarria, Guillaume; Sterckeman, Thibault; Deng, Tenghaobo; Tang, YeTao; Morel, Jean-Louis

    2015-08-01

    The dissolved nickel (Ni) isotopic composition of rivers and oceans presents an apparent paradox. Even though rivers represent a major source of Ni in the oceans, seawater is more enriched in the heavier isotopes than river-water. Additional sources or processes must therefore be invoked to account for the isotopic budget of dissolved Ni in seawater. Weathering of continental rocks is thought to play a major role in determining the magnitude and sign of isotopic fractionation of metals between a rock and the dissolved product. We present a study of Ni isotopes in the rock-soil-plant systems of several ultramafic environments. The results reveal key insights into the magnitude and the control of isotopic fractionation during the weathering of continental ultramafic rocks. This study introduces new constraints on the influence of vegetation during the weathering process, which should be taken into account in interpretations of the variability of Ni isotopes in rivers. The study area is located in a temperate climate zone within the ophiolitic belt area of Albania. The serpentinized peridotites sampled present a narrow range of heavy Ni isotopic compositions (δ60Ni = 0.25 ± 0.16 ‰, 2SD n = 2). At two locations, horizons within two soil profiles affected by different degrees of weathering all presented light isotopic compositions compared to the parent rock (Δ60Nisoil-rock up to - 0.63 ‰). This suggests that the soil pool takes up the light isotopes, while the heavier isotopes remain in the dissolved phase. By combining elemental and mineralogical analyses with the isotope compositions determined for the soils, the extent of fractionation was found to be controlled by the secondary minerals formed in the soil. The types of vegetation growing on ultramafic-derived soils are highly adapted and include both Ni-hyperaccumulating species, which can accumulate several percent per weight of Ni, and non-accumulating species. Whole-plant isotopic compositions were found

  1. Hydrogen isotope separation in hydrophobic catalysts between hydrogen and liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Linsen, E-mail: yls2005@mail.ustc.edu.cn [China Academy of Engineering Physics, Mianyang 621900 (China); Luo, Deli [Science and Technology on Surface Physics and Chemistry Laboratory, Jiangyou 621907 (China); Tang, Tao; Yang, Wan; Yang, Yong [China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-11-15

    Hydrogen isotope catalytic exchange between hydrogen and liquid water is a very effective process for deuterium-depleted potable water production and heavy water detritiation. To improve the characteristics of hydrophobic catalysts for this type of reaction, foamed and cellular structures of hydrophobic carbon-supported platinum catalysts were successfully prepared. Separation of deuterium or tritium from liquid water was carried out by liquid-phase catalytic exchange. At a gas–liquid ratio of 1.53 and exchange temperature of 70 °C, the theoretical plate height of the hydrophobic catalyst (HETP = 34.2 cm) was slightly lower than previously reported values. Changing the concentration of the exchange column outlet water yielded nonlinear changes in the height of the packing layer. Configurations of deuterium-depleted potable water and detritiation of heavy water provide references for practical applications.

  2. Extending the Rayleigh equation to allow competing isotope fractionating pathways to improve quantification of biodegradation

    NARCIS (Netherlands)

    van Breukelen, B.M.

    2007-01-01

    The Rayleigh equation relates the change in isotope ratio of an element in a substrate to the extent of substrate consumption via a single kinetic isotopic fractionation factor (α). Substrate consumption is, however, commonly distributed over several metabolic pathways each potentially having a

  3. Equilibrium mercury isotope fractionation between dissolved Hg(II) species and thiol-bound Hg

    NARCIS (Netherlands)

    Wiederhold, Jan G.; Cramer, Christopher J.; Daniel, Kelly; Infante, Ivan; Bourdon, Bernard; Kretzschmar, Ruben

    2010-01-01

    Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound

  4. 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

  5. Hydrogen and carbon isotopes of petroleum and related organic matter

    International Nuclear Information System (INIS)

    Yeh, H.W.; Epstein, S.

    1981-01-01

    D/H and 13 C/ 12 C ratios were measured for 114 petroleum samples and for several samples of related organic matter. DeltaD of crude oil ranges from -85 to -181 per thousand except for one distillate (-250 per thousand) from the Kenai gas field; delta 13 C of crude oil ranges from -23.3 to -32.5 per thousand. Variation in deltaD and delta 13 C values of compound-grouped fractions of a crude oil is small, 3 and 1.1 per thousand, respectively, and the difference in deltaD and delta 13 C between oil and coeval wax is slight. Gas fractions are 53 to 70 and 22.6 to 23.2 per thousand depleted in D and 13 C, respectively, relative to the coexisting oil fractions. The deltaD and delta 13 C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant. (author)

  6. Experimental evidence for Mo isotope fractionation between metal and silicate liquids

    Science.gov (United States)

    Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

    2013-10-01

    Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

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

    Science.gov (United States)

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

    2018-06-01

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

  8. Round robin analyses of hydrogen isotope thin films standards

    Energy Technology Data Exchange (ETDEWEB)

    Banks, J.C. E-mail: jcbanks@sandia.gov; Browning, J.F.; Wampler, W.R.; Doyle, B.L.; LaDuca, C.A.; Tesmer, J.R.; Wetteland, C.J.; Wang, Y.Q

    2004-06-01

    Hydrogen isotope thin film standards have been manufactured at Sandia National Laboratories for use by the materials characterization community. Several considerations were taken into account during the manufacture of the ErHD standards, with accuracy and stability being the most important. The standards were fabricated by e-beam deposition of Er onto a Mo substrate and the film stoichiometrically loaded with hydrogen and deuterium. To determine the loading accuracy of the standards two random samples were measured by thermal desorption mass spectrometry and atomic absorption spectrometry techniques with a stated combined accuracy of {approx}1.6% (1{sigma}). All the standards were then measured by high energy RBS/ERD and RBS/NRA with the accuracy of the techniques {approx}5% (1{sigma}). The standards were then distributed to the IBA materials characterization community for analysis. This paper will discuss the suitability of the standards for use by the IBA community and compare measurement results to highlight the accuracy of the techniques used.

  9. Palladium alloy membrane process for the treatment of hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Hongsuk; Paek, Seungwoo; Lee, Minsoo; Kim, Kwangrag; Yim, Sungpaal; Ahn, Dohee [KAERI, Daejeon (Korea, Republic of); Shim, Myunghwa [Univ. of Science and Technology, Daejeon (Korea, Republic of)

    2005-11-15

    Tritium is a radioactive isotope of hydrogen and it has a half-life of 12.3 years; it decays to He-3 by emitting a low energy beta radiation with an average energy of 5.7 keV and a maximum energy of 18.6 keV. Transfer of environmentally tritiated water to humans takes place via an inhalation, diffusion through the skin and ingestion. Radioactive waste containing tritium is continuously generated by the nuclear industry in, for example, nuclear reactor operations and a radioisotope production, as well as in medical research. Methods for removing tritium from liquid waste provide an alternative to the control of tritium emissions and a personnel exposure. A combined electrolysis and catalytic exchange process is a very effective method to remove small quantities of tritium from light or heavy waste water streams. The process consists of three main steps: (a) A front end step that exchanges the tritium to a less toxic hydrogen phase. This can be performed either through a chemical exchange in the presence of a platinum supported catalyst or through the decomposition of water. (b) A back end process that purifies the tritiated hydrogen gas which evolved from the electrolysis. This can be performed through a palladium alloy membrane separator. (c) A means of storing the concentrated gas safely. Uranium is used if the storage is temporary; titanium is usually employed for long term storage. To gain a better understanding of the tritiated hydrogen gas purification process, a mathematical model of the palladium alloy membrane has been used. This model is described herein, and the representative results of the model calculations are presented. The authors selected the palladium alloy membrane for the hydrogen purification process by considering the membrane properties, such as a chemical resistance, mechanical stability, thermal stability, high permeability, and a stable operation. The solution-diffusion model can be a useful tool for designing a membrane permeator. The

  10. Release of hydrogen isotopes from carbon based fusion reactor materials

    International Nuclear Information System (INIS)

    Vainonen-Ahlgren, E.

    2000-01-01

    The purpose of this study is to understand the annealing behavior of hydrogen isotopes in carbon based materials. Also, the density of the material and structural changes after thermal treatment and ion irradiation are examined. The study of hydrogen diffusion in diamondlike carbon films revealed an activation energy of 2.0 eV, while the deuterium diffusion, due to better measuring sensitivity, is found to be concentration dependent with the effective diffusion coefficient becoming smaller with decreasing deuterium concentration. To explain the experimentally observed profiles, a model according to which atomic deuterium diffuses and deuterium in clusters is immobile is developed. The concentration of immobile D was assumed to be an analytical function of the total D concentration. To describe the annealing behavior of D incorporated in diamondlike carbon films during the deposition process, a model taking into account diffusion of free D and thermal detrapping and trapping of D was developed. The difference in the analysis explains the disagreement of activation energy (1.5 ± 0.2 eV) with the value of 2,9± 0.1 eV obtained for D implanted samples earlier. The same model was applied to describe the experimental profiles in Si doped diamondlike carbon films. Si affects the retention of D in diamondlike carbon films. The amount of D depends on Si content in the co-deposited but not implanted samples. Besides, Si incorporation into carbon coating decreases to some extent the graphitization of the films and leads to formation of a structure which is stable under thermal treatment and ion irradiation. Hydrogen migration in the hydrogen and methane co-deposited films was also studied. In samples produced in methane atmosphere and annealed at different temperatures, the hydrogen concentration level decreases in the bulk, with more pronounced release at the surface region. In the case of coatings deposited by a methane ion beam, the H level also decreases with increasing

  11. Palladium alloy membrane process for the treatment of hydrogen isotopes

    International Nuclear Information System (INIS)

    Chung, Hongsuk; Paek, Seungwoo; Lee, Minsoo; Kim, Kwangrag; Yim, Sungpaal; Ahn, Dohee; Shim, Myunghwa

    2005-01-01

    Tritium is a radioactive isotope of hydrogen and it has a half-life of 12.3 years; it decays to He-3 by emitting a low energy beta radiation with an average energy of 5.7 keV and a maximum energy of 18.6 keV. Transfer of environmentally tritiated water to humans takes place via an inhalation, diffusion through the skin and ingestion. Radioactive waste containing tritium is continuously generated by the nuclear industry in, for example, nuclear reactor operations and a radioisotope production, as well as in medical research. Methods for removing tritium from liquid waste provide an alternative to the control of tritium emissions and a personnel exposure. A combined electrolysis and catalytic exchange process is a very effective method to remove small quantities of tritium from light or heavy waste water streams. The process consists of three main steps: (a) A front end step that exchanges the tritium to a less toxic hydrogen phase. This can be performed either through a chemical exchange in the presence of a platinum supported catalyst or through the decomposition of water. (b) A back end process that purifies the tritiated hydrogen gas which evolved from the electrolysis. This can be performed through a palladium alloy membrane separator. (c) A means of storing the concentrated gas safely. Uranium is used if the storage is temporary; titanium is usually employed for long term storage. To gain a better understanding of the tritiated hydrogen gas purification process, a mathematical model of the palladium alloy membrane has been used. This model is described herein, and the representative results of the model calculations are presented. The authors selected the palladium alloy membrane for the hydrogen purification process by considering the membrane properties, such as a chemical resistance, mechanical stability, thermal stability, high permeability, and a stable operation. The solution-diffusion model can be a useful tool for designing a membrane permeator. The

  12. Nickel distribution and isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES

    Science.gov (United States)

    Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimarães, E.; Monvoisin, G.; Nouet, J.; Ponzevera, E.; Quantin, C.

    2018-06-01

    Ultramafic (UM) rocks are known to be nickel (Ni) rich and to weather quickly, which makes them a good candidate to look at the Ni isotope systematics during weathering processes at the Earth's surface. The present study aims at identifying the Ni solid speciation and discussing the weathering processes that produce Ni isotope fractionation in two deep laterite profiles under tropical conditions (Barro Alto, Goiás State, Brazil). While phyllosilicates and to a lower extent goethite are the main Ni-bearing phases in the saprolitic part of the profile, iron (Fe) oxides dominate the Ni budget in the lateritic unit. Nickel isotopic composition (δ60Ni values) has been measured in each unit of the regolith, i.e., rock, saprock, saprolite and laterite (n = 52). δ60Ni varies widely within the two laterite profiles, from -0.10 ± 0.05‰ to 1.43 ± 0.05‰, showing that significant Ni isotope fractionation occurs during the weathering of UM rocks. Overall, our results show that during weathering, the solid phase is depleted in heavy Ni isotopes due to the preferential sorption and incorporation of light Ni isotopes into Fe oxides; the same mechanisms likely apply to the incorporation of Ni into phyllosilicates (type 2:1). However, an isotopically heavy Ni pool is observed in the solid phase at the bottom of the saprolitic unit. This feature can be explained by two hypotheses that are not mutually exclusive: (i) a depletion in light Ni isotopes during the first stage of weathering due to the preferential dissolution of light Ni-containing minerals, and (ii) the sorption or incorporation of isotopically heavy Ni carried by percolating waters (groundwater samples have δ60Ni of 2.20 and 2.27‰), that were enriched in heavy Ni isotopes due to successive weathering processes in the overlying soil and laterite units.

  13. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yunde [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Laboratory of Basin Hydrology and Wetland Eco-restoration, China University of Geosciences, Wuhan 430074 (China); Zhou, Aiguo, E-mail: aiguozhou@cug.edu.cn [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China); Gan, Yiqun; Li, Xiaoqian [State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074 (China); School of Environmental Studies, China University of Geosciences, Wuhan 430074 (China)

    2016-05-05

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO{sub 3}{sup −}, or SO{sub 4}{sup 2−}. • Cl{sup −} significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  14. Effects of inorganic anions on carbon isotope fractionation during Fenton-like degradation of trichloroethene

    International Nuclear Information System (INIS)

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-01-01

    Highlights: • The effect of inorganic anions on carbon isotope fractionation was evaluated. • The enrichment factors was independent concentration of NO_3"−, or SO_4"2"−. • Cl"− significantly influenced the carbon isotope fractionation. - Abstract: Understanding the magnitude and variability in isotope fractionation with respect to specific processes is crucial to the application of stable isotopic analysis as a tool to infer and quantify transformation processes. The variability of carbon isotope fractionation during Fenton-like degradation of trichloroethene (TCE) in the presence of different inorganic ions (nitrate, sulfate, and chloride), was investigated to evaluate the potential effects of inorganic anions on carbon isotope enrichment factor (ε value). A comparison of ε values obtained in deionized water, nitrate solution, and sulfate solution demonstrated that the ε values were identical and not affected by the presence of nitrate and sulfate. In the presence of chloride, however, the ε values (ranging from −6.3 ± 0.8 to 10 ± 1.3‰) were variable and depended on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during Fenton-like degradation of TCE. Thus, caution should be exercised in selecting appropriate ε values for the field application of stable isotope analysis, as various chloride concentrations may be present due to naturally present or introduced with pH adjustment and iron salts during Fenton-like remediation. Furthermore, the effects of chloride on carbon isotope fractionation may be able to provide new insights about reaction mechanisms of Fenton-like processes.

  15. Biological fractionation of lead isotopes in Sprague-Dawley rats lead poisoned via the respiratory tract.

    Directory of Open Access Journals (Sweden)

    Jing Wu

    Full Text Available It was considered that lead isotope ratios did not change during physical, chemical, or biological processes. Thus, lead isotope ratios have been used as fingerprints to identify possible lead sources. However, recent evidence has shown that the lead isotope ratios among different biological samples in human are not always identical from its lead origins in vitro. An animal experiment was conducted to explore the biological fractionation of lead isotopes in biological systems.24 male Sprague-Dawley (SD rats were divided into groups that received acute lead exposure (0, 0.02, 0.2, or 2 mg/kg body weight of lead acetate via the respiratory route every day for 5 days. Biological samples (i.e., blood, urine, and feces were collected for comparison with the lead acetate (test substance and the low-lead animal feed (diet administered to the rats. The lead isotope ratios were determined by inductively coupled plasma mass spectrometry (ICP-MS.There are significant differences (p<0.05 in lead isotope ratios between blood, urine, and feces. Moreover, a nonlinear relationship between the blood lead concentration and the blood lead isotope ratios was observed. There is also a threshold effect to the fractionation function. Only the blood isotope ratio of (204Pb/(206Pb matches the test substance well. As for feces, when (204Pb/(206Pb ratio is considered, there is no significant difference between feces-test substance pairs in medium and high dose group.The biological fractionation of lead isotopes in SD rats was observed. Moreover, there might be a threshold for the biological fractionation of lead isotopes which is depending on whole blood lead level. It is considered to be more reliable that we compared the isotope ratios of potential lead hazards with both blood and feces lead fingerprints especially for (204Pb/(206Pb ratio under high-dose exposure.

  16. Hydrogen apparent fractionation between source water and epicuticular waxes of Pinus sylvestris in North East Finland

    Science.gov (United States)

    Newberry, S. L.; Grace, J.; Pedentchouk, N.

    2010-12-01

    Hydrogen isotopic composition of plant biomass provides crucial information about plant ecophysiology and local hydrology. Little is known about the apparent fractionation between hydrogen in source water and epicuticular leaf waxes of coniferous tree species that dominate the boreal forest ecosystem exposed to prolonged periods of sunlight during the growing season. In this study, single rope canopy access techniques were used to harvest needle and twig material from the upper, middle and lower crown of north and south facing branches of Pinus sylvestris within the subarctic forest of North East Finland. Samples were collected towards the beginning of the growing season in July and repeated in late September 2010. Leaf and twig waters were extracted cryogenically and analysed for D-enrichment. Individual n-alkanes are currently being quantified and analyzed for 13C/12C and D/H compositions. The molecular and isotopic data are supplemented by long-term in-situ cuvette photosynthetic assimilation measurements as well as relative humidity (RH), air temperature, precipitation and wind speed data collected by Helsinki University (SMEAR I). In addition RH, air temperature, wind speed and incoming solar radiation measurements were made at each individual sample point at the time of harvesting to quantify meteorological and microclimatological variation within individual trees. The outcome of this investigation will provide important insights into plant biochemistry and physiology of a crucial climate sensitive higher plant species subjected to continuous low light throughout the season. Furthermore, this work will expand our understanding of modern and palaeo-hydrology not only in northern Finland but also in other boreal forests around the world.

  17. Stable carbon, nitrogen and sulfur isotopes in non-carbonate fractions of cold-seep carbonates

    Science.gov (United States)

    Feng, Dong; Peng, Yongbo; Peckmann, Jörn; Roberts, Harry; Chen, Duofu

    2017-04-01

    Sulfate-driven anaerobic oxidation of methane (AOM) supports chemosynthesis-based communities and limits the release of methane from marine sediments. This process promotes the formation of carbonates close to the seafloor along continental margins. The geochemical characteristics of the carbonate minerals of these rocks are increasingly understood, questions remain about the geochemical characteristics of the non-carbonate fractions. Here, we report stable carbon, nitrogen and sulfur isotope patterns in non-carbonate fractions of seep carbonates. The authigenic carbonates were collected from three modern seep provinces (Black Sea, Gulf of Mexico, and South China Sea) and three ancient seep deposits (Marmorito, northern Italy, Miocene; SR4 deposit of the Lincoln Creek Formation and Whiskey Creek, western Washington, USA, Eocene to Oligocene). The δ13C values of non-carbonate fractions range from ˜-25‰ to -80‰ VPDB. These values indicate that fossil methane mixed with varying amounts of pelagic organic matter is the dominant source of carbon in these fractions. The relatively small offset between the δ34S signatures of the non-carbonate fractions and the respective sulfide minerals suggests that locally produced hydrogen sulfide is the main source of sulfur in seep environments. The δ15N values of the non-carbonate fractions are generally lower than the corresponding values of deep-sea sediments, suggesting that organic nitrogen is mostly of a local origin. This study reveals the potential of using δ13C, δ15N, δ34S values to discern seep and non-seep deposits. In cases where δ13Ccarbonate values are only moderately low due to mixing processes and lipid biomarkers have been erased in the course of burial, it is difficult to trace back AOM owing to the lack of other records. This problem is even more pronounced when authigenic carbonate is not available in ancient seep environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support

  18. Study of hydrogen isotopes super permeation through vanadium membrane on 'Prometheus' setup

    International Nuclear Information System (INIS)

    Musyaev, R. K.; Yukhimchuk, A. A.; Lebedev, B. S.; Busnyuk, A. O.; Notkin, M. E.; Samartsev, A. A.; Livshits, A. I.

    2008-01-01

    To develop the membrane pumping technology by means of superpermeable membranes at RFNC-VNIIEF in the 'Prometheus' setup, the experiments on superpermeation of hydrogen isotopes through metal membranes were carried out. The experimental results on superpermeation of thermal atoms of hydrogen isotopes including tritium through a cylindrical vanadium membrane are presented. The possibility of effective pumping, compression and recuperation of hydrogen isotopes by means of superpermeable membrane was demonstrated. The evaluation of membrane pumping rates and asymmetry degree of pure vanadium membrane was given. The work was performed under the ISTC-2854 project. (authors)

  19. Parameter study on Japanese proposal of ITER hydrogen isotope separation system

    International Nuclear Information System (INIS)

    Yoshida, Hiroshi; Enoeda, Mikio; Tanaka, Shigeru; Ohokawa, Yoshinao; Ohara, Atsushi; Nagakura, Masaaki; Naito, Taisei; Nagashima, Kazuhiro.

    1991-01-01

    As part of Japanese design contribution in the ITER activity, conceptual design of an entire ITER tritium system and their safety analysis have been carried out through the three-year period since 1988. The tritium system includes the following subsystems; - Fuelling (gas puffing and pellet injection) subsystem, - Torus vacuum pumping subsystem, - Plasma exhaust gas purification subsystem, - Hydrogen isotope separation subsystem, - NBI gas processing subsystem, - Blanket tritium recovery subsystem, - Tritiated water processing subsystem, - Tritium safety subsystem. Hydrogen isotope separation system is a key subsystem in the ITER tritium system because it is connected to all above subsystems. This report describes an analytical study on the Japanese concept of hydrogen isotope separation system. (author)

  20. Hydrogen isotopic messages in sulfate reducer lipids: a recorder of metabolic state?

    Science.gov (United States)

    Bradley, A. S.; Leavitt, W.; Zhou, A.; Cobban, A.; Suess, M.

    2017-12-01

    A significant range in microbial lipid 2H/1H ratios is observed in modern marine sediments. The magnitude of hydrogen isotope fractionation between microbial lipids and growth water (2ɛlipid-H2O) is hypothesized to relate to the central carbon and energy metabolism. These observations raise the possibility for culture independent identification of the dominant metabolic pathways operating in a given environment [Zhang et al. 2009]. One such metabolism we aim to track is microbial sulfate reduction. To-date, sulfate reducing bacteria have been observed to produce lipids that are depleted in fatty acid H-isotope composition, relative to growth water (2ɛlipid-H2O -50 to -175 ‰) [Campbell et al. 2009; Dawson et al. 2015; Osburn et al.], with recent work demonstrating a systematic relationship between lipid/water fractionation and growth rate when the electron-bifurcating NAD(P)(H) transhydrogenase (ebTH) activity was disrupted and the available electron requires the ebTH [Leavitt et al. 2016. Front Microbio]. Recent work in aerobic methylotrophs [Bradley et al. 2014. AGU] implicates non-bifurcating NAD(P)(H) transhydrogenase activity is a critical control on 2ɛlipid-H2O. This suggests a specific mechanism to control the range in fractionation is the ratio of intracellular NADPH/NADH/NADP/NAD in aerobes and perhaps the same in anaerobes with some consideration for FADH/FAD. Fundamentally this implies 2ɛlipid-H2O records intracellular redox state. In our sulfate reducer model system Desulfovibrio alaskensis strain G20 a key component of energy metabolism is the activity of ebTH. Nonetheless, this strain contains two independent copies of the genes, only one of which generates a distinctive isotopic phenotype [Leavitt et al. 2016. Front Microbio]. In this study we extend the recent work in G20 to continuous culture experiments comparing WT to nfnAB-2 transposon interruptions, where both organisms are cultivated continuously, at the rate of the slower growing mutant

  1. 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.

  2. Application of hydrogen isotopes and metal hydrides in future energy source

    Energy Technology Data Exchange (ETDEWEB)

    Guoqiang, Jiang [Sichuan Inst. of Materials and Technology, Chengdu, SC (China)

    1994-12-01

    The probable application of hydrogen isotopes and metal hydrides to future energy source is reviewed. Starting from existing state of China`s energy source, the importance for developing hydrogen energy and fusion energy is explained. It is suggested that the application investigation of hydrogen energy and hydrogen storage materials should be spurred and encouraged; keeping track of the development on tritium technology for fusion reactor is stressed.

  3. Application of hydrogen isotopes and metal hydrides in future energy source

    International Nuclear Information System (INIS)

    Jiang Guoqiang

    1994-12-01

    The probable application of hydrogen isotopes and metal hydrides to future energy source is reviewed. Starting from existing state of China's energy source, the importance for developing hydrogen energy and fusion energy is explained. It is suggested that the application investigation of hydrogen energy and hydrogen storage materials should be spurred and encouraged; keeping track of the development on tritium technology for fusion reactor is stressed

  4. Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

    Science.gov (United States)

    Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

    2018-02-01

    Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in

  5. Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

    Energy Technology Data Exchange (ETDEWEB)

    Dahl, Tais W.; Wirth, Stefanie B.

    2017-06-01

    The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past ~ 9800 years in one of the best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to

  6. Observations of Isotope Fractionation in Prestellar Cores: Interstellar Origin of Meteoritic Hot Spot?

    Science.gov (United States)

    Milam, S. N.; Charnley, S. B.

    2011-01-01

    Isotopically fractionated material is found in many solar system objects, including meteorites and comets. It is thought, in some cases, to trace interstellar material that was incorporated into the solar system without undergoing significant processing. Here, we show the results of models and observations of the nitrogen and carbon fractionation in proto-stellar cores.

  7. Joint interpretation of enantiomer and stable isotope fractionation for chiral pesticides degradation

    DEFF Research Database (Denmark)

    Jin, Biao; Rolle, Massimo

    2016-01-01

    introduce a modeling approach with the aim of unifying and integrating the interpretation of isotopic and enantiomeric fractionation. The model is based on the definition of enantiomer-specific isotopologues and jointly predicts the evolution of concentration, enantiomer fractionation, as well as changes...

  8. Biological fractionation of lead isotopes in Sprague-Dawley rats lead poisoned via the respiratory tract.

    Science.gov (United States)

    Wu, Jing; Liu, Duojian; Xie, Qing; Wang, Jingyu

    2012-01-01

    It was considered that lead isotope ratios did not change during physical, chemical, or biological processes. Thus, lead isotope ratios have been used as fingerprints to identify possible lead sources. However, recent evidence has shown that the lead isotope ratios among different biological samples in human are not always identical from its lead origins in vitro. An animal experiment was conducted to explore the biological fractionation of lead isotopes in biological systems. 24 male Sprague-Dawley (SD) rats were divided into groups that received acute lead exposure (0, 0.02, 0.2, or 2 mg/kg body weight of lead acetate) via the respiratory route every day for 5 days. Biological samples (i.e., blood, urine, and feces) were collected for comparison with the lead acetate (test substance) and the low-lead animal feed (diet) administered to the rats. The lead isotope ratios were determined by inductively coupled plasma mass spectrometry (ICP-MS). There are significant differences (pblood, urine, and feces. Moreover, a nonlinear relationship between the blood lead concentration and the blood lead isotope ratios was observed. There is also a threshold effect to the fractionation function. Only the blood isotope ratio of (204)Pb/(206)Pb matches the test substance well. As for feces, when (204)Pb/(206)Pb ratio is considered, there is no significant difference between feces-test substance pairs in medium and high dose group. The biological fractionation of lead isotopes in SD rats was observed. Moreover, there might be a threshold for the biological fractionation of lead isotopes which is depending on whole blood lead level. It is considered to be more reliable that we compared the isotope ratios of potential lead hazards with both blood and feces lead fingerprints especially for (204)Pb/(206)Pb ratio under high-dose exposure.

  9. 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

  10. Kinetic fractionation of stable nitrogen isotopes during amino acid transamination

    International Nuclear Information System (INIS)

    Macko, S.A.; Fogel Estep, M.L.; Engel, M.H.; Hare, P.E.

    1986-01-01

    This study evaluates a kinetic isotope effect involving 15 N, during the transamination reactions catalyzed by glutamic oxalacetic transaminase. During the transfer of amino nitrogen from glutamic acid to oxaloacetate to form aspartic acid, 14 NH 2 reacted 1.0083 times faster than 15 NH 2 . In the reverse reaction transferring NH 2 from aspartic acid to α-ketoglutarate, 14 NH 2 was incorporated 1.0017 times faster than 15 NH 2 . Knowledge of the magnitude and sign of these isotope effects will be useful in the interpretation of the distribution of 15 N in biological and geochemical systems. (author)

  11. Hydrogen-isotope motion in scandium studied by ultrasonic measurements

    International Nuclear Information System (INIS)

    Leisure, R.G.; Schwarz, R.B.; Migliori, A.; Torgeson, D.R.; Svare, I.

    1993-01-01

    Resonant ultrasound spectroscopy has been used to investigate ultrasonic attenuation in single crystals of Sc, ScH 0.25 , and ScD 0.18 over the temperature range of 10--300 K for frequencies near 1 MHz. Ultrasonic-attenuation peaks were observed in the samples containing H or D with the maximum attenuation occurring near 25 K for ScH 0.25 and near 50 K for ScD 0.18 . The general features of the data suggest that the motion reflected in the ultrasonic attenuation is closely related to the low-temperature motion seen in nulcear-magnetic-resonance spin-lattice-relaxation measurements. The ultrasonic results were fit with a two-level-system (TLS) model involving tunneling between highly asymmetric sites. The relaxation of the TLS was found to consist of two parts: a weakly temperature-dependent part, probably due to coupling to electrons; and a much more strongly temperature-dependent part, attributed to multiple-phonon processes. The strongly temperature-dependent part was almost two orders of magnitude faster in ScH 0.25 than in ScD 0.18 , in accordance with the idea that tunneling is involved in the motion. Surprisingly, the weakly temperature-dependent part was found to be about the same for the two isotopes. The asymmetries primarily responsible for coupling the TLS to the ultrasound are attributed to interactions between hydrogen ions that lie on adjacent c axes. The results are consistent with an isotope-independent strength for the coupling of the TLS to the ultrasound

  12. Separation of Hydrogen Isotopes by Palladium Alloy Membranes Separator

    International Nuclear Information System (INIS)

    Jiangfeng, S.; Deli, L.; Yifu, X.; Congxian, L.; Zhiyong, H.

    2007-01-01

    Full text of publication follows: Separation of hydrogen isotope with palladium alloy membranes is one of the promising methods for hydrogen isotope separation. It has several advantages, such as high separation efficiency, smaller tritium inventory, simple separation device, ect. Limited by the manufacture of membrane and cost of gas transportation pump, this method is still at the stage of conceptual study. The relationship between separation factors and temperatures, feed gas components, split ratios have not been researched in detail, and the calculated results of cascade separation have not been validated with experimental data. In this thesis, a palladium alloy membrane separator was designed to further study its separation performance between H 2 and D 2 . The separation factor of the single stage was affected by the temperature, the feed gas component, the split ratio and the gas flow rate, etc. The experimental results showed that the H 2 -D 2 separation factor decreased with the increasing of temperature. On the temperature from 573 K to 773 K, when the feed rate was 5 L/min, the separation factor of 66.2%H 2 - 33.8%D 2 decreased from 2.09 to 1.85 when the split ratio was 0.1 and from 1.74 to 1.52 when the split ratio was 0.2.The separation factor also decreased with the increasing of split ratio. At 573 K and the feed rate of 5 L/min, the separation factor of 15.0%H 2 and 85.0%D 2 decreased from 2.43 to 1.35 with the increasing of split ratio from 0.050 to 0.534,and for 66.2%H 2 -33.8%D 2 , the separation factor decreased from 2.87 to 1.30 with the increasing of split ratio from 0.050 to 0.688. When the separation factor was the biggest, the flow rate of feed gas was in a perfect value. To gain a best separation performance, perfect flow rate, lower temperature and reflux ratio should be chosen. (authors)

  13. Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

    DEFF Research Database (Denmark)

    Dideriksen, Knud; Baker, Joel A.; Stipp, Susan Louise Svane

    2008-01-01

    be controlled by isotope fractionation between the free and complexed iron.We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fedesferrioxamine B (at pH 2). The two......-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of a56Fesolution-solid=1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically...... and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within...

  14. A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

    Science.gov (United States)

    Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

    2011-01-01

    Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of

  15. Using hydrogen isotopes to assign origins of bats in the eastern United States

    Science.gov (United States)

    Eric R. Britzke; Susan C. Loeb; Keith A. Hobson; Christopher S. Romanek; Maarten J. Vonhof

    2009-01-01

    Stable hydrogen isotopes (dDs) in metabolically inert tissues such as feathers and hair provide a set of endogenous markers that may be useful for establishing migratory connectivity in animals. We tested the assumption...

  16. Equilibrium properties of dense hydrogen isotope gases based on the theory of simple fluids.

    Science.gov (United States)

    Kowalczyk, Piotr; MacElroy, J M D

    2006-08-03

    We present a new method for the prediction of the equilibrium properties of dense gases containing hydrogen isotopes. The proposed approach combines the Feynman-Hibbs effective potential method and a deconvolution scheme introduced by Weeks et al. The resulting equations of state and the chemical potentials as functions of pressure for each of the hydrogen isotope gases depend on a single set of Lennard-Jones parameters. In addition to its simplicity, the proposed method with optimized Lennard-Jones potential parameters accurately describes the equilibrium properties of hydrogen isotope fluids in the regime of moderate temperatures and pressures. The present approach should find applications in the nonlocal density functional theory of inhomogeneous quantum fluids and should also be of particular relevance to hydrogen (clean energy) storage and to the separation of quantum isotopes by novel nanomaterials.

  17. CRYOCOL a computer program to calculate the cryogenic distillation of hydrogen isotopes

    International Nuclear Information System (INIS)

    Douglas, S.R.

    1993-02-01

    This report describes the computer model and mathematical method coded into the AECL Research computer program CRYOCOL. The purpose of CRYOCOL is to calculate the separation of hydrogen isotopes by cryogenic distillation. (Author)

  18. Stable isotope fractionation during bacterial sulfate reduction is controlled by reoxidation of intermediates

    Science.gov (United States)

    Mangalo, Muna; Meckenstock, Rainer U.; Stichler, Willibald; Einsiedl, Florian

    2007-09-01

    Bacterial sulfate reduction is one of the most important respiration processes in anoxic habitats and is often assessed by analyzing the results of stable isotope fractionation. However, stable isotope fractionation is supposed to be influenced by the reduction rate and other parameters, such as temperature. We studied here the mechanistic basics of observed differences in stable isotope fractionation during bacterial sulfate reduction. Batch experiments with four sulfate-reducing strains ( Desulfovibrio desulfuricans, Desulfobacca acetoxidans, Desulfonatronovibrio hydrogenovorans, and strain TRM1) were performed. These microorganisms metabolize different carbon sources (lactate, acetate, formate, and toluene) and showed broad variations in their sulfur isotope enrichment factors. We performed a series of experiments on isotope exchange of 18O between residual sulfate and ambient water. Batch experiments were conducted with 18O-enriched (δ 18O water = +700‰) and depleted water (δ 18O water = -40‰), respectively, and the stable 18O isotope shift in the residual sulfate was followed. For Desulfovibrio desulfuricans and Desulfonatronovibrio hydrogenovorans, which are both characterized by low sulfur isotope fractionation ( ɛS > -13.2‰), δ 18O values in the remaining sulfate increased by only 50‰ during growth when 18O-enriched water was used for the growth medium. In contrast, with Desulfobacca acetoxidans and strain TRM1 ( ɛS factor ( ɛS exchange with water during sulfate reduction. However, this neither takes place in the sulfate itself nor during formation of APS (adenosine-5'-phosphosulfate), but rather in intermediates of the sulfate reduction pathway. These may in turn be partially reoxidized to form sulfate. This reoxidation leads to an incorporation of oxygen from water into the "recycled" sulfate changing the overall 18O isotopic composition of the remaining sulfate fraction. Our study shows that such incorporation of 18O is correlated with the

  19. Iron isotope fractionation during pyrite formation in a sulfidic Precambrian ocean analogue

    Science.gov (United States)

    Rolison, John M.; Stirling, Claudine H.; Middag, Rob; Gault-Ringold, Melanie; George, Ejin; Rijkenberg, Micha J. A.

    2018-04-01

    The chemical response of the Precambrian oceans to rising atmospheric O2 levels remains controversial. The iron isotope signature of sedimentary pyrite is widely used to trace the microbial and redox states of the ocean, yet the iron isotope fractionation accompanying pyrite formation in nature is difficult to constrain due to the complexity of the pyrite formation process, difficulties in translating the iron isotope systematics of experimental studies to natural settings, and insufficient iron isotope datasets for natural euxinic (i.e. anoxic and sulfidic) marine basins where pyrite formation occurs. Herein we demonstrate, that a large, permil-level shift in the isotope composition of dissolved iron occurs in the Black Sea euxinic water column during syngenetic pyrite formation. Specifically, iron removal to syngenetic pyrite gives rise to an iron isotope fractionation factor between Fe(II) and FeS2 of 2.75 permil (‰), the largest yet reported for reactions under natural conditions that do not involve iron redox chemistry. These iron isotope systematics offer the potential to generate permil-level shifts in the sedimentary pyrite iron isotope record due to partial drawdown of the oceanic iron inventory. The implication is that the iron stable isotope signatures of sedimentary pyrites may record fundamental regime shifts between pyrite formation under sulfur-limited conditions and pyrite formation under iron-limited conditions. To this end, the iron isotope signatures of sedimentary pyrite may best represent the extent of euxinia in the past global ocean, rather than its oxygenation state. On this basis, the reinterpreted sedimentary pyrite Fe isotope record suggests a fundamental shift towards more sulfidic oceanic conditions coincident with the 'Great Oxidation Event' around 2.3 billion years ago. Importantly, this does not require the chemical state of the ocean to shift from mainly de-oxygenated to predominantly oxygenated in parallel with the permanent rise

  20. Mg isotope systematics during magmatic processes: Inter-mineral fractionation in mafic to ultramafic Hawaiian xenoliths

    Science.gov (United States)

    Stracke, A.; Tipper, E. T.; Klemme, S.; Bizimis, M.

    2018-04-01

    Observed differences in Mg isotope ratios between bulk magmatic rocks are small, often on a sub per mill level. Inter-mineral differences in the 26Mg/24Mg ratio (expressed as δ26Mg) in plutonic rocks are on a similar scale, and have mostly been attributed to equilibrium isotope fractionation at magmatic temperatures. Here we report Mg isotope data on minerals in spinel peridotite and garnet pyroxenite xenoliths from the rejuvenated stage of volcanism on Oahu and Kauai, Hawaii. The new data are compared to literature data and to theoretical predictions to investigate the processes responsible for inter-mineral Mg isotope fractionation at magmatic temperatures. Theory predicts up to per mill level differences in δ26Mg between olivine and spinel at magmatic temperatures and a general decrease in Δ26Mgolivine-spinel (=δ26Mgolivine - δ26Mgspinel) with increasing temperature, but also with increasing Cr# in spinel. For peridotites with a simple petrogenetic history by melt depletion, where increasing depletion relates to increasing melting temperatures, Δ26Mgolivine-spinel should thus systematically decrease with increasing Cr# in spinel. However, most natural peridotites, including the Hawaiian spinel peridotites investigated in this study, are overprinted by variable extents of melt-rock reaction, which disturb the systematic primary temperature and compositionally related olivine-spinel Mg isotope systematics. Diffusion, subsolidus re-equilibration, or surface alteration may further affect the observed olivine-spinel Mg isotope fractionation in peridotites, making Δ26Mgolivine-spinel in peridotites a difficult-to-apply geothermometer. The available Mg isotope data on clinopyroxene and garnet suggest that this mineral pair is a more promising geothermometer, but its application is restricted to garnet-bearing igneous (garnet pyroxenites) and metamorphic rocks (eclogites). Although the observed δ26Mg variation is on a sub per mill range in bulk magmatic rocks

  1. Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

    International Nuclear Information System (INIS)

    Mahieu, Koenraad; De Visscher, Alex; Vanrolleghem, Peter A.; Van Cleemput, Oswald

    2008-01-01

    A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between 12 CH 4 , 13 CH 4 , and 12 CH 3 D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per mille in the δ 13 C value, with δ 13 C the relative 13 C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods

  2. Influence of the enzyme dissimilatory sulfite reductase on stable isotope fractionation during sulfate reduction

    Science.gov (United States)

    Mangalo, Muna; Einsiedl, Florian; Meckenstock, Rainer U.; Stichler, Willibald

    2008-03-01

    The stable isotopes of sulfate are often used as a tool to assess bacterial sulfate reduction on the macro scale. However, the mechanisms of stable isotope fractionation of sulfur and oxygen at the enzymatic level are not yet fully understood. In batch experiments with water enriched in 18O we investigated the effect of different nitrite concentrations on sulfur isotope fractionation by Desulfovibrio desulfuricans. With increasing nitrite concentrations, we found sulfur isotope enrichment factors ranging from -11.2 ± 1.8‰ to -22.5 ± 3.2‰. Furthermore, the δ18O values in the remaining sulfate increased from approximately 50-120‰ when 18O-enriched water was supplied. Since 18O-exchange with ambient water does not take place in sulfate, but rather in intermediates of the sulfate reduction pathway (e.g. SO32-), we suggest that nitrite affects the steady-state concentration and the extent of reoxidation of the metabolic intermediate sulfite to sulfate during sulfate reduction. Given that nitrite is known to inhibit the production of the enzyme dissimilatory sulfite reductase, our results suggest that the activity of the dissimilatory sulfite reductase regulates the kinetic isotope fractionation of sulfur and oxygen during bacterial sulfate reduction. Our novel results also imply that isotope fractionation during bacterial sulfate reduction strongly depends on the cell internal enzymatic regulation rather than on the physico-chemical features of the individual enzymes.

  3. Mercury isotope fractionation during ore retorting in the Almadén mining district, Spain

    Science.gov (United States)

    Gray, John E.; Pribil, Michael J.; Higueras, Pablo L.

    2013-01-01

    Almadén, Spain, is the world's largest mercury (Hg) mining district, which has produced over 250,000 metric tons of Hg representing about 30% of the historical Hg produced worldwide. The objective of this study was to measure Hg isotopic compositions of cinnabar ore, mine waste calcine (retorted ore), elemental Hg (Hg0(L)), and elemental Hg gas (Hg0(g)), to evaluate potential Hg isotopic fractionation. Almadén cinnabar ore δ202Hg varied from − 0.92 to 0.15‰ (mean of − 0.56‰, σ = 0.35‰, n = 7), whereas calcine was isotopically heavier and δ202Hg ranged from − 0.03‰ to 1.01‰ (mean of 0.43‰, σ = 0.44‰, n = 8). The average δ202Hg enrichment of 0.99‰ between cinnabar ore and calcines generated during ore retorting indicated Hg isotopic mass dependent fractionation (MDF). Mass independent fractionation (MIF) was not observed in any of the samples in this study. Laboratory retorting experiments of cinnabar also were carried out to evaluate Hg isotopic fractionation of products generated during retorting such as calcine, Hg0(L), and Hg0(g). Calcine and Hg0(L) generated during these retorting experiments showed an enrichment in δ202Hg of as much as 1.90‰ and 0.67‰, respectively, compared to the original cinnabar ore. The δ202Hg for Hg0(g) generated during the retorting experiments was as much as 1.16‰ isotopically lighter compared to cinnabar, thus, when cinnabar ore was roasted, the resultant calcines formed were isotopically heavier, whereas the Hg0(g) generated was isotopically lighter in Hg isotopes.

  4. ITER hydrogen isotope separation system conceptual design description

    International Nuclear Information System (INIS)

    Busigin, A.; Sood, S.K.; Kveton, O.K.; Dinner, P.J.; Murdoch, D.K.; Leger, D.

    1990-01-01

    This paper presents integrated hydrogen Isotope Separation System (ISS) designs for ITER based on requirements for plasma exhaust processing, neutral beam injection deuterium cleanup, pellet injector propellant detritiation, waste water detritiation, and breeding blanket detritiation. Specific ISS designs are developed for a machine with an aqueous lithium salt blanket (ALSB) and a machine with a solid ceramic breeding blanket (SBB). The differences in the ISS designs arising from the different blanket concepts are highlighted. It is found that the ISS designs for the two blanket concepts considered are very similar with the only major difference being the requirement for an additional large water distillation column for ALSB water detritiation. The extraction of tritium from the ALSB is based on flash evaporation to separate the blanket water from the dissolved Li salt, with the tritiated water then being fed to the ISS for detritiation. This technology is considered to be relatively well understood in comparison to front-end processes for SBB detritiation. In the design of the cryogenic distillation portion of the ISS, it was found that the tritium inventory could be very large (> 600 g) unless specific design measures were taken to reduce it. In the designs which are presented, the tritium inventory has been reduced to about 180 g, which is less than the ITER single-failure release limit of 200 g. Further design optimization and isolation of components is expected to reduce the inventory further. (orig.)

  5. Advanced mass spectrometers for hydrogen-isotope analyses

    International Nuclear Information System (INIS)

    Chastagner, P.; Daves, H.L.; Hess, W.B.

    1982-01-01

    Two advanced mass spectrometers for the accurate analysis of mixtures of the hydrogen isotopes were evaluated by Du Pont personnel at the Savannah River Laboratory. One is a large double-focusing instrument with a resolution of 2000 at mass 4 and an abundance sensitivity of >100,000 for the HT-D 2 doublet. The second is a smaller, simpler, stigmatic focusing instrument with exceptionally high ion intensities (>1 x 10 - 9 A at 600 resolution and about 1 x 10 - 10 A at 1300 resolution) for high signal-to-noise ratios. Both instruments are computer controlled. Once a scan is started, peak switching, scanning, mass discrimination control, data collection, and data reduction are done without operator intervention. Utility routines control hysteresis effects and instrument calibration. A containment facility, with dual inlet systems and a standard distribution system, permits testing with tritium mixtures. Helium flow standards and tritium activity meters provide independent verification of the mass spectrometer calibrations. A recovery system prevents the release of tritium to the environment. The performance of the mass spectrometers was essentially equal under simulated process control conditions. Precision and accuracy for the D/T ratio was <0.5% (rel 2sigma limits). Performance factors were: sample equilibration <300 ppM; linearity within +-0.3%; and gas interference <0.1%. Mass discrimination was controlled reliably by the computers

  6. Retention characteristics of hydrogen isotopes in JT-60U

    International Nuclear Information System (INIS)

    Masaki, K.; Sugiyama, K.; Hayashi, T.; Ochiai, K.; Gotoh, Y.; Shibahara, T.; Hirohata, Y.; Oya, Y.; Miya, N.; Tanabe, T.

    2005-01-01

    Erosion/deposition distribution and hydrogen isotope behavior in the JT-60U plasma-facing wall were investigated. Distribution of the tritium, which was produced by D-D nuclear reaction, was not correlated with erosion/deposition distribution. The tritium distribution can be explained by the distribution of high-energy tritium ion-implantation due to ripple loss. Deuterium distribution in the divertor region was different from the tritium distribution and not well correlated with the deposition. The highest D/C was ∼0.05 at the bottom of the outer dome wing, which is much less than that observed in other tokamaks. For the deuterium retention, at least two retention processes (ion-implantation and co-deposition) were found on the dome region. The systematic dust collection gave the small amount of dust (∼7 g: 0.2 mg/s production) in the whole vessel of JT-60U. Deposition was observed at the remote area of the outer divertor region

  7. On order reduction in hydrogen isotope distillation models

    International Nuclear Information System (INIS)

    Sarigiannis, D.A.

    1994-01-01

    The design integration of the fuel processing system for the next generation fusion reactor plants (such as ITER and beyond) requires the enhancement of safety features related to the operation of the system. The current drive for inherent safety of hazardous chemical plants warrants the minimization of active toxic or radioactive inventories and the identification of process pathways with minimal risk of accidental or routine releases. New mathematical and numerical tools have been developed for the dynamic simulation and optimization of the safety characteristics related to tritium in all its forms in the fusion fuel processing system. The separation of hydrogen isotopes by cryogenic distillation is a key process therein, due to the importance of the separation performance for the quality of the fuel mixture and the on site inventory, the increased energy requirements for cryogenic operation, and the high order of mathematical complexity required for accurate models, able to predict the transient as well as the steady state behavior of the process. The modeling methodology described here is a part of a new dynamic simulation code that captures the inventory dynamics of all the species in the fusion fuel processing plant. The significant reduction of the computational effort and time required by this code will permit designers to easily explore a variety of design and technology options and assess their impact on the overall power plant safety

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

    International Nuclear Information System (INIS)

    Kinoshita, Masahiro; Naruse, Yuji

    1981-08-01

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

  9. Adaptation of Boynton's mathematical model to hydrogen isotope separation column by cryogenic distillation

    International Nuclear Information System (INIS)

    Kinoshita, Masahiro; Naruse, Yuji

    1981-08-01

    Boynton's mathematical simulation procedure for multi-component distillation calculations has the advantage that the Jacobian matrix is calculated analytically. The purpose of the present study is to adapt this procedure to hydrogen isotope separation columns by cryogenic distillation. The Boynton's model is modified so that the model can incorporate decay heat of tritium, nonideality of the hydrogen isotope solutions, multiple feeds and multiple sidestreams. Basic equations are derived and the mathematical simulation procedure is briefly explained. (author)

  10. Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

    Science.gov (United States)

    Goevert, Dennis; Conrad, Ralf

    2008-11-01

    Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

  11. Tellurium stable isotope fractionation in chondritic meteorites and some terrestrial samples

    Science.gov (United States)

    Fehr, Manuela A.; Hammond, Samantha J.; Parkinson, Ian J.

    2018-02-01

    New methodologies employing a 125Te-128Te double-spike were developed and applied to obtain high precision mass-dependent tellurium stable isotope data for chondritic meteorites and some terrestrial samples by multiple-collector inductively coupled plasma mass spectrometry. Analyses of standard solutions produce Te stable isotope data with a long-term reproducibility (2SD) of 0.064‰ for δ130/125Te. Carbonaceous and enstatite chondrites display a range in δ130/125Te of 0.9‰ (0.2‰ amu-1) in their Te stable isotope signature, whereas ordinary chondrites present larger Te stable isotope fractionation, in particular for unequilibrated ordinary chondrites, with an overall variation of 6.3‰ for δ130/125Te (1.3‰ amu-1). Tellurium stable isotope variations in ordinary chondrites display no correlation with Te contents or metamorphic grade. The large Te stable isotope fractionation in ordinary chondrites is likely caused by evaporation and condensation processes during metamorphism in the meteorite parent bodies, as has been suggested for other moderately and highly volatile elements displaying similar isotope fractionation. Alternatively, they might represent a nebular signature or could have been produced during chondrule formation. Enstatite chondrites display slightly more negative δ130/125Te compared to carbonaceous chondrites and equilibrated ordinary chondrites. Small differences in the Te stable isotope composition are also present within carbonaceous chondrites and increase in the order CV-CO-CM-CI. These Te isotope variations within carbonaceous chondrites may be due to mixing of components that have distinct Te isotope signatures reflecting Te stable isotope fractionation in the early solar system or on the parent bodies and potentially small so-far unresolvable nucleosynthetic isotope anomalies of up to 0.27‰. The Te stable isotope data of carbonaceous and enstatite chondrites displays a general correlation with the oxidation state and hence might

  12. Features of the spectroscopic determination of the isotope composition of trace amounts of hydrogen in helium

    International Nuclear Information System (INIS)

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

    1986-01-01

    The investigation of the magnitude of the isotope effect in the intensiti of the beta lines of the Balmer series was carried out with the excitation of a high-frequency discharge in a quartz tube having a diameter of ca.6.5 at pressures of the gaseous mixture ranging from 1 to 70 kPa. From the experimental results here it follows that as the isotopes of hydrogen are diluted with helium, the value of K decreases from 1.2-1.1 to 0.84-0.86, and the maximum of the plots of K= f(P) broaden and move toward higher pressures. In order to account for the laws obtained, the authors examined a set of elementary processes and reactions for which the isotope-related differences in the rate constants (alpha) can influence the relative concentrations of the excited atoms of the isotopes of hydrogen in a discharge. The physical model presented in this paper of the shaping of the isotope effects in the atomic spectrum of hydrogen makes it possible to account for the observed laws governing the excitation of a discharge in a mixture of the isotopes of hydrogen with helium and thus greatly facilitates the selection of the optimal conditions for the excitation of the analytical spectrum in devising procedures for the spectroscopic isotope determination of trace impurities of hydrogen in helium

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

    International Nuclear Information System (INIS)

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

    1977-01-01

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

  14. On depth profiling of hydrogen and helium isotopes and its application to ion-implantation studies

    International Nuclear Information System (INIS)

    Boettiger, J.

    1979-01-01

    The thesis is divided into two parts, the first being a general review of the experimental methods for depth profiling of light isotopes, where ion beams are used. In the second part, studies of ion implantation of hydrogen and helium isotopes, applying the techniques discussed in the first part, are described. The paper summarizes recent experimental results and discusses recent developments. (Auth.)

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

    Science.gov (United States)

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

    2011-01-01

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

  16. Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

    Science.gov (United States)

    Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

    2018-02-01

    The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at

  17. Evidence from Hydrogen Isotopes in Meteorites for a Subsurface Hydrogen Reservoir on Mars

    Science.gov (United States)

    Usui, Tomohiro; Alexander, Conel M. O'D.; Wang, Jianhua; Simon, Justin I.; Jones, John H.

    2015-01-01

    The surface geology and geomorphology of Mars indicates that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have conducted in situ hydrogen isotope (D/H) analyses of quenched and impact glasses in three Martian meteorites (Yamato 980459, EETA79001, LAR 06319) by Cameca ims-6f at Digital Terrain Models (DTM) following the methods of [1]. The hydrogen isotope analyses provide evidence for the existence of a distinct but ubiquitous water/ice reservoir (D/H = 2-3 times Earth's ocean water: Standard Mean Ocean Water (SMOW)) that lasted from at least the time when the meteorites crystallized (173-472 Ma) to the time they were ejected by impacts (0.7-3.3 Ma), but possibly much longer [2]. The origin of this reservoir appears to predate the current Martian atmospheric water (D/H equals approximately 5-6 times SMOW) and is unlikely to be a simple mixture of atmospheric and primordial water retained in the Martian mantle (D/H is approximately equal to SMOW [1]). Given the fact that this intermediate-D/H reservoir (2-3 times SMOW) is observed in a diverse range of Martian materials with different ages (e.g., SNC (Shergottites, Nakhlites, Chassignites) meteorites, including shergottites such as ALH 84001; and Curiosity surface data [3]), we conclude that this intermediate-D/H reservoir is likely a global surficial feature that has remained relatively intact over geologic time. We propose that this reservoir represents either hydrated crust and/or ground ice interbedded within sediments. Our results corroborate the hypothesis that a buried cryosphere accounts for a large part of the initial water budget of Mars.

  18. Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

    Science.gov (United States)

    Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

    2012-04-01

    Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of

  19. Temperature and Pressure Depences on the Isotopic Fractionation Effect in the Thermal Decomposition of Ozone

    Directory of Open Access Journals (Sweden)

    Su-Ju Kim

    1997-12-01

    Full Text Available To understand the mass-independent isotopic fractionation effects, thermal decomposition of ozone was performed. Initial oxygen gas was converted to ozone completely. Then, the ozone was decomposed to oxygen at various temperatures(30~150C. Isotopic compositions of product oxygen and residual ozone were measured using a stable isotope mass spectrometer. The experimental results were compared with the studies which were peformed at the similar conditions. From the raw experimental data, the functions of the instantaneous fractionation factors were calculated by the least square fit. The results clearly showed the temperature dependence. They also showed the pressure dependence and the surface effect. This study may play an important role in the study of ozone decomposition mechanism. It can be applied to explain the mass-independent isotopic pattern found in stratospheric ozone and in meteorites.

  20. On-line hydrogen-isotope measurements of organic samples using elemental chromium: An extension for high temperature elemental-analyzer techniques

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B.; Meijer, Harro A.J.; Brand, Willi A.; Schimmelmann, Arndt

    2015-01-01

    The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while

  1. On-line hydrogen-isotope measurements of organic samples using elemental chromium: an extension for high temperature elemental-analyzer techniques.

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Gilevska, Tetyana; Qi, Haiping; Coplen, Tyler B; Meijer, Harro A J; Brand, Willi A; Schimmelmann, Arndt

    2015-01-01

    The high temperature conversion (HTC) technique using an elemental analyzer with a glassy carbon tube and filling (temperature conversion/elemental analysis, TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ(2)H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions, heteroelements like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogen-isotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ(2)H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation) scale, and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while

  2. Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

    Science.gov (United States)

    de La Rocha, Christina L.

    2003-05-01

    The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

  3. Mass fractionation of noble gases in diffusion-limited hydrodynamic hydrogen escape

    International Nuclear Information System (INIS)

    Zahnle, K.; Pollack, J.B.; Kasting, J.F.

    1990-01-01

    The theory of mass fractionation by hydrogen is presently extended to atmospheres in which hydrogen is not the major constituent. This theoretical framework is applied to three different cases. In the first, it is shown that the fractionation of terrestrial atmospheric neon with respect to mantle neon is explainable as a consequence of diffusion-limited hydrogen escape from a steam atmosphere toward the end of the accretion process. In the second, the anomalously high Ar-38/Ar-36 ratio of Mars is shown to be due to hydrodynamic fractionation by a vigorously escaping and very pure hydrogen wind. In the last case, it is speculated that the currently high Martian D/H ratio emerged during the hydrodynamic escape phase which fractionated Ar. 35 refs

  4. Observations of nitrogen isotope fractionation in deeply embedded protostars

    DEFF Research Database (Denmark)

    Wampfler, Susanne Franziska; Jørgensen, Jes Kristian; Bizzarro, Martin

    2014-01-01

    (Abridged) The terrestrial planets, comets, and meteorites are significantly enriched in 15N compared to the Sun and Jupiter. While the solar and jovian nitrogen isotope ratio is believed to represent the composition of the protosolar nebula, a still unidentified process has caused 15N...... HCN and HNC with respect to the solar composition. Solar composition cannot be excluded for the third source, OMC-3 MMS6. Furthermore, there are indications of a trend toward increasing 14N/15N ratios with increasing outer envelope temperature. The enhanced 15N abundances in HCN and HNC found in two...

  5. Hydrogen solubility measurements of analyzed tall oil fractions and a solubility model

    International Nuclear Information System (INIS)

    Uusi-Kyyny, Petri; Pakkanen, Minna; Linnekoski, Juha; Alopaeus, Ville

    2017-01-01

    Highlights: • Hydrogen solubility was measured in four tall oil fractions between 373 and 597 K. • Continuous flow synthetic isothermal and isobaric method was used. • A Henry’s law model was developed for the distilled tall oil fractions. • The complex composition of the samples was analyzed and is presented. - Abstract: Knowledge of hydrogen solubility in tall oil fractions is important for designing hydrotreatment processes of these complex nonedible biobased materials. Unfortunately measurements of hydrogen solubility into these fractions are missing in the literature. This work reports hydrogen solubility measured in four tall oil fractions between 373 and 597 K and at pressures from 5 to 10 MPa. Three of the fractions were distilled tall oil fractions their resin acids contents are respectively 2, 20 and 23 in mass-%. Additionally one fraction was a crude tall oil (CTO) sample containing sterols as the main neutral fraction. Measurements were performed using a continuous flow synthetic isothermal and isobaric method based on the visual observation of the bubble point. Composition of the flow was changed step-wise for the bubble point composition determination. We assume that the tall oil fractions did not react during measurements, based on the composition analysis performed before and after the measurements. Additionally the densities of the fractions were measured at atmospheric pressure from 293.15 to 323.15 K. A Henry’s law model was developed for the distilled tall oil fractions describing the solubility with an absolute average deviation of 2.1%. Inputs of the solubility model are temperature, total pressure and the density of the oil at 323.15 K. The solubility of hydrogen in the CTO sample can be described with the developed model with an absolute average deviation of 3.4%. The solubility of hydrogen increases both with increasing pressure and/or increasing temperature. The more dense fractions of the tall oil exhibit lower hydrogen

  6. Isotope fractionation during the anaerobic consumption of acetate by methanogenic and sulfate-reducing microorganisms

    Science.gov (United States)

    Gövert, D.; Conrad, R.

    2009-04-01

    During the anaerobic degradation of organic matter in anoxic sediments and soils acetate is the most important substrate for the final step in production of CO2 and/or CH4. Sulfate-reducing bacteria (SRB) and methane-producing archaea both compete for the available acetate. Knowledge about the fractionation of 13C/12C of acetate carbon by these microbial groups is still limited. Therefore, we determined carbon isotope fractionation in different cultures of acetate-utilizing SRB (Desulfobacter postgatei, D. hydrogenophilus, Desulfobacca acetoxidans) and methanogens (Methanosarcina barkeri, M. acetivorans). Including literature values (e.g., Methanosaeta concilii), isotopic enrichment factors (epsilon) ranged between -35 and +2 permil, possibly involving equilibrium isotope effects besides kinetic isotope effects. The values of epsilon were dependent on the acetate-catabolic pathway of the particular microorganism, the methyl or carboxyl position of acetate, and the relative availability or limitation of the substrate acetate. Patterns of isotope fractionation in anoxic lake sediments and rice field soil seem to reflect the characteristics of the microorganisms actively involved in acetate catabolism. Hence, it might be possible using environmental isotopic information to determine the type of microbial metabolism converting acetate to CO2 and/or CH4.

  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. 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

  9. Estimation of Physical Properties for Hydrogen Isotopes Using Aspen Plus Simulator

    International Nuclear Information System (INIS)

    Cho, Jung Ho; Yun, Sei Hun; Cho, Seung Yon; Chang, Min Ho; Kang, Hyun Goo; Jung, Ki Jung; Kim, Dong Min

    2009-01-01

    Hydrogen isotopes are H 2 , HD, D 2 , H 2 , HD, D 2 , HT, DT and T 2 . Among the hydrogen isotopes, the physical properties of H2, HD and D+2 are included in the Aspen Plus, however HT, D T and T 2 are not included. In this study, various thermodynamic properties were estimated for six components of isotopes by use of the fixed properties and temperature-dependent properties. To estimate thermodynamic properties, Soave modified Redlich-Kwong equation of state and Aspenplus simulator was used. The results were verified and compared with by PRO/II with PROVISION of Invensys

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

    Energy Technology Data Exchange (ETDEWEB)

    Rustad, James R.; Zarzycki, Piotr

    2008-07-29

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

  11. Carbon-13 isotopic composition of distillation fractions of some Egyptian crude oils

    International Nuclear Information System (INIS)

    Aly, A.I.M.; Hamza, M.S.; Abd Elsamie, S.G.

    1991-01-01

    13 C/ 13 C ratios were determined for some crude oil fields in the Gulf of Suez and Western Desert provinces. The crude oil was subjected to distillation at atmospheric pressure and subsequently under vacuum. Distillation fractions were collected at 25 degree C intervals. Carbon-13 content of these distillation fractions showed some differences in the degree of isotopic fractionation. The results were interpreted in view of the age of the source rocks and the degree of maturation process. The carbon-13 content of distillation fractions may be helpful in revealing petroleum mechanisms which can be exploited in exploration.4 fig

  12. Assessment of methods for analyzing gaseous mixtures of hydrogen isotopes and helium

    International Nuclear Information System (INIS)

    Attalla, A.; Bishop, C.T.; Bohl, D.R.; Buxton, T.L.; Sprague, R.E.; Warner, D.K.

    1976-01-01

    Mass spectrographic methods have served well in the past to analyze gaseous mixtures of the hydrogen isotopes. Alternate methods of analyses are reviewed which offer wider ranges and variety of isotopic determinations. This report describes possible improvements of the mass spectrographic determinations, gas chromatography, anti-Stokes Raman spectroscopy, microwave-induced optical emission spectroscopy, and methods of measuring tritium using radiation detection devices. Precision, accuracy, limitations, and costs are included for some of the methods mentioned. Costs range from $70,000 for the anti-Stokes Raman spectroscopy equipment, which can determine hydrogen isotopes but not helium, to less than $10,000 for the gas chromatographic equipment, which can determine hydrogen isotopes and helium with precision and accuracy comparable to those of the mass spectrometer

  13. The Influence of Irradiation Regimes on Retention Hydrogen Isotopes in Structural Materials

    International Nuclear Information System (INIS)

    Zaluzhnyi, A.

    2007-01-01

    Full text of publication follows: In the present work was investigated the influence of irradiation regimes on retention hydrogen isotopes in samples of austenitic steel during heating. The samples of studied materials were irradiated both in the reactor and by hydrogen isotopes ions of different energies and fluencies bombardment in an accelerator. Kinetic of hydrogen release from the samples worked with deuterium plasma was investigated. The following results were obtained. Heating the irradiate d samples of steel (irradiated in the reactor or by hydrogen isotopes ions bombardment), which have been kept in normal temperature during quite a long period after the irradiation, a shift of the diffusion peak of hydrogen release to higher temperatures, comparing to no irradiated samples, was observed. It means that atoms of hydrogen in the irradiated sample were caught by radiation defects, which are very effective as traps for hydrogen atoms till quite high temperatures (700 K). The worked out analysis of the received results supposes that vacancy complexes. On thermodesorption curves of hydrogen release from irradiated samples of austenitic steels a high temperature peak (900-1000 K) was observed because of dissociation of hydrogen containing compounds in micro pores. During investigations of hydrogen release from irradiated samples of austenitic steel, after it had been saturated with hydrogen plasma, abnormally big blisters were registered with cover thickness of about 1 mkm. Three peaks were observed on the thermodesorption curves of hydrogen release from irradiated samples, contained blisters. The low temperature spike (∼500 K) was showed to correspond to hydrogen release because of its resolution from blisters, where it was in molecular form. The high temperature peak (∼900 K) corresponds to hydrogen release from dissociating blisters, which contain hydrocarbons. The mechanism of abnormal blisters generation is offered. Inasmuch methane is not soluble in

  14. 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)

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

    International Nuclear Information System (INIS)

    Sato, Takuya; Oi, Takao

    2015-01-01

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

  16. Carbon isotope fractionation by thermophilic phototrophic sulfur bacteria: evidence for autotrophic growth in natural populations

    Science.gov (United States)

    Madigan, M. T.; Takigiku, R.; Lee, R. G.; Gest, H.; Hayes, J. M.

    1989-01-01

    Purple phototrophic bacteria of the genus Chromatium can grow as either photoautotrophs or photoheterotrophs. To determine the growth mode of the thermophilic Chromatium species, Chromatium tepidum, under in situ conditions, we have examined the carbon isotope fractionation patterns in laboratory cultures of this organism and in mats of C. tepidum which develop in sulfide thermal springs in Yellowstone National Park. Isotopic analysis (13C/12C) of total carbon, carotenoid pigments, and bacteriochlorophyll from photoautotrophically grown cultures of C. tepidum yielded 13C fractionation factors near -20%. Cells of C. tepidum grown on excess acetate, wherein synthesis of the Calvin cycle enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase ribulose bisphosphate carboxylase) was greatly repressed, were isotopically heavier, fractionation factors of ca. -7% being observed. Fractionation factors determined by isotopic analyses of cells and pigment fractions of natural populations of C. tepidum growing in three different sulfide thermal springs in Yellowstone National Park were approximately -20%, indicating that this purple sulfur bacterium grows as a photoautotroph in nature.

  17. Stable Isotope Fractionation Caused by Glycyl Radical Enzymes during Bacterial Degradation of Aromatic Compounds

    Science.gov (United States)

    Morasch, Barbara; Richnow, Hans H.; Vieth, Andrea; Schink, Bernhard; Meckenstock, Rainer U.

    2004-01-01

    Stable isotope fractionation was studied during the degradation of m-xylene, o-xylene, m-cresol, and p-cresol with two pure cultures of sulfate-reducing bacteria. Degradation of all four compounds is initiated by a fumarate addition reaction by a glycyl radical enzyme, analogous to the well-studied benzylsuccinate synthase reaction in toluene degradation. The extent of stable carbon isotope fractionation caused by these radical-type reactions was between enrichment factors (ɛ) of −1.5 and −3.9‰, which is in the same order of magnitude as data provided before for anaerobic toluene degradation. Based on our results, an analysis of isotope fractionation should be applicable for the evaluation of in situ bioremediation of all contaminants degraded by glycyl radical enzyme mechanisms that are smaller than 14 carbon atoms. In order to compare carbon isotope fractionations upon the degradation of various substrates whose numbers of carbon atoms differ, intrinsic ɛ (ɛintrinsic) were calculated. A comparison of ɛintrinsic at the single carbon atoms of the molecule where the benzylsuccinate synthase reaction took place with compound-specific ɛ elucidated that both varied on average to the same extent. Despite variations during the degradation of different substrates, the range of ɛ found for glycyl radical reactions was reasonably narrow to propose that rough estimates of biodegradation in situ might be given by using an average ɛ if no fractionation factor is available for single compounds. PMID:15128554

  18. Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

    Science.gov (United States)

    Vinson, David S.; Blair, Neal E.; Martini, Anna M.; Larter, Steve; Orem, William H.; McIntosh, Jennifer C.

    2017-01-01

    Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH4, δD-H2O, δ13C-CH4, and δ13C-CO2) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.Isotopic fingerprinting techniques that combine δ13C-CH4 with δD-CH4 and/or δ13C-CO2have significant limitations: (1) The consistent ~ 160‰ offset between δD-H2O and δD-CH4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon

  19. Early evaluation of hydrogen isotopes separation by V4Cr4Ti-based sorbents at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Kulsartov, Timur, E-mail: tima@physics.kz [Institute of Experimental and Theoretical Physics of Kazakh National University, 050038 Almaty (Kazakhstan); Institute of Atomic Energy of National Nuclear Center, 071100 Kurchatov (Kazakhstan); Shestakov, Vladimir; Chikhray, Yevgen; Kenzhina, Inesh; Askerbekov, Saulet [Institute of Experimental and Theoretical Physics of Kazakh National University, 050038 Almaty (Kazakhstan); Gordienko, Yuriy; Ponkratov, Yuriy; Zaurbekova, Zhanna [Institute of Atomic Energy of National Nuclear Center, 071100 Kurchatov (Kazakhstan)

    2016-12-15

    This paper presents the results of experiments on hydrogen isotopes sorption with V4Cr4Ti vanadium alloys from a mixture of hydrogen isotopes. The studies were carried out at temperatures of 353 K, 393 K, 423 K; and pressures of 10{sup 3}–10{sup 4} Pa in gas mixture of hydrogen isotopes. The α-phase domain of V-H (D) system was studied, where the concentration of hydrogen isotopes atoms should not exceed 0.015H (D) atoms per metal atom. The separation parameters were derived for several saturation conditions accordingly to registered time dependences of hydrogen isotopes partial pressure drop. The conclusion was made about the prospects of using vanadium alloys in hydrogen isotopes separation and purification systems.

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

    Science.gov (United States)

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

    2018-05-01

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

  1. New insight on Li and B isotope fractionation during serpentinization derived from batch reaction investigations

    Science.gov (United States)

    Hansen, Christian T.; Meixner, Anette; Kasemann, Simone A.; Bach, Wolfgang

    2017-11-01

    Multiple batch experiments (100 °C, 200 °C; 40 MPa) were conducted, using Dickson-type reactors, to investigate Li and B partitioning and isotope fractionation between rock and water during serpentinization. We reacted fresh olivine (5 g; Fo90; [B] = anti-correlated with temperature, we argue for an overall attenuation of the isotopic effect through changes in B speciation in saline solutions (NaB(OH)4(aq) and B(OH)3Cl-) as well as variable B fixation and fractionation for different serpentinization product minerals (brucite, chrysotile). Breakdown of the Li-rich olivine and limited Li incorporation into product mineral phases resulted in an overall lower Li content of the final solid phase assemblage at 200 °C ([Li]final_200 °C = 0.77 μg/g; DS/FLi200 °C = 1.58). First order changes in Li isotopic compositions were defined by mixing of two isotopically distinct sources i.e. the fresh olivine and the fluid rather than by equilibrium isotope fraction. At 200 °C primary olivine is dissolved, releasing its Li budget into the fluid which shifts towards a lower δ7LiF of +38.62‰. Newly formed serpentine minerals (δ7LiS = +30.58‰) incorporate fluid derived Li with a minor preference of the 6Li isotope. At 100 °C Li enrichment of secondary phases exceeded Li release by olivine breakdown ([Li]final_100 °C = 2.10 μg/g; DS/FLi100 °C = 11.3) and it was accompanied by preferential incorporation of heavier 7Li isotope that might be due to incorporation of a 7Li enriched fluid fraction into chrysotile nanotubes.

  2. Uranium isotope fractionation resulting from UF6 vapor distillation from containers

    International Nuclear Information System (INIS)

    Hedge, W.D.; Turner, C.M.

    1985-01-01

    This empirical study for possible isotopic fractionation due to UF 6 vapor distillation from valved containers was performed to determine the effects of repeated vapor sampling. Four different experiments were performed, each of which varied by the method of measuring the isotopic contents and/or by the difference in temperature gradients as follows: The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature and homogenized was measured by sampling the containers. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature and homogenized was measured by direct comparison to each other without subsampling. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen and ice-water temperatures and homogenized was measured by indirect comparison to a common UF 6 reference material without subsampling. The ratio of the parent UF 6 to the desublimed UF 6 collected at liquid nitrogen temperature without homogenizing was measured by indirect comparison to a common UF 6 reference. Gas-phase, relative mass spectrometry was used for all isotopic measurements. Results of the study indicate that fractionation does occur. The U-235 isotope becomes more enriched in the parent container as the UF 6 is vaporized from it and desublimed into the receiving cylinder; i.e., the vaporized fraction is enriched in the U-238 isotope. The degree of fractionation indicates that the separation is due to the U-238 isotope of UF 6 having a higher vapor pressure than the U-235 isotope of UF 6 . 3 refs., 4 figs., 4 tabs

  3. Insights Into Nitrogen Isotope Fractionation in Coral Reefs

    Science.gov (United States)

    Lamb, K. A.; Swart, P. K.; Ellis, G. S.

    2002-12-01

    Environmental integrity in the Florida Reef tract and the Caribbean has been the center of concern for the past 15-20 years. Both the recreational and scientific communities alike have noticed an overall decline in coral reef health. This decline has manifested itself in the form of increased fleshy macroalgae growth and reduced coral cover, and in some cases, wide-scale coral mortality. Given the increasing dependence on a tourism-oriented economy in both South Florida and the Caribbean, much attention has been focused on maintaining reef longevity. A high nutrient load is believed to be the leading cause of degradation in the predominantly oligotrophic environment. Various studies have cited increased run off and input of anthropogenic wastes as the origin of these nutrients. It has also been suggested that the stable isotopes of nitrogen may provide a tracer with which to recognize the impact of anthropogenic nutrients within the coral reefs ecosystem. However, in utilizing both nitrogen and carbon stable isotopic methods on samples of particulate organic matter (POM) taken over the last three years, we find little evidence of the input of anthropogenic waste. δ15N values of POM fluctuate between +1 and +9 per mille, but usually remain in the +4 to +6 per mille range. Additionally, δ13C values are even more consistent, maintaining a balance between -19 to -21 per mille. These data are consistent with natural open-ocean values for δ15N and δ13C, indicating a lack of intense and prolonged exposure to anthropogenic wastes in the Florida Keys.

  4. Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

    Science.gov (United States)

    Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

    2010-01-01

    Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

  5. 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.

  6. 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)

  7. Hydrogen production characteristics of the organic fraction of municipal solid wastes by anaerobic mixed culture fermentation

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Li; Yu, Zhang [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640 (China)]|[Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Zhenhong, Yuan; Yongming, Sun; Xiaoying, Kong [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2009-01-15

    The hydrogen production from the organic fraction of municipal solid waste (OFMSW) by anaerobic mixed culture fermentation was investigated using batch experiments at 37 C. Seven varieties of typical individual components of OFMSW including rice, potato, lettuce, lean meat, oil, fat and banyan leaves were selected to estimate the hydrogen production potential. Experimental results showed that the boiling treated anaerobic sludge was effective mixed inoculum for fermentative hydrogen production from OFMSW. Mechanism of fermentative hydrogen production indicates that, among the OFMSW, carbohydrates is the most optimal substrate for fermentative hydrogen production compared with proteins, lipids and lignocelluloses. This conclusion was also substantiated by experimental results of this study. The hydrogen production potentials of rice, potato and lettuce were 134 mL/g-VS, 106 mL/g-VS, and 50 mL/g-VS respectively. The hydrogen percentages of the total gas produced from rice, potato and lettuce were 57-70%, 41-55% and 37-67%. (author)

  8. Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

    Science.gov (United States)

    Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

    2011-12-01

    The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed

  9. Determination of Hydrogen and Carbon contents in crude oil and Petroleum fractions by NMR Spectroscopy

    International Nuclear Information System (INIS)

    Khadim, Mohammad A.; Wolny, R.A.; Al-Dhuwaihi, Abdullah S.; Al-Hajri, E.A.; Al-Ghamdi, M.A.

    2003-01-01

    Proton and carbon-13 NMR spectroscopic methods were developed for determining hydrogen and carbon contents in petroleum products. These methods are applicable to a wide of petroleum streams. A new reference standard, bis (trimethylsilyl) methane, BTMSM, is introduced fro both proton and carbon-13 NMR for the first time, which offers several advantages over those customarily employed. These methods are important for the calculation of the mass balance and hydrogen consumption in pilot plant studies. Unlike the ASTM D-5291 combustion method, the NMR methods also allow for the measurement of hydrogen and carbon content in low boiling fractions and those containing hydrogen as low as 1%. The NMR methods can also determine aromatic and aliphatic hydrogens carbons in a given sample without additional experimentation. The precision and accuracy of the newly developed NMR methods are compared with those of currently employed ASTM D-5291 combustion method. Using the proton NMR method, hydrogen content was determined in fifteen model compounds and sixty-eight petroleum fractions. The NMR and ASTM methods show an agreement within +5%for 48 out of a total number of 68 oil fractions. Using carbon-13 NMR, the carbon content was determined for four representative compounds and three fractions of crude oil. Both carbon-13 NMR and ASTM methods give comparable carbon content in model compounds and crude oil fractions. (author)

  10. Pyrolysis compound specific isotopic analysis (δ13C and δD Py-CSIA) of soil organic matter size fractions under four vegetation covers.

    Science.gov (United States)

    Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.; Almendros, Gonzalo; De la Rosa, José M.; González-Pérez, José A.

    2015-04-01

    compounds released directly from pyrolysis (Py-CSIA); lipids (Alkenes), aromatic unspecific (alkylphenols), lignin (methoxyphenols) and polysaccharides (anhydrosugars) derived molecules. For all coarse fractions the δ13C and δD values had the same general behavior with sugar derived molecules being enriched in the heavy isotope. Regarding alkenes δ13C isotopic signature, this was variable and dependent upon the main cover vegetation that may reflect different fractionations at different synthesis stages (Chikaraishi & Naraoka, 2001), The δD values for specific compounds had a similar behavior to that for δ13C, being the sugar derived compounds the most deuterium enriched in comparison with lipid and lignin derived pyrolysis products. A conspicuous δD fractionation was observed for the sugar derived compounds in the fine fractions as compared with the coarse ones, with a depletion in deuterium, mainly for the PA sample where the depletion was the highest (c. -140 ‰). This may points to the occurrence of biological reworking with a higher microbiological activity fixing the lighter isotope in the soil fine organic fractions. It is known that lipid hydrogen is deuterium depleted relative to bulk organic hydrogen (Smith and Epstein, 1970). In line with this, in our study the lipid derived compounds had the largest deuterium depleted signature with a difference between bulk and lipid δD values was c. -35‰. This fractionation was highest in Pine (PP) and Rockrose (HH). The combination of traditional techniques for the study of SOM i.e. Py-GC/MS and IRMS, with new hyphenated analytical pyrolysis techniques i.e. Py-CSIA opens new possibilities and windows of information in SOM research. Our findings points to the occurrence of more or less complex processes that affects SOM chemical characteristics; whereas the coarse fraction resembles the chemical structure of the above vegetation, this SOM "memory" is less defined in the fine fractions, probably due to biologically

  11. Tracing low-temperature aqueous metal migration in mineralized watersheds with Cu isotope fractionation

    International Nuclear Information System (INIS)

    Mathur, R.; Munk, L.A.; Townley, B.; Gou, K.Y.; Gómez Miguélez, N.; Titley, S.; Chen, G.G.; Song, S.; Reich, M.; Tornos, F.; Ruiz, J.

    2014-01-01

    Highlights: • Cu isotope fractionation of ores and waters identifies copper sulfide weathering. • Redox reactions cause isotopic shift measured in areas of sulfide weathering. • Consistent isotope signature in different deposit, climate, or concentration. - Abstract: Copper isotope signatures in waters emanating from mineralized watersheds provide evidence for the source aqueous copper in solution. Low-temperature aqueous oxidation of Cu sulfide minerals produces significant copper isotopic fractionation between solutions and residues. Abiotic experimental data of fractionation (defined as Δ liquid–solid ‰ = δ 65 Cu liquid − δ 65 Cu solid ) are on the order of 1–3‰ and are unique for copper rich-sulfide minerals. Data presented here from ores and waters within defined boundaries of porphyry copper, massive sulfide, skarn, and epithermal ore deposits mimic abiotic experiments. Thus, the oxidation of sulfide minerals appears to cause the signatures in the waters although significant biological, temperature, and pH variations exist in the fluids. Regardless of the deposit type, water type, concentration of Cu in solution, or location, the data provide a means to trace sources of metals in solutions. This relationship allows for tracking sources and degree of metal migration in low temperature aqueous systems and has direct application to exploration geology and environmental geochemistry

  12. An Investigation into the Relationship Between Distillate Yield and Stable Isotope Fractionation

    Science.gov (United States)

    Sowers, T.; Wagner, A. J.

    2016-12-01

    Recent breakthroughs in laser spectrometry have allowed for faster, more efficient analyses of stable isotopic ratios in water samples. Commercially available instruments from Los Gatos Research and Picarro allow users to quickly analyze a wide range of samples, from seawater to groundwater, with accurate isotope ratios of D/H to within ± 0.2 ‰ and 18O/16O to within ± 0.03 ‰. While these instruments have increased the efficiency of stable isotope laboratories, they come with some major limitations, such as not being able to analyze hypersaline waters. The Los Gatos Research Liquid Water Isotope Analyzer (LWIA) can accurately and consistently measure the stable isotope ratios in waters with salinities ranging from 0 to 4 grams per liter (0 to 40 parts per thousand). In order to analyze water samples with salinities greater than 4 grams per liter, however, it was necessary to develop a consistent method through which to reduce salinity while causing as little fractionation as possible. Using a consistent distillation method, predictable fractionation of δ 18O and δ 2 H values was found to occur. This fractionation occurs according to a linear relationship with respect to the percent yield of the water in the sample. Using this method, samples with high salinity can be analyzed using laser spectrometry instruments, thereby enabling laboratories with Los Gatos or Picarro instruments to analyze those samples in house without having to dilute them using labor-intensive in-house standards or expensive premade standards.

  13. 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...

  14. Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short-strong hydrogen bonded cluster

    NARCIS (Netherlands)

    Li, X. H.; Oomens, J.; Eyler, J. R.; Moore, D. T.; Iyengar, S. S.

    2010-01-01

    We investigate and analyze the vibrational properties, including hydrogen/deuterium isotope effects, in a fundamental organic hydrogen bonded system using multiple experimental (infrared multiple photon dissociation and argon-tagged action spectroscopy) and computational techniques. We note a

  15. Hydrogen production via catalytic steam reforming of fast pyrolysis oil fractions

    International Nuclear Information System (INIS)

    Wang, D.; Czernik, S.; Montane, D.; Mann, M.; Chornet, E.

    1997-01-01

    Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells, and as a co-adjuvant or autonomous transportation fuel in internal combustion engines. The conversion of biomass to hydrogen can be carried out through two distinct thermochemical strategies: (a) gasification followed by shift conversion; (b) catalytic steam reforming and shift conversion of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper shows that fast pyrolysis of biomass results in a bio-oil that can be adequately fractionated into valuable co-products leaving as by-product an aqueous fraction containing soluble organics (a mixture of alcohols, aldehydes and acids). This fraction can be converted to hydrogen by catalytic steam reforming followed by a shift conversion step. The methods used, the yields obtained and their economic significance will be discussed. (author)

  16. Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.

    Science.gov (United States)

    Baune, Claudia; Bottcher, Michael E

    2010-12-01

    The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H

  17. Cr-isotope fractionation during oxidative weathering of ultramafic rocks and its impact on river waters

    DEFF Research Database (Denmark)

    Paulukat, Cora Stefanie; Døssing, Lasse Nørbye; Mondal, Sisir K.

    We investigated Cr isotope fractionation during soil formation from Precambrian ultramafic rocks. A soil profile was logged in an active open-cast chromite mine (Sukinda Valley, India). In addition, mine and river waters, as well as seawater were collected to trace the Cr-isotope signal...... values as heavy as +1.33±0.05‰. Where the drainage water merges with the river water, a slightly positively fractionated δ53Cr value (0.03±0.019‰) reflects a mixed isotope signal. With increasing distance from the mine, river water δ53Cr again becomes increasingly positively fractionated, indicating...... into the sea. The aim of the study is to recognize Cr isotope fractionation processes within the mining-area and the impact of the mine runoff on the δ53Cr of the nearby river. The weathering profile shows a distinct upward trend to more negative δ53Cr values. While the well preserved rocks at the base closely...

  18. Liquid--vapor isotope fractionation factors in argon--krypton binary mixtures

    International Nuclear Information System (INIS)

    Lee, M.W.; Neufeld, P.; Bigeleisen, J.

    1977-01-01

    An equilibrium isotope effect has been studied as a continuous function of the potential field acting on the atom undergoing isotopic exchange. This has been accomplished through a study of the liquid vapor isotope fractionation factors for both, 36 Ar/ 40 Ar and 80 Kr/ 84 Kr in a series of binary mixtures which span the range between the pure components at 117.5 0 K. The 36 Ar/ 40 Ar fractionation factor increases (linearly) from (lnα)2.49 x 10 -3 in pure liquid argon to 2.91 x 10 -3 in an infinitely dilute solution in liquid krypton. Conversely, the 80 Kr/ 84 Kr fractionation factor decreases (linearly) from (lnα)0.98 x 10 -3 in pure liquid krypton to 0.64 x 10 -3 in an infinetely dilute solution in pure liquid argon. The mean force constants 2 U>/sub c/ on both argon and krypton atoms in the mixtures are derived from the respective isotope fractionation factors.The mean force constants for argon and krypton as a function of composition have been calculated by a modified corresponding states theory which uses the pure liquids as input parameters. The discrepancy is 8 percent at X/sub Ar/ + O. A systematic set of calculations has been made of 2 U> (Ar) and 2 U> (Kr) as a function of composition using radial distribution functions generated by the Weeks--Chandler--Anderson perturbation theory

  19. Chapter 2. Peculiarities of radioactive particle formation and isotope fractionation resulted from underground nuclear explosions

    International Nuclear Information System (INIS)

    1996-01-01

    Radioactive particles, forming terrain fallouts from underground nuclear explosion differ sufficiently from radioactive particles, produced by atmospheric nuclear explosions. Patterns of underground nuclear explosion development, release of radioactivity to the atmosphere, formation of a cloud and base surge, peculiarities of formed radioactive particles, data on isotope fractionation in radioactive particles are presented. Scheme of particle activation, resulted from underground explosions is given

  20. Effect of Different Carbon Substrates on Nitrate Stable Isotope Fractionation During Microbial Denitrification

    DEFF Research Database (Denmark)

    Wunderlich, Anja; Meckenstock, Rainer; Einsiedl, Florian

    2012-01-01

    -labeled water and 18O-labeled nitrite were added to the microcosm experiments to study the effect of putative backward reactions of nitrite to nitrate on the stable isotope fractionation. We found no evidence for a reverse reaction. Significant variations of the stable isotope enrichment factor ε were observed......In batch experiments, we studied the isotope fractionation in N and O of dissolved nitrate during dentrification. Denitrifying strains Thauera aromatica and “Aromatoleum aromaticum strain EbN1” were grown under strictly anaerobic conditions with acetate, benzoate, and toluene as carbon sources. 18O...... of nitrate transport across the cell wall compared to the kinetics of the intracellular nitrate reduction step of microbial denitrification....

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-15

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

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

  3. Diffusion-driven magnesium and iron isotope fractionation in Hawaiian olivine

    Science.gov (United States)

    Teng, F.-Z.; Dauphas, N.; Helz, R.T.; Gao, S.; Huang, S.

    2011-01-01

    Diffusion plays an important role in Earth sciences to estimate the timescales of geological processes such as erosion, sediment burial, and magma cooling. In igneous systems, these diffusive processes are recorded in the form of crystal zoning. However, meaningful interpretation of these signatures is often hampered by the fact that they cannot be unambiguously ascribed to a single process (e.g., magmatic fractionation, diffusion limited transport in the crystal or in the liquid). Here we show that Mg and Fe isotope fractionations in olivine crystals can be used to trace diffusive processes in magmatic systems. Over sixty olivine fragments from Hawaiian basalts show isotopically fractionated Mg and Fe relative to basalts worldwide, with up to 0.4??? variation in 26Mg/24Mg ratios and 1.6??? variation in 56Fe/54Fe ratios. The linearly and negatively correlated Mg and Fe isotopic compositions [i.e., ??56Fe=(??3.3??0.3)????26Mg], co-variations of Mg and Fe isotopic compositions with Fe/Mg ratios of olivine fragments, and modeling results based on Mg and Fe elemental profiles demonstrate the coupled Mg and Fe isotope fractionation to be a manifestation of Mg-Fe inter-diffusion in zoned olivines during magmatic differentiation. This characteristic can be used to constrain the nature of mineral zoning in igneous and metamorphic rocks, and hence determine the residence times of crystals in magmas, the composition of primary melts, and the duration of metamorphic events. With improvements in methodology, in situ isotope mapping will become an essential tool of petrology to identify diffusion in crystals. ?? 2011 Elsevier B.V.

  4. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by 13C nuclear magnetic resonance spectrometry

    International Nuclear Information System (INIS)

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

    2015-01-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by 13 C NMR (irm- 13 C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources. - Highlights: • Position-Specific Isotope Analysis (PSIA) by 13 C NMR spectrometry. • PSIA on isotope fractionation during several vaporization processes. • PSIA for isotope profiling in environment pollutants. • Intramolecular 13 C reveal normal and inverse effects, bulk values being unchanged. - PSIA in pollutants during evaporation processes shows more detailed information for discerning the nature of the process involved than does bulk isotope measurements

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

    International Nuclear Information System (INIS)

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

    1983-01-01

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

  6. Tracking transformation processes of organic micropollutants in aquatic environments using multi-element isotope fractionation analysis

    International Nuclear Information System (INIS)

    Hofstetter, Thomas B.; Bolotin, Jakov; Skarpeli-Liati, Marita; Wijker, Reto; Kurt, Zohre; Nishino, Shirley F.; Spain, Jim C.

    2011-01-01

    The quantitative description of enzymatic or abiotic transformations of man-made organic micropollutants in rivers, lakes, and groundwaters is one of the major challenges associated with the risk assessment of water resource contamination. Compound-specific isotope analysis enables one to identify (bio)degradation pathways based on changes in the contaminants' stable isotope ratios even if multiple reactive and non-reactive processes cause concentrations to decrease. Here, we investigated how the magnitude and variability of isotope fractionation in some priority pollutants is determined by the kinetics and mechanisms of important enzymatic and abiotic redox reactions. For nitroaromatic compounds and substituted anilines, we illustrate that competing transformation pathways can be assessed via trends of N and C isotope signatures.

  7. Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

    Science.gov (United States)

    Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

    2018-06-01

    We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

  8. 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

  9. Studies about interaction of hydrogen isotopes with metals and intermetallic compounds

    International Nuclear Information System (INIS)

    Vasut, F.; Anisoara, P.; Zamfirache, M.

    2003-01-01

    Hydrogen is a non-toxic but highly inflammable gas. Compared to other inflammable gases, its range of inflammability in air is much broader (4-74.5%) but it also vaporizes much more easily. Handling of hydrogen in form of hydrides enhances safety. The interaction of hydrogen with metals and intermetallic compounds is a major field within physical chemistry. Using hydride-forming metals and intermetallic compounds, for example, recovery, purification and storage of heavy isotopes in tritium containing system can solve many problems arising in the nuclear-fuel cycle. The paper presents the thermodynamics and the kinetics between hydrogen and metal or intermetallic compounds. (author)

  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. Thorium isotopes in colloidal fraction of water from San Marcos Dam, Chihuahua, Mexico

    Science.gov (United States)

    Cabral-Lares, M.; Melgoza, A.; Montero-Cabrera, M. E.; Renteria-Villalobos, M.

    2013-07-01

    The main interest of this stiidy is to assess the contents and distribution of Th-series isotopes in colloidal fraction of surface water from San Marcos dam, because the suspended particulate matter serves as transport medium for several pollutants. The aim of this work was to assess the distribution of thorium isotopes (232Th and 230Th) contained in suspended matter. Samples were taken from three surface points along the San Marcos dam: water input, midpoint, and near to dam wall. In this last point, a depth sampling was also carried out. Here, three depth points were taken at 0.4, 8 and 15 meters. To evaluate the thorium behavior in surface water, from every water sample the colloidal fraction was separated, between 1 and 0.1 μm. Thorium isotopes concentraron in samples were obtained by alpha spectrometry. Activity concentrations obtained of 232Th and 230Th in surface points ranged from 0.3 to 0.5 Bq ṡ L-1, whereas in depth points ranged from 0.4 to 3.2 Bq ṡ L-1, respectively. The results show that 230Th is in higher concentration than 232Th in colloidal fraction. This can be attributed to a preference of these colloids to adsorb uranium. Thus, the activity ratio 230Th/232Th in colloidal fraction showed values from 2.3 to 10.2. In surface points along the dam, 230Th activity concentration decreases while 232Th concentration remains constant. On the other hand, activity concentrations of both isotopes showed a pointed out enhancement with depth. The results have shown a possible lixiviation of uranium from geological substrate into the surface water and an important fractionation of thorium isotopes, which suggest that thorium is non-homogeneously distributed along San Marcos dam.

  12. Assessment for ion beam analysis methods about hydrogen isotope in hydrogen storaged metal

    International Nuclear Information System (INIS)

    Ding Wei; Long Xinggui; Shi Liqun

    2006-01-01

    In this paper, experimental arrangements of measuring hydrogen isotope concentration and distribution in metal hydride with ion beam analysis methods were reported, and the advantage and disadvantage of different methods were analyzed too. Experiment results show that it can get abundant information and accurate value by these ways. It can get an accurate value since it's the Rutherford cross-section, and the Mylar film used in the experiment is thin enough for H, D and T distinguishing each other while using ERD analysis method with 6.0 MeV O ion beam to proceed this work, but the disadvantage of this method is that the sample preparing is more difficult, and the analysis depth is lower. It could get the distribution information of H, D and T and the analysis depth is about 3.0 μm while using ERD analysis method with 7.4 MeV 4 He ion beam, but the disadvantage is that the spectra of H, D and T overlap each other, which makes a big error in simulated calculation. If using PBS method with 3.0 MeV proton, the analysis depth is deeper, but it couldn't get the H distribution information. (authors)

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

    Science.gov (United States)

    Koehler, Geoff; Wassenaar, Leonard I

    2012-04-17

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

  14. Nitrogen isotope fractionations in the Fischer-Tropsch synthesis and in the Miller-Urey reaction

    International Nuclear Information System (INIS)

    Chun-Chan Kung; Hayatsu, R.; Studier, M.H.; Clayton, R.N.; Chicago Univ., IL; Chicago Univ., IL

    1979-01-01

    Nitrogen isotope fractionations have been measured in Fischer-Tropsch and Miller-Urey reactions in order to determine whether these processes can account for the large 15 N/ 14 N ratios found in organic matter in carbonaceous chondrites. Polymeric material formed in the Fischer-Tropsch reaction was enriched in 15 N by only 3 promille relative to the starting material (NH 3 ). The 15 N enrichment in polymers from the Miller-Urey reaction was 10-12 promille. Both of these fractionations are small compared to the 80-90 promille differences observed between enstatite chondrites and carbonaceous chondrites. These large differences are apparently due to temporal or spatial variations in the isotopic composition of nitrogen in the solar nebula, rather than to fractionation during the production of organic compounds. (orig.)

  15. Peatland Microbial Carbon Use Under Warming using Isotopic Fractionation

    Science.gov (United States)

    Gutknecht, J.

    2016-12-01

    Peatlands are a critical natural resource, especially in their role as carbon sinks. Most of the world's peatlands are located in Northern ecosystems where the climate is changing at a rapid pace, and there is great interest and concern with how climate change will influence them. Although studies regarding the response of peatlands to climate change have emerged, the microbial mediation of C cycling in these systems is still less well understood. In this study, 13CPLFA analysis was used to characterize the microbial community and it's carbon use at the Spruce and Peatland Responses Under Climatic and Environmental Change (SPRUCE) Project. The SPRUCE project is an extensive study of the response of peatlands to climatic manipulation in the Marcell Experimental Forest in northern Minnesota. Heating rods were installed in peatland plots where peat is being warmed at several levels including ambient, +2.5, +4.5, +6.75, and +9 degrees Celsius, at a depth of 3 meters, beginning July of 2014. Samples were taken June 2014, September 2014, and June 2015, throughout the depth profile. We found very high microbial, and especially fungal growth at shallow depths, owing in part to the influence of fungal-like lipids present in Sphagnum stems, and in part to dense mycorrhizal colonization in shrub and tree species. Isotopic data shows that microbial biomass has an enriched δ13C lower in the peat profile, indicating as expected that microbes at depth utilize older carbon or carbon more enriched in 13C. The increase over depth in the δ13C signature may also reflect the increased dominance of pre-industrial carbon that is more enriched in 13C. In this early period of warming we did not see clear effects of warming, either due to the highly heterogeneous microbial growth across the bog, or to the short term deep warming only. We expect that with the initiation of aboveground warming in July 2016, warming will begin to show stronger effects on microbial C cycling.

  16. Low-temperature diffusion of hydrogen isotopes in tantalum

    International Nuclear Information System (INIS)

    Peichl, R.; Ziegler, P.; Weidinger, A.

    1987-01-01

    The mobility of hydrogen and deuterium in tantalum is investigated in the temperature range between 4.2 and 30 K. On the time scale of the present experiment (25 μs) we find that hydrogen begins to move above 15 K whereas deuterium remains immobile at least up to 30 K. Since the interpretation of the data depends critically on the exact hydrogen configurations a major part of the paper is devoted to this problem. We suggest that hydrogen can exist in fairly localized or more extended states depending on the local homogeneity of the crystal. (orig.)

  17. Mass-Dependent and -Independent Fractionation of Mercury Isotopes in Aquatic Systems

    Science.gov (United States)

    Bergquist, B. A.; Joel, B. D.; Jude, D. J.

    2008-12-01

    Mercury is a globally distributed and highly toxic pollutant. Although Hg is a proven health risk, much of the natural cycle of Hg is not well understood and new approaches are needed to track Hg and the chemical transformations it undergoes in the environment. Recently, we demonstrated that Hg isotopes exhibit two types of isotope fractionation: (1) mass dependent fractionation (MDF) and (2) mass independent fractionation (MIF) of only the odd isotopes (Bergquist and Blum, 2007). The observation of large MIF of Hg isotopes (up to 5 permil) is exciting because only a few other isotopic systems have been documented to display large MIF, the most notable of which are oxygen and sulfur. In both cases, the application of MIF has proven very useful in a variety of fields including cosmochemistry, paleoclimatology, physical chemistry, atmospheric chemistry, and biogeochemistry. Both MDF and MIF isotopic signatures are observed in natural samples, and together they open the door to a new method for tracing Hg pollution and for investigating Hg behavior in the environment. For example, fish record MDF that appears to be related to size and age. Additionally, fish display MIF signatures that are consistent with the photo-reduction of methylmercury (Bergquist and Blum, 2007). If the MDF and MIF in ecosystems can be understood, the signatures in fish could inform us about the sources and processes transforming Hg and why there are differences in the bioaccumulation of Hg in differing ecosystems and populations of fish. This requires sampling of a variety of ecosystems, the sampling of many components of the ecosystems, and the use of other tracers such as carbon and nitrogen isotopes. We have expanded our studies of aquatic ecosystems to include several lakes in North America. Similar to other isotopic systems used to study food web dynamics and structure (i.e., C and N), the MDF of Hg in fish appears to be related to size and age. The MDF recorded in fish likely reflects

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

    International Nuclear Information System (INIS)

    Varlam, Mihai; Steflea, Dumitru

    2001-01-01

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

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

    International Nuclear Information System (INIS)

    Varlam, Mihai; Steflea, Dumitru

    1999-01-01

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

  20. Use of nuclear reactions and ion channeling techniques for depth profiling hydrogen isotopes in solids

    International Nuclear Information System (INIS)

    Appleton, B.R.

    1979-01-01

    Hydrogen has always played a preeminent role in materials science because it so readily alters the physical and chemical properties of materials. However, it is often difficult to determine its role because it is one of the most elusive constituents to detect. More recently hydrogen detection has become necessary in numerous energy-related fields. In fusion energy one must understand plasma particle (hydrogen isotope) recycling, trapping and reemission, as well as the effects of hydrogen on the materials properties of first wall structures in plasma devices (i.e., hydrogen embrittlement, sputtering, blistering, etc.). In geology the presence of hydrogen in various forms alters the mechanical properties of many minerals in the earth's crust and enters directly into studies of tectonic processes. Evaluation of hydrogen in moon rocks increases our understanding of solar wind activity. In solar energy, hydrogen plays an important role in amorphous silicon used in fabricating solar cells. Detection of hydrogen is clearly important in the fossil fuel area. Many of the conventional elemental analysis techniques are not directly applicable to hydrogen determination and others can only detect hydrogen when it is in combination with other elements (i.e., H 2 O, OH, etc.). In this paper we discuss the use of ion beam techniques for obtaining quantitative depth information on hydrogen in materials and discuss the application of these techniques to several problems important in some of the areas mentioned

  1. MEASUREMENTS OF COSMIC-RAY HYDROGEN AND HELIUM ISOTOPES WITH THE PAMELA EXPERIMENT

    International Nuclear Information System (INIS)

    Adriani, O.; Bongi, M.; Barbarino, G. C.; Bazilevskaya, G. A.; Bellotti, R.; Bruno, A.; Boezio, M.; Bonvicini, V.; Formato, V.; Bogomolov, E. A.; Bottai, S.; Cafagna, F.; Campana, D.; Carlson, P.; Casolino, M.; Santis, C. De; Castellini, G.; Donato, C. De; Simone, N. De; Felice, V. Di

    2016-01-01

    The cosmic-ray hydrogen and helium ( 1 H, 2 H, 3 He, 4 He) isotopic composition has been measured with the satellite-borne experiment PAMELA, which was launched into low-Earth orbit on board the Resurs-DK1 satellite on 2006 June 15. The rare isotopes 2 H and 3 He in cosmic rays are believed to originate mainly from the interaction of high-energy protons and helium with the galactic interstellar medium. The isotopic composition was measured between 100 and 1100 MeV/n for hydrogen and between 100 and 1400 MeV/n for helium isotopes using two different detector systems over the 23rd solar minimum from 2006 July to 2007 December

  2. MEASUREMENTS OF COSMIC-RAY HYDROGEN AND HELIUM ISOTOPES WITH THE PAMELA EXPERIMENT

    Energy Technology Data Exchange (ETDEWEB)

    Adriani, O.; Bongi, M. [University of Florence, Department of Physics, I-50019 Sesto Fiorentino, Florence (Italy); Barbarino, G. C. [University of Naples “Federico II,” Department of Physics, I-80126 Naples (Italy); Bazilevskaya, G. A. [Lebedev Physical Institute, RU-119991, Moscow (Russian Federation); Bellotti, R.; Bruno, A. [University of Bari, Department of Physics, I-70126 Bari (Italy); Boezio, M.; Bonvicini, V.; Formato, V. [INFN, Sezione di Trieste, I-34149 Trieste (Italy); Bogomolov, E. A. [Ioffe Physical Technical Institute, RU-194021 St. Petersburg (Russian Federation); Bottai, S. [INFN, Sezione di Florence, I-50019 Sesto Fiorentino, Florence (Italy); Cafagna, F. [INFN, Sezione di Bari, I-70126 Bari (Italy); Campana, D. [INFN, Sezione di Naples, I-80126 Naples (Italy); Carlson, P. [KTH, Department of Physics, and the Oskar Klein Centre for Cosmoparticle Physics, AlbaNova University Centre, SE-10691 Stockholm (Sweden); Casolino, M.; Santis, C. De [University of Rome “Tor Vergata,” Department of Physics, I-00133 Rome (Italy); Castellini, G. [IFAC, I-50019 Sesto Fiorentino, Florence (Italy); Donato, C. De; Simone, N. De; Felice, V. Di [INFN, Sezione di Rome “Tor Vergata,” I-00133 Rome (Italy); and others

    2016-02-10

    The cosmic-ray hydrogen and helium ({sup 1}H, {sup 2}H, {sup 3}He, {sup 4}He) isotopic composition has been measured with the satellite-borne experiment PAMELA, which was launched into low-Earth orbit on board the Resurs-DK1 satellite on 2006 June 15. The rare isotopes {sup 2}H and {sup 3}He in cosmic rays are believed to originate mainly from the interaction of high-energy protons and helium with the galactic interstellar medium. The isotopic composition was measured between 100 and 1100 MeV/n for hydrogen and between 100 and 1400 MeV/n for helium isotopes using two different detector systems over the 23rd solar minimum from 2006 July to 2007 December.

  3. Micro-scale novel stable isotope fractionation during weathering disclosed by femtosecond laser ablation

    Science.gov (United States)

    Schuessler, J. A.; von Blanckenburg, F.

    2012-12-01

    The stable isotope fractionation of metals and metalloids during chemical weathering and alteration of rocks at low temperature is a topic receiving increasing scientific attention. For these systems, weathering of primary minerals leads to selective partitioning of isotopes between the secondary minerals formed from them, and the dissolved phase of soil or river water. While the isotopic signatures of these processes have been mapped-out at the catchment or the soil scale, the actual isotopic fractionation is occurring at the mineral scale. To identify the processes underlying such micro-scale fractionation, the development of micro-analytical tools allows to investigate mechanisms of isotope fractionation in-situ, in combination with textural information of weathering reactions. We have developed a second-generation UV femtosecond (fs) laser system at GFZ Potsdam. The advantage of UV-fs laser ablation is the reduction of laser-induced isotopic and elemental fractionation by avoiding 'thermal effects' during ablation, such that accurate isotope ratios can be measured by standard-sample-standard bracketing using laser ablation multicollector ICP-MS; where the matrix of the bracketing standard does not need to match that of the sample [1]. Our system consists of the latest generation femtosecond solid-state laser (Newport Spectra Physics Solstice), producing an ultra short pulse width of about 100 femtoseconds at a wavelength of 196 nm. The system is combined with a custom-build computer-controlled sample stage and allows fully automated isotope analyses through synchronised operation of the laser with the Neptune MC-ICP-MS. To assess precision and accuracy of our laser ablation method, we analysed various geological reference materials. We obtained δ30Si values of -0.31 ± 0.23 (2SD, n = 13) for basalt glass BHVO-2G, and -1.25 ± 0.21 (2SD, n = 27) for pure Si IRMM17 when bracketed against NBS-28 quartz. δ56Fe and δ26Mg values obtained from non-matrix matched

  4. Iron Isotope Fractionation in Microbial and Non-Biological Precipitates, and the Human Body

    Science.gov (United States)

    von Blanckenburg, F.; Boettcher, M. E.; Hofmann, B.; Walczyk, T.

    2001-12-01

    We have investigated biotic and abiotic stable iron isotope fractionation pathways in experiments, the low-T natural environment, and the human body. Fe samples were analysed using a Nu Plasma Multicollector ICP-MS. All measured samples plot on the theoretically predicted exponential fractionation line in the Delta57Fe versus Delta56Fe space, demonstrating absence of ArN or ArO interferences. An experimental calibration of Fe isotope fractionation during abiotic formation of iron (III) oxyhydroxide and iron(II) minerals from aqueous solution resulted in significant differences: (a) During fast precipitation of FeOOH during alkalization of a Fe(III)Cl3 solution at room temperature the solid is only slightly enriched by about 0.1permil in 57Fe compared to the solution. (b) Slow precipitation of akaganeite (beta-FeOOH) from aqueous Fe(III)Cl3 solution leads to a depletion of 57Fe by about -2.2permil in the solid phase without a significant influence of temperature. (c) Precipitation of FeOOH during oxidation of aqueous Fe(II) solutions by oxygen yields an enrichment of up to 4.8permil in 57Fe in the solid phase. (d) Iron(II) carbonate precipitation between 20 and 60C leads to an almost negligible depletion in 57Fe compared to aqueous ferrous ions. Interpretation: Large enrichment of the heavy isotope is observed where Fe is oxidised, whereas small to interme-diate depletions of heavy Fe isotopes occur upon forma-tion of Fe-minerals without change in redox state. Addi-tionally, kinetic effects, the speciation of the aqueous solution, or the effect of crystal structures may have to be considered. Biotic isotope fractionation by microorganisms was investigated at two field sites. In a Fe mine (Gonzen, Switzerland), Fe-precipitating microbes (Gallionella ferrugina and Leptohrix ochtraceae) have formed Fe(III)-oxyhydroxides that are ca. 0.6permil heavier in Delta57Fe than the Fe-rich parent solutions. At Cady Mts, California, filamentous fabrics of goethite, thought to

  5. Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

    Science.gov (United States)

    Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

    2017-12-01

    In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr

  6. 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

  7. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment

    International Nuclear Information System (INIS)

    Marchesi, Massimo; Thomson, Neil R.; Aravena, Ramon; Sra, Kanwartej S.; Otero, Neus; Soler, Albert

    2013-01-01

    Highlights: • Treatability and C fractionation of 1,1,1-TCA by base-catalyzed S 2 O 8 2− was studied. • The rate of degradation of 1,1,1-TCA increased with a higher OH − :S 2 O 8 2− ratio. •Base-catalyzed S 2 O 8 2− can potentially treat recalcitrant compound like 1,1,1-TCA. • An enrichment factor of −7.0‰ independent of the OH − :S 2 O 8 2− ratio was obtained. • Carbon isotope can potentially be used to estimate the ISCO treatment efficacy. -- Abstract: The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S 2 O 8 2− ) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S 2 O 8 2− molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S 2 O 8 2− molar ratio of −7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S 2 O 8 2− molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system

  8. The temperature dependent strontium isotope fractionation (δ88/86Sr) during calcium carbonate precipitation

    International Nuclear Information System (INIS)

    Fietzke, J.; Eisenhauer, A.

    2006-01-01

    Full text: In order to study the influence of stable isotope fractionation during inorganic and biologically controlled CaCO 3 precipitation we have developed the analytical principles for the measurement of strontium (Sr) isotope fractionation. We have established a measurement protocol for the application on a MC-ICP-MS (AXIOM) using the common bracketing standard technique. The Sr-standard CRM NBS987 was used as reference material for all measurements and to calculate the Sr fractionation. Latter value is expressed by the δ-notation defined as: δ 88/86 Sr = [( 88 Sr/ 86 Sr)sample / ( 88 Sr/ 86 Sr)standard ] * 1000 -1. A first set of experiments focused on the temperature dependency of Sr-isotope fractionation. For this purpose inorganically precipitated aragonite and calcite was prepared under controlled conditions in a temperature range from 10 to 50 o C. In addition, cultured and naturally grown corals were analyzed for their δ 88/86 Sr values. Repeated measurements of IAPSO seawater standard showed a mean δ 88/86 Sr value of 0.383 ± 0.008 (2 SEM) being the isotopically heaviest material measured so far. The first results of the inorganically precipitated aragonite and the natural corals revealed a clear temperature dependency of the δ 88/86 Sr values. For inorganic aragonite the slope of this correlation is about 0.0055 permil/ o C. However, for naturally grown corals (Pavona clavus) a 6 fold steeper slope of 0.033 permil/ o C was determined. This strong temperature dependency implies the potential to use stable Sr isotopes as a new marine (paleo)temperature proxy. (author)

  9. On dewetting dynamics of solid films of hydrogen isotopes and its influence on tritium β spectroscopy

    International Nuclear Information System (INIS)

    Fleischmann, L.; Bonn, J.; Bornschein, B.; Otten, E.W.; Przyrembel, M.; Weinheimer, Ch.

    2000-01-01

    The dewetting dynamics of solid films of hydrogen isotopes, quench-condensed on a graphite substrate, was measured at various temperatures below desorption by observing the stray light from the film. A schematic model describing the dewetting process by surface diffusion is presented, which agrees qualitatively with our data. The activation energies of different hydrogen isotopes for surface diffusion were determined. The time constant for dewetting of a quench-condensed T 2 film at the working temperature of 1.86 K of the mainz neutrino mass experiment was extrapolated. (orig.)

  10. 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

  11. 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

  12. Effect of coexistent hydrogen isotopes on tracer diffusion of tritium in alpha phase of group-V metal-hydrogen systems

    International Nuclear Information System (INIS)

    Sakamoto, Kan; Hashizume, Kenichi; Sugisaki, Masayasu

    2009-01-01

    Tracer diffusion coefficients of tritium in the alpha phase of group-V metal-hydrogen systems, α-MH(D)xTy (M=V and Ta; x>>y), were measured in order to clarify the effects of coexistent hydrogen isotopes on the tritium diffusion behavior. The hydrogen concentration dependence of such behavior and the effects of the coexistent hydrogen isotopes (protium and deuterium) were determined. The results obtained in the present (for V and Ta) and previous (for Nb) studies revealed that tritium diffusion was definitely dependent on hydrogen concentration but was not so sensitive to the kind of coexistent hydrogen isotopes. By summarizing those data, it was found that the hydrogen concentration dependence of the tracer diffusion coefficient of tritium in the alpha phase of group-V metals could be roughly expressed by a single empirical curve. (author)

  13. Fractionation of silver isotopes in native silver explained by redox reactions

    Science.gov (United States)

    Mathur, Ryan; Arribas, Antonio; Megaw, Peter; Wilson, Marc; Stroup, Steven; Meyer-Arrivillaga, Danilo; Arribas, Isabel

    2018-03-01

    Scant data exist on the silver isotope composition of native silver specimens because of the relative newness of the technique. This study increases the published dataset by an order of magnitude and presents 80 silver new isotope analyses from native silver originating from a diverse set of worldwide deposits (8 deposit types, 33 mining districts in five continents). The measured isotopic range (defined as δ109Ag/107Ag in per mil units compared to NIST 978 Ag isotope standard) is +2.1 to -0.86‰ (2σ errors less than 0.015); with no apparent systematic correlations to date with deposit type or even within districts. Importantly, the data centering on 0‰ all come from high temperature hypogene/primary deposits whereas flanking and overlapping data represent secondary supergene deposits. To investigate the causes for the more fractionated values, several laboratory experiments involving oxidation of silver from natural specimens of Ag-rich sulfides and precipitation and adsorption of silver onto reagent grade MnO2 and FeOOH were conducted. Simple leach experiments demonstrate little Ag isotope fractionation occurred through oxidation of Ag from native Ag (Δsolution-native109Ag = 0.12‰). In contrast, significant fractionation occurred through precipitation of native Ag onto MnO2 (up to Δsolution-MnO2109Ag = 0.68‰, or 0.3amu). Adsorption of silver onto the MnO2 and FeOOH did not produce as large fractionation as precipitation (mean value of Δsolution-MnO2109Ag = 0.10‰). The most likely cause for the isotopic variations seen relates to redox effects such as the reduction of silver from Ag (I) to Ag° that occurs during precipitation onto the mineral surface. Since many Ag deposits have halos dominated by MnO2 and FeOOH phases, potential may exist for the silver isotope composition of ores and surrounding geochemical haloes to be used to better understand ore genesis and potential exploration applications. Aside from the Mn oxides, surface fluid silver

  14. Hydrogen isotopic spectral determination in inert gases with the use of light source with contracted discharge

    International Nuclear Information System (INIS)

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

    1981-01-01

    Isotopic-spectral technique for hydrogen determination in helium, neon and argon is developed. It employs a contracted high-frequency discharge as a light source to decrease the distorting effect. of a dummy signal and the ''memory'' effect of the discharge tube. The discharge is realized in a quartz tube approximately 7 mm dia. and gas pressure in it approximately 6x10 4 Pa. The analysis technique comprises sampling of gas, dosed introduction of deuterium into the sample, selection of a mixture portion into the discharge tube, spectroscopic determination of hydrogen isotope ratio and calculation of the sought for hydrogen concentration. The lower boundary of the determined concentrations of hydrogen constitutes 7x10 - 5 , 2x10 - 4 and 4x10 - 4 volumetric per cent in helium, neon, and argon, respectively

  15. CO2-dependent carbon isotope fractionation in the dinoflagellate Alexandrium tamarense

    Science.gov (United States)

    Wilkes, Elise B.; Carter, Susan J.; Pearson, Ann

    2017-09-01

    The carbon isotopic composition of marine sedimentary organic matter is used to resolve long-term histories of pCO2 based on studies indicating a CO2-dependence of photosynthetic carbon isotope fractionation (εP). It recently was proposed that the δ13C values of dinoflagellates, as recorded in fossil dinocysts, might be used as a proxy for pCO2. However, significant questions remain regarding carbon isotope fractionation in dinoflagellates and how such fractionation may impact sedimentary records throughout the Phanerozoic. Here we investigate εP as a function of CO2 concentration and growth rate in the dinoflagellate Alexandrium tamarense. Experiments were conducted in nitrate-limited chemostat cultures. Values of εP were measured on cells having growth rates (μ) of 0.14-0.35 d-1 and aqueous carbon dioxide concentrations of 10.2-63 μmol kg-1 and were found to correlate linearly with μ/[CO2(aq)] (r2 = 0.94) in accord with prior, analogous chemostat investigations with eukaryotic phytoplankton. A maximum fractionation (εf) value of 27‰ was characterized from the intercept of the experiments, representing the first value of εf determined for an algal species employing Form II RubisCO-a structurally and catalytically distinct form of the carbon-fixing enzyme. This value is larger than theoretical predictions for Form II RubisCO and not significantly different from the ∼25‰ εf values observed for taxa employing Form ID RubisCO. We also measured the carbon isotope contents of dinosterol, hexadecanoic acid, and phytol from each experiment, finding that each class of biomarker exhibits different isotopic behavior. The apparent CO2-dependence of εP values in our experiments strengthens the proposal to use dinocyst δ13C values as a pCO2 proxy. Moreover, the similarity between the εf value for A. tamarense and the consensus value of ∼25‰ indicates that the CO2-sensitivity of carbon isotope fractionation saturates at similar CO2 levels across all three

  16. 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

  17. Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe{sup 2+} activated persulfate

    Energy Technology Data Exchange (ETDEWEB)

    Marchesi, Massimo, E-mail: m2marche@uwaterloo.ca [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Aravena, Ramon [Earth and Environmental Department, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Sra, Kanwartej S. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada); Thomson, Neil R. [Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1 (Canada); Otero, Neus; Soler, Albert [Departament de Cristallografia, Mineralogia i Diposits Minerals, Universitat de Barcelona, Barcelona, Catalunya 08028 (Spain); Mancini, Silvia [Golder Associates Inc, Toronto, Ontario, Canada L5N 5Z7 (Canada)

    2012-09-01

    The increased use of persulfate (S{sub 2}O{sub 8}{sup 2-}) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe{sup 2+}). An average carbon isotope enrichment factor {epsilon}{sub bulk} of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cis-DCE were obtained in batch experiments. Variations in the initial S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S{sub 2}O{sub 8}{sup 2-}/Fe{sup 2+}/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe{sup 2+} activated persulfate. Highlights: Black-Right-Pointing-Pointer The performance of in situ chemical oxidation (ISCO) is still difficult to assess. Black-Right-Pointing-Pointer We investigated the potential of carbon isotope analysis as a new assessing tool. Black-Right-Pointing-Pointer C isotope of PCE, TCE and DCE oxidized by persulfate activated by Fe{sup 2+} was measured. Black-Right-Pointing-Pointer Enrichment factors of - 4.9 Per-Mille-Sign for PCE, - 3.6 Per-Mille-Sign for TCE and - 7.6 Per-Mille-Sign for cisDCE were obtained. Black-Right-Pointing-Pointer Carbon isotope can potentially be used to estimate the ISCO treatment efficacy.

  18. Isotopic fractionation associated with [NiFe]- and [FeFe]-hydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hui; Gandhi, Hasand; Cornish, Adam J.; Moran, James J.; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

    2016-01-30

    Hydrogenases catalyze the reversible formation of H2 from electrons and protons with high efficiency. Understanding the relationships between H2 production, H2 uptake, and H2-H2O exchange can provide insight into the metabolism of microbial communities in which H2 is an essential component in energy cycling. In this manuscript, we used stable H isotopes (1H and 2H) to probe the isotope effects associated with three [FeFe]-hydrogenases and three [NiFe]-hydrogenases. All six hydrogenases displayed fractionation factors for H2 formation that were significantly less than 1, producing H2 that was severely depleted in 2H relative to the substrate, water. Consistent with differences in their active site structure, the fractionation factors for each class appear to cluster, with the three [NiFe]-hydrogenases (α = 0.27-0.40) generally having smaller values than the three [FeFe]-hydrogenases (α = 0.41-0.55). We also obtained isotopic fractionation factors associated with H2 uptake and H2-H2O exchange under conditions similar to those utilized for H2 production, providing us with a more complete picture of the three reactions catalyzed by hydrogenases. The fractionation factors determined in our studies can be used as signatures for different hydrogenases to probe their activity under different growth conditions and to ascertain which hydrogenases are most responsible for H2 production and/or uptake in complex microbial communities.

  19. Isotopic fractionation of gases during its migration: experiments and 2D numerical simulation

    Science.gov (United States)

    Kara, S.; Prinzhofer, A.

    2003-04-01

    Several works have been developed in the last decade on the experimental isotope fractionation of gases during migration (Prinzhofer et al., 1997 and Zhang &Krooss, 2001 among others). We add to these results new experiments on diffusion of CO_2, which becomes currently a crucial subject for environmental purpose. Our experiments showed that transport by diffusion of CO_2 through a water saturated shale induces a significant and systematic carbon isotopic fractionation with heavier (13C enriched) CO_2 migrating first. In all experiments, significant isotope fractionation was found but still remains without quantitative interpretation. To interpret these data, we developed a 2D numerical model at the pore scale. The general principle of this model is the study of transport by water solubilization/diffusion of gas in a capillary saturated with water with two different media : a mobile zone representing free water and a immobile zone representing bounded water. The model takes also into account solubilization coefficients of gas in water, as well as the migration distance and the volume of upstream and downstream reservoirs. Using our numerical model, we could reproduce the evolution of isotopic fractionations and the velocity of CO_2 migration versus the production factor F (proportion of diffused gas). We determined some physical parameters of the porous medium (bentonite) which are not directly measurable at the present time. Furthermore, we used these parameters to reproduce the curves of isotopic fractionation obtained by Pernaton (1998) on methane migration with the same porous rock. We used also a modified version of this model with infinite reservoirs to reproduce the curves of isotopic fractionation of Zhang &Krooss (2001). Application of this model to geological scale is under progress, in order to implement it into sedimentary basins modelling. REFERENCES: Zhang T. and Krooss M. (2001). Geochim. Cosmochim. Acta, Vol. 65, No.16, pp. 2723-2742. Pernaton E

  20. Experimental studies and modeling of processes of hydrogen isotopes interaction with beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Tazhibaeva, I.L.; Chikhray, Y.V.; Romanenko, O.G.; Klepikov, A.Kh.; Shestakov, V.P.; Kulsartov, T.V. [Science Research Inst. of Experimental and Theoretical Physics of Kazakh State Univ., Almaty (Kazakhstan); Kenzhin, E.A.

    1998-01-01

    The objective of this work was to clarify the surface beryllium oxide influence on hydrogen-beryllium interaction characteristics. Analysis of experimental data and modeling of processes of hydrogen isotopes accumulation, diffusion and release from neutron irradiated beryllium was used to achieve this purpose as well as the investigations of the changes of beryllium surface element composition being treated by H{sup +} and Ar{sup +} plasma glowing discharge. (author)

  1. Study of peculiarities of hydrogen isotopes mixture permeation through low activated steel F82H

    International Nuclear Information System (INIS)

    Kenzhin, Ye.A.; Tazhibayeva, I.L; Kulsartov, T.V.; Shestakov, V.P.; Chikhray, Ye.V.; Afanasev, S.E.; Zheldak, Yu.L.

    2003-01-01

    Full text: The problem of diffusion tritium leakage through blanket materials of future fusion device makes some constructive difficulties concerned with protection of personnel and environment and also with losses of tritium, which is planned to be used in the same device. One of the little-studied problems in the tritium leakage process in Fusion Power Plant is that in fact tritium will penetrate through materials while other hydrogen isotopes are present. These are deuterium and hydrogen which always are present in metals. Therefore, for evaluation of tritium leakage in future Fusion Power Plant under such conditions it is necessary to have experimental data about permeation of these hydrogen isotopes through the structure materials.One of proposed structure materials of fusion reactor blanket is low activated steel F82H. The experiment results on evaluation of .hydrogen, deuterium and its mixture interaction parameters with steel F82H are shown in this work. The tests were carried out within temperature range 273-973 K under inlet hydrogen pressure of 100-2000 Pa. Diffusivity, deuterium and hydrogen permeation constants for low activated steel F82H was determined from experiment results. Those experimental results were used for created phenomenology model which describes hydrogen isotope penetration through tube sample from hydrogen isotopes mixture. That model was used so determining the ratios of desorption rates (D-D, D-H, H-H) on outlet side of sample. Using of so obtained results, we can correctly evaluate, the titanium leakage from blanket of fusion machine which will be constructed using low activated steel F82H

  2. Hydrogen isotope response to changing salinity and rainfall in Australian mangroves.

    Science.gov (United States)

    Ladd, S Nemiah; Sachs, Julian P

    2015-12-01

    Hydrogen isotope ratios ((2) H/(1) H, δ(2) H) of leaf waxes covary with those in precipitation and are therefore a useful paleohydrologic proxy. Mangroves are an exception to this relationship because their δ(2) H values are also influenced by salinity. The mechanisms underlying this response were investigated by measuring leaf lipid δ(2) H and leaf and xylem water δ(2) H and δ(18) O values from three mangrove species over 9.5 months in a subtropical Australian estuary. Net (2) H/(1) H fractionation between surface water and leaf lipids decreased by 0.5-1.0‰ ppt(-1) for n-alkanes and 0.4-0.8‰ ppt(-1) for isoprenoids. Xylem water was (2) H depleted relative to surface water, reflecting (2) H discrimination of 4-10‰ during water uptake at all salinities and opportunistic uptake of freshwater at high salinity. However, leaf water (2) H enrichment relative to estuary water was insensitive to salinity and identical for all species. Therefore, variations in leaf and xylem water δ(2) H values cannot explain the salinity-dependent (2) H depletion in leaf lipids, nor the 30‰ range in leaf lipid δ(2) H values among species. Biochemical changes in direct response to salt stress, such as increased compatible solute production or preferential use of stored carbohydrates, and/or the timing of lipid production and subsequent turnover rates, are more likely causes. © 2015 John Wiley & Sons Ltd.

  3. Selected bibliography on heavy water, tritiated water and hydrogen isotopes (1981-1992)

    International Nuclear Information System (INIS)

    Gopalakrishnan, V.T.; Sutawane, U.B.; Rathi, B.N.

    1994-01-01

    A selected bibliography on heavy water, tritiated water and hydrogen isotopes is presented. This bibliography covers the period 1981-1992 and is in continuation to Division's earlier report BARC-1192 (1983). The sources of information for this compilation are Chemical Abstracts, INIS Atom Index and also some scattered search through journals and reports available in our library. No claim is made towards exhaustiveness of this bibliography even though sincere attempts have been made for a wide coverage. The bibliography is arranged under the headings: (1) production, purification, recovery, reprocessing and storage, (2) isotope exchange, 3) isotope analysis, (4) properties and (5) miscellaneous. Total number of references in the bibliography are 1762. (author)

  4. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël, E-mail: imfeld@unistra.fr

    2016-07-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ{sup 65}Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ{sup 65}Cu value of the untreated soil (0.08‰). However, δ{sup 65}Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20{sup th} July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ{sup 65}Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ{sup 65}Cu values differed between the particle-size soil

  5. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes

    International Nuclear Information System (INIS)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

    2016-01-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ"6"5Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (− 0.12 to 0.24‰ ± 0.08‰). The values were in the range of those of the fungicides (− 0.21 to 0.11‰) and included the geogenic δ"6"5Cu value of the untreated soil (0.08‰). However, δ"6"5Cu values significantly differed between particle-size soil fractions (− 0.37 ± 0.10‰ in fine clays and 0.23 ± 0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20"t"h July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ"6"5Cu values from 0.52 to 1.35‰ in the dissolved phase (< 0.45 μm) compared to − 0.34 to − 0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. - Highlights: • We investigated Cu sorption processes in vineyard soils and runoff transport. • Cu export by runoff from the catchment accounted for 1% of the applied Cu mass. • δ"6"5Cu values differed between the particle-size soil fractions. • The clay soil

  6. Kinetic hydrogen isotope effects in the concerted mechanism for the hydrolysis of acetals, ketals, and ortho esters

    International Nuclear Information System (INIS)

    Eliason, R.; Kreevoy, M.M.

    1978-01-01

    The hydrolysis of many ortho esters, and some acetals and ketals, is general acid catalyzed, and in some examples these generate linear Bronsted plots over substantial ranges of catalyst acidity. This suggests that the reaction coordinate is primarily a reorganization of heavy atoms since proton transfer from one oxygen to another has been shown to generate strongly curved Bronsted plots. However, the isotopic fractionation factor for the catalytically active proton in these transition states is substantially less than 1.0; in several examples it is less than 0.5. Such values have been thought to require that the reaction coordinate be largely a motion of the hydrogen giving the low fractionation factor. This dilemma has been resolved by the observation and rationalization of fractionation factors as low as 0.28 for stable, hydrogen bridge-bonded complexes, AHA - . A similar, bounded coordinate is now suggested for the catalytically active protons in question. This permits the reaction coordinate to be pictured. 3 figures, 2 tables

  7. Mass dependent fractionation of stable chromium isotopes in mare basalts: Implications for the formation and the differentiation of the Moon

    Science.gov (United States)

    Bonnand, Pierre; Parkinson, Ian J.; Anand, Mahesh

    2016-02-01

    We present the first stable chromium isotopic data from mare basalts in order to investigate the similarity between the Moon and the Earth's mantle. A double spike technique coupled with MC-ICP-MS measurements was used to analyse 19 mare basalts, comprising high-Ti, low-Ti and KREEP-rich varieties. Chromium isotope ratios (δ53Cr) for mare basalts are positively correlated with indices of magmatic differentiation such as Mg# and Cr concentration which suggests that Cr isotopes were fractionated during magmatic differentiation. Modelling of the results provides evidence that spinel and pyroxene are the main phases controlling the Cr isotopic composition during fractional crystallisation. The most evolved samples have the lightest isotopic compositions, complemented by cumulates that are isotopically heavy. Two hypotheses are proposed to explain this fractionation: (i) equilibrium fractionation where heavy isotopes are preferentially incorporated into the spinel lattice and (ii) a difference in isotopic composition between Cr2+ and Cr3+ in the melt. However, both processes require magmatic temperatures below 1200 °C for appreciable Cr3+ to be present at the low oxygen fugacities found in the Moon (IW -1 to -2 log units). There is no isotopic difference between the most primitive high-Ti, low-Ti and KREEP basalts, which suggest that the sources of these basalts were homogeneous in terms of stable Cr isotopes. The least differentiated sample in our sample set is the low-Ti basalt 12016, characterised by a Cr isotopic composition of -0.222 ± 0.025‰, which is within error of the current BSE value (-0.124 ± 0.101‰). The similarity between the mantles of the Moon and Earth is consistent with a terrestrial origin for a major fraction of the lunar Cr. This similarity also suggests that Cr isotopes were not fractionated by core formation on the Moon.

  8. Ice-liquid isotope fractionation factors for O-18 and H-2 deduced from the isotopic correction constants for the triple point of water

    NARCIS (Netherlands)

    Wang, Xing; Meijer, Harro A. J.

    2018-01-01

    The stable isotopes of water are extensively used as tracers in many fields of research. For this use, it is essential to know the isotope fractionation factors connected to various processes, the most important of which being phase changes. Many experimental studies have been performed on phase

  9. 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

  10. Fractionation of mercury stable isotopes during coal combustion and seawater flue gas desulfurization

    International Nuclear Information System (INIS)

    Huang, Shuyuan; Yuan, Dongxing; Lin, Haiying; Sun, Lumin; Lin, Shanshan

    2017-01-01

    In the current study, fractionation of mercury isotopes during coal combustion and seawater flue gas desulfurization (SFGD) in a coal-fired power plant using a SFGD system was investigated. Fourteen samples were collected from the power plant. The samples were pretreated with a combustion-trapping method and were analyzed with a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS). Compared with the raw coal, the bottom ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −0.45 to −0.03‰. The fly ash was enriched with lighter mercury isotopes with δ 202 Hg values ranging from −1.49 to −0.73‰ for Chinese coal and from −1.47 to −0.62‰ for Indonesian coal. The δ 202 Hg of fresh seawater and desulfurized seawater was found to be −1.32 and −0.32‰ respectively. These δ 202 Hg values indicated that the desulfurized seawater was enriched with heavier mercury isotopes. Based upon the calculated results obtained from the mass balance equation, it was suggested that the stack emissions were enriched with lighter mercury isotopes. Mass independent fractionation was observed in most of the samples with a Δ 199 Hg/Δ 201 Hg ratio of approximately 0.96. The results help in improving the understanding of mercury isotope fractionation during coal combustion and SFGD, and are also useful in tracing the mercury emissions from coal fired power plants. - Highlights: • Spread of 1.5‰ was observed in δ 202 Hg values of raw coals and coal related samples. • The δ 202 Hg values were more negative in fly ash than those in the raw coal. • The flue gas had a significant Hg fractionation after desulfurization. • The stack emissions were enriched with lighter isotopes compared with the raw coal.

  11. Hypoxia induces copper stable isotope fractionation in hepatocellular carcinoma, in a HIF-independent manner.

    Science.gov (United States)

    Bondanese, Victor P; Lamboux, Aline; Simon, Melanie; Lafont, Jérôme E; Albalat, Emmanuelle; Pichat, Sylvain; Vanacker, Jean-Marc; Telouk, Philippe; Balter, Vincent; Oger, Philippe; Albarède, Francis

    2016-11-09

    Hepatocellular carcinoma (HCC) is the most frequent type of primary liver cancer, with increasing incidence worldwide. The unrestrained proliferation of tumour cells leads to tumour hypoxia which in turn promotes cancer aggressiveness. While changes in the concentration of copper (Cu) have long been observed upon cancerization, we have recently reported that the isotopic composition of copper is also altered in several types of cancer. In particular, we showed that in hepatocellular carcinoma, tumour tissue contains heavier copper compared to the surrounding parenchyma. However, the reasons behind such isotopic signature remained elusive. Here we show that hypoxia causes heavy copper enrichment in several human cell lines. We also demonstrate that this effect of hypoxia is pH, HIF-1 and -2 independent. Our data identify a previously unrecognized cellular process associated with hypoxia, and suggests that in vivo tumour hypoxia determines copper isotope fractionation in HCC and other solid cancers.

  12. 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.

  13. Isotopic fractionation of NBS oxalic acid and its influence in the calculated age of materials

    International Nuclear Information System (INIS)

    Nehmi, V.A.

    1979-10-01

    The intensity of the isotopic fractionation during the oxidation of NBS oxalic acid to carbon dioxide was checked. 30 reactions of oxidation of NBS oxalic acid with potassium permanganate were made. The resultant isotopic composition of CO 2 has been determined with a mass-spectrometer. A conclusion has been reached that the average of Δ 13 C is - 18.9% o with variation between - 17.7 and - 21.2%o. For values of Δ 13 C equal to - 22.0%o, the calculated age with isotopic correction shows the following deviations in relation to non-corrected age: 4% for materials of 1,000 years and 0.3% for 20,000 years.(Author) [pt

  14. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Xiaoli [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Environmental Engineering, Quzhou University, Quzhou 324000 (China); Xu, Zemin [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Zhang, Xichang [Laboratory for Teaching in Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Yang, Fangxing, E-mail: fxyang@zju.edu.cn [MOE Key Laboratory of Environmental Remediation and Ecosystem Health, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058 (China); Department of Effect-Directed Analysis, Helmholtz Centre for Environmental Research — UFZ, Leipzig 04318 (Germany)

    2015-11-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰.

  15. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin

    International Nuclear Information System (INIS)

    Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

    2015-01-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2 mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10 mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from − 29.0‰ to − 26.5‰ in soil spiked with 2 mg/kg lambda-cyhalothrin, and to − 27.5‰ with 10 mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as − 2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. - Highlights: • Abiotic and biotic degradation of lambda-cyhalothrin were observed in soil. • Biodegradation of lambda-cyhalothrin was evaluated by CSIA. • Biodegradation of lambda-cyhalothrin leads to carbon isotope fractionation. • An enrichment factor ε of lambda-cyhalothrin was determined as − 2.53‰

  16. Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

    Energy Technology Data Exchange (ETDEWEB)

    Maggi, F.M.; Riley, W.J.

    2009-06-01

    The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O production and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.

  17. Normal and Inverse Diffusive Isotope Fractionation of Deuterated Toluene and Benzene in Aqueous Systems

    DEFF Research Database (Denmark)

    Rolle, Massimo; Jin, Biao

    2017-01-01

    Diffusive isotope fractionation of organic contaminants in aqueous solution is difficult to quantify, and only a few experimental data sets are available for compounds of environmental interest. In this study, we investigate diffusive fractionation of perdeuterated and nondeuterated benzene...... and toluene. Multitracer experiments were carried out in 1-D gel dissection tubes and in a quasi-2-D flow-through porous medium. The experiments allowed us to simultaneously and directly compare the diffusive and dispersive behavior of benzene and toluene. We observed an unexpected, opposite behavior...... of the two monoaromatic hydrocarbons. Toluene showed a normal diffusive isotope effect (DC7D8/DC7H8 = 0.96) with enrichment of the nondeuterated isotopologue in the direction of the diffusive and transverse dispersive fluxes. Conversely, the measured trends for benzene indicate inverse diffusive...

  18. Assessment of diffusive isotopic fractionation in polar firn, and application to ice core trace gas records

    DEFF Research Database (Denmark)

    Buizert, C.; Sowers, T.; Blunier, T.

    2013-01-01

    During rapid variations of the atmospheric mixing ratio of a trace gas, diffusive transport in the porous firn layer atop ice sheets and glaciers alters the isotopic composition of that gas relative to the overlying atmosphere. Records of past atmospheric trace gas isotopic composition from ice...... cores and firn need to be corrected for this diffusive fractionation artifact. We present a novel, semi-empirical method to accurately estimate the magnitude of the diffusive fractionation in the ice core record. Our method (1) consists of a relatively simple analytical calculation; (2) requires only...... commonly available ice core data; (3) is not subject to the uncertainties inherent to estimating the accumulation rate, temperature, close-off depth and depth-diffusivity relationship back in time; (4) does not require knowledge of the true atmospheric variations, but uses the smoothed records obtained...

  19. Assessing the stability of soil organic matter by fractionation and 13C isotope techniques

    Science.gov (United States)

    Larionova, A. A.; Zolotareva, B. N.; Kvitkina, A. K.; Evdokimov, I. V.; Bykhovets, S. S.; Stulin, A. F.; Kuzyakov, Ya. V.; Kudeyarov, V. N.

    2015-02-01

    Carbon pools of different stabilities have been separated from the soil organic matter of agrochernozem and agrogray soil samples. The work has been based on the studies of the natural abundance of the carbon isotope composition by C3-C4 transition using the biokinetic, size-density, and chemical fractionation (6 M HCl hydrolysis) methods. The most stable pools with the minimum content of new carbon have been identified by particle-size and chemical fractionation. The content of carbon in the fine fractions has been found to be close to that in the nonhydrolyzable residue. This pool makes up 65 and 48% of Corg in the agrochernozems and agrogray soils, respectively. The combination of the biokinetic approach with particle-size fractionation or 6 M HCl hydrolysis has allowed assessing the size of the medium-stable organic carbon pool with a turnover time of several years to several decades. The organic matter pool with this turnover rate is usually identified from the variation in the 13C abundance by C3-C4 transition. In the agrochernozems and agrogray soils, the medium-stable carbon pool makes up 35 and 46% of Corg, respectively. The isotope indication may be replaced by a nonisotope method to significantly expand the study of the inert and mediumstable organic matter pools in the geographical aspect, but this requires a comparative analysis of particle-size and chemical fractionation data for all Russian soils.

  20. Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Sera, Shoji; Goromaru, Tsuyoshi [Fukuyama Univ., Hiroshima (Japan). Faculty of Pharmacy and Pharmaceutical Sciences; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

    1998-07-01

    Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT-{sup 2}H{sub 19}), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT-{sup 2}H{sub 10}). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

  1. Isotope dilution analysis for urinary fentanyl and its main metabolite, norfentanyl, in patients by isotopic fractionation using capillary gas chromatography

    International Nuclear Information System (INIS)

    Sera, Shoji; Goromaru, Tsuyoshi; Sameshima, Teruko; Kawasaki, Koichi; Oda, Toshiyuki

    1998-01-01

    Isotope dilution analysis was applied to determine urinary excretion of fentanyl (FT) and its main metabolite, norfentanyl (Nor-FT), by isotopic fractionation using a capillary gas chromatograph equipped with a surface ionization detector (SID). Urinary FT was determined quantitatively in the range of 0.4-40 ng/ml using deuterium labeled FT (FT- 2 H 19 ), as an internal standard. We also performed isotope dilution analysis of Nor-FT in urine. N-Alkylation was necessary to sensitively detect Nor-FT with SID. Methyl derivative was selected from 3 kinds of N-alkyl derivatives to increase sensitivity and peak resolution, and to prevent interference with urinary compound. Nor-FT concentration was quantitatively determined in the range of 10-400 ng/ml using deuterium labeled Nor-FT (Nor-FT- 2 H 10 ). No endogenous compounds or concomitant drugs interfered with the detection of FT and Nor-FT in the urine of patients. The present method will be useful for pharmacokinetic studies and the evaluation of drug interactions in FT metabolism. (author)

  2. Solubility of hydrogen isotopes in stressed hydride-forming metals

    International Nuclear Information System (INIS)

    Coleman, C.E.; Ambler, J.F.R.

    1983-01-01

    Components made from hydride-forming metals can be brittle when particles of hydride are present. The solid solubility limit of hydrogen in these metals needs to be known so that fracture resistance can be properly assessed. Stress affects the solubility of hydrogen in metals. As hydrogen dissolves the metal volume increases, an applied hydrostatic tensile stress supplies work to increase the solubility. Precipitation of hydrides increases the volume further. A hydrostatic tensile stress promotes the formation of hydrides and tends to reduce the terminal solubility. For materials containing hydrogen in solution in equilibrium with hydrides, the effect of stress on the terminal solubility is given. Hydrogen migrates up tensile stress gradients because of the effect of stress on the solubility and solubility limit. Consequently, hydrogen concentrates at flaws. When hydrides are present in the metal matrix, those remote from the flaw tip will preferentially dissolve in favor of those precipitated at the flaw. If the stress is large enough, at some critical condition the hydrides at the flaw will crack. This is delayed hydrogen cracking. Notched and fatigue-cracked cantilever beam specimens (6) (38 x 4 x 3 mm) were machined from the circumferential direction of several cold-worked Zr-2.5 at. % Nb pressure tubes. The chemical compositions had the ranges (in atomic %) Nb - 2.5 to 2.7; O - 0.58 to 0.71; H - 0.018 to 0.18. The effect of test temperature is for a specimen containing 0.13 at. % protium and 0.29 at .% deuterium. Between 505 K and 530 K was less than 1 hr, between 530 K and 537 K it increased to 25.8 h, while at 538 K no cracking was observed up to the 54 h

  3. A calculation of the surface recombination rate constant for hydrogen isotopes on metals

    International Nuclear Information System (INIS)

    Baskes, M.J.

    1980-01-01

    The surface recombination rate constant for hydrogen isotopes on a metal has been calculated using a simple model whose parameters may be determined by direct experimental measurements. Using the experimental values for hydrogen diffusivity, solubility, and sticking coefficient at zero surface coverage a reasonable prediction of the surface recombination constant may be made. The calculated recombination constant is in excellent agreement with experiment for bcc iron. A heuristic argument is developed which, along with the rate constant calculation, shows that surface recombination is important in those metals in which hydrogen has an exothermic heat of solution. (orig.)

  4. Stable carbon isotope fractionation during the biodegradation of lambda-cyhalothrin.

    Science.gov (United States)

    Shen, Xiaoli; Xu, Zemin; Zhang, Xichang; Yang, Fangxing

    2015-11-01

    In this study, the microbial degradation of lambda-cyhalothrin in soil was investigated using compound-specific stable isotope analysis. The results revealed that lambda-cyhalothrin was biodegraded in soil under laboratory conditions. The half-lives of lambda-cyhalothrin were determined to be 49 and 161 days in non-sterile and sterile soils spiked with 2mg/kg lambda-cyhalothrin and 84 and 154 days in non-sterile and sterile soils spiked with 10mg/kg lambda-cyhalothrin, respectively. The biodegradation of lambda-cyhalothrin resulted in carbon isotope fractionation, which shifted from -29.0‰ to -26.5‰ in soil spiked with 2mg/kg lambda-cyhalothrin, and to -27.5‰ with 10mg/kg lambda-cyhalothrin. A relationship was established between the stable carbon isotope fraction and the residual concentrations of lambda-cyhalothrin by the Rayleigh equation in which the carbon isotope enrichment factor ε of the microbial degradation of lambda-cyhalothrin in the soil was calculated as -2.53‰. This study provides an approach to quantitatively evaluate the biodegradation of lambda-cyhalothrin in soil in field studies. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. 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.

  6. Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes.

    Science.gov (United States)

    Babcsányi, Izabella; Chabaux, François; Granet, Mathieu; Meite, Fatima; Payraudeau, Sylvain; Duplay, Joëlle; Imfeld, Gwenaël

    2016-07-01

    Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Constraining calcium isotope fractionation (δ44/40Ca) in modern and fossil scleractinian coral skeleton

    OpenAIRE

    Pretet, Chloé; Samankassou, Elias; Felis, Thomas; Reynaud, Stéphanie; Böhm, Florian; Eisenhauer, Anton; Ferrier-Pagès, Christine; Gattuso, Jean-Pierre; Camoin, Gilbert

    2013-01-01

    The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (δ44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the δ44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals f...

  8. Model for the isotopic fractionation of water in the Amazon basin

    International Nuclear Information System (INIS)

    Dall'Olio, A.; Azevedo, C.T. de

    1979-01-01

    Two models on the isotopic fractionation of water are presented. In the first model. It is assumed that the only source of water vapour for the Amazon region is the Atlantic Ocean, introduced by the predominant easterly winds. The second model contains the assumption that the forest also serves as a source of water vapour contributing an equal volume of water to the regional rains as the vapour of oceanic origin. (Author) [pt

  9. 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...

  10. Studies on the magnetic after-effect of hydrogen isotopes in hexagonal crystals

    International Nuclear Information System (INIS)

    Herbst, G.

    1979-01-01

    The behaviour of hydrogen isotopes in hexagonal gadolinium, in intermetallic compounds of the RECo 5 type (RE = rare earth metal), and in cobalt alloys with small concentrations of alloyed impurity atoms was studied using the magnetic after-effect method in the temperature range between 4.2 K and 300 K. (orig./WBU) [de

  11. Multi-saline sample distillation apparatus for hydrogen isotope analyses : design and accuracy

    Science.gov (United States)

    Hassan, Afifa Afifi

    1981-01-01

    A distillation apparatus for saline water samples was designed and tested. Six samples may be distilled simultaneously. The temperature was maintained at 400 C to ensure complete dehydration of the precipitating salts. Consequently, the error in the measured ratio of stable hydrogen isotopes resulting from incomplete dehydration of hydrated salts during distillation was eliminated. (USGS)

  12. Isotopic and spin-nuclear effects in solid hydrogens (Review Article)

    Science.gov (United States)

    Freiman, Yuri A.; Crespo, Yanier

    2017-12-01

    The multiple isotopic family of hydrogens (H2, HD, D2, HT, DT, T2) due to large differences in the de Boer quantum parameter and inertia moments displays a diversity of pronounced quantum isotopic solid-state effects. The homonuclear members of this family (H2, D2, T2) due to the permutation symmetry are subjects of the constraints of quantum mechanics which link the possible rotational states of these molecules to their total nuclear spin giving rise to the existence of two spin-nuclear modifications, ortho- and parahydrogens, possessing substantially different properties. Consequently, hydrogen solids present an unique opportunity for studying both isotope and spin-nuclear effects. The rotational spectra of heteronuclear hydrogens (HD, HT, DT) are free from limitations imposed by the permutation symmetry. As a result, the ground state of these species in solid state is virtually degenerate. The most dramatic consequence of this fact is an effect similar to the Pomeranchuk effect in 3He which in the case of the solid heteronuclear hydrogens manifests itself as the reentrant broken symmetry phase transitions. In this review article we discuss thermodynamic and kinetic effects pertaining to different isotopic and spin-nuclear species, as well as problems that still remain to be solved.

  13. 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.

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

    NARCIS (Netherlands)

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

    2013-01-01

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

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

    NARCIS (Netherlands)

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

    2013-01-01

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

  16. Mercury isotope fractionation during transfer from post-desulfurized seawater to air.

    Science.gov (United States)

    Huang, Shuyuan; Lin, Kunning; Yuan, Dongxing; Gao, Yaqin; Sun, Lumin

    2016-12-15

    Samples of dissolved gaseous mercury (DGM) in the post-desulfurized seawater discharged from a coal-fired power plant together with samples of gaseous elemental mercury (GEM) over the post-desulfurized seawater surface were collected and analyzed to study the mercury isotope fractionation during transfer from post-desulfurized seawater to air. Experimental results showed that when DGM in the seawater was converted to GEM in the air, the δ 202 Hg and Δ 199 Hg values were changed, ranging from -2.98 to -0.04‰ and from -0.31 to 0.64‰, respectively. Aeration played a key role in accelerating the transformation of DGM to GEM, and resulted in light mercury isotopes being more likely to be enriched in the GEM. The ratio Δ 199 Hg/Δ 201 Hg was 1.626 in all samples, suggesting that mercury mass independent fractionation occurred owing to the nuclear volume effect during the transformation. In addition, mass independent fractionation of mercury even isotopes was found in the GEM above the post-desulfurized seawater surface in the aeration pool. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Water containing deuterium electrolysis to obtain gaseous hydrogen isotope in a high state of purity

    International Nuclear Information System (INIS)

    Bellanger, Gilbert

    1992-01-01

    In this paper, the basic concept is to prepare hydrogen in a high state of purity by electrolysing water using a palladium cathode. During electrolysis, hydrogen is at first adsorbed at the palladium surface, and next it diffuses through it till opposite face of its entry where it is desorbed; thus permitting to regain it in a very pure state for storage. The method can be used from water containing deuterium. To improve hydrogen adsorption, surface effect of palladium must be studied. It was found that heat treatment of palladium improved the hydrogen permeation flux. The diffusivity of hydrogen is controlled by Fick and Sieverts equations in which temperature has a significant influence on permeation rates. Anyway, hydrogen desorption does not cause any difficulty. In a second part, we have studied the isotopic separation factor using water containing deuterium. We remarked in fact that it depends on current density, overpotential, diffusivity of hydrogen and deuterium and isotopic composition of electrolyte as expected. In the last part, we realized an original electrolysis model in a glove-box in which are taken into account the results given before and also the technology components employed in processes involving the use of tritium. (author) [fr

  18. The high pressure equation of state of the isotopes of solid hydrogen and helium

    International Nuclear Information System (INIS)

    Driessen, A.

    1982-01-01

    The initial aim of this thesis was to provide the high pressure equipment and the knowledge about the equation of state (EOS) necessary for a research program in a laboratory dealing with spectroscopy of solid hydrogen under high pressure. Once this first goal was reached, a logical step was to extend the work on the EOS to all three hydrogen isotopes and later also to the helium isotpes. During the experiments on the EOS of hydrogen, the effects of the concentration C 1 of the rotationally excited molecules provoked interest, resulting in an extensive experimental and theoretical study. Chapter I describes the results and experience with high pressure equipment for hydrogen up to 7 kbar and chapter II gives a short general introduction to the calculation of the EOS by introducing the Mie-Grueneisen picture and the Silvera-Goldman (SG) potential for hydrogen. Chapter III gives the results of the first EOS of H 2 and D 2 and chapter IV gives a prediction of the EOS of solid T 2 with aid of the SG potential and the experimental results of H 2 and D 2 . Chapter V presents calculations on the thermal expansion of the hydrogen isotopes, which are compared with direct experiments and chapter VI deals in detail with the influence of C 1 on the EOS of H 2 . Ortho-para conversion in hydrogen is considered in chapter VII, and chapter VIII describes experiments on 4 He. (Auth.)

  19. Ion fractions in the scattering of hydrogen on silicon surfaces

    International Nuclear Information System (INIS)

    Garcia, Evelina A.; Gonzalez Pascual, C.; Bolcatto, P.G.; Passeggi, M.C.G.; Goldberg, E.C.

    2005-01-01

    We present a theoretical calculation of the resonant charge-exchange process occurring in H 0 scattering by Si(100)2 x 1 surfaces. In the atom-surface interacting system the core states of the surface atoms are included and the parameters of the Hamiltonian are calculated in an ab initio basis taking into account the extended features of the surface and the localized atom-atom interactions within a mean-field approximation. The density of states of the surface and sub-surface atoms are obtained from a molecular dynamic-density functional theory in the local density approximation. An elastic binary collision is assumed to fix the projectile trajectory, while the inelastic processes are determined by the interaction of the projectile atom with all the surface atoms 'seen' along its trajectory. The ion fractions are calculated by using the Green-Keldysh formalism to solve the time dependent process. The results, obtained as an average over different possibilities for the scattering center, reproduce the general trends of the experiment. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

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

    Science.gov (United States)

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

    2017-12-01

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

  1. Chromatographic measurement of hydrogen isotopic and permanent gas impurities in tritium

    International Nuclear Information System (INIS)

    Warner, D.K.; Kinard, C.; Bohl, D.C.

    1976-01-01

    This paper describes a gas chromatograph that was designed for dedicated analysis of hydrogen isotopic and permanent gas impurities in tritium and tritium-deuterium mixtures. The instrument that was developed substantially improved the accuracy and precision of hydrogen isotopic analysis in the 20 ppM to one mole percent range as compared with other analytical methods. Several unique design features of the instrument were required due to the radiation and isotopic exchange properties of the tritium in the samples; descriptions of these features are presented along with details of the complete chromatographic system. The experimental procedures used to calibrate the detector and statistically evaluate its performance are given, and the sources of analytical error are cited. The limitations of the present system are also discussed

  2. 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

  3. Silicon isotope fractionation during silica precipitation from hot-spring waters

    Science.gov (United States)

    Geilert, Sonja; Vroon, Pieter; Keller, Nicole; Gudbrnadsson, Snorri; Stefánsson, Andri; van Bergen, Manfred

    2014-05-01

    Hot-spring systems in the Geysir geothermal area, Iceland, have been studied to explore silicon isotope fractionation in a natural setting where sinter deposits are actively formed over a temperature interval between 20° and 100° C. The SiO2(aq)concentrations in spring and stream waters range between 290 and 560ppm and stay relatively constant along downstream trajectories, irrespective of significant cooling gradients. The waters are predominantly oversaturated in amorphous silica at the temperatures measured in the field. Correlations between the saturation indices, temperature and amounts of evaporative water loss suggest that cooling and evaporation are the main causes of subaqueous silica precipitation. The δ30Si values of dissolved silica in spring water and outflowing streams average around +1o probably due to the small quantities of instantaneously precipitating silica relative to the dissolved amount. Siliceous sinters, in contrast, range between -0.1o to -4.0o consistent with a preferred incorporation of the light silicon isotope and with values for precipitated silica becoming more negative with downstream decreasing temperatures. Larger fractionation magnitudes are inversely correlated with the precipitation rate, which itself is dependent on temperature, saturation state and the extent of a system. The resulting magnitudes of solid-fluid isotopic fractionation generally decline from -3.5o at 10° C to -2.0o at 90° C. These values confirm a similar relationship between fractionation magnitude and temperature that we found in laboratory-controlled silica-precipitation experiments. However, a relatively constant offset of ca. -2.9o between field and experimental fractionation values indicates that temperature alone cannot be responsible for the observed shifts. We infer that precipitation kinetics are a prominent control of silicon isotope fractionation in aqueous environments, whereby the influence of the extent of the system on the precipitation

  4. Impurity effects of hydrogen isotope retention on boronized wall in LHD

    International Nuclear Information System (INIS)

    Oya, Yasuhisa; Okuno, Kenji; Ashikawa, Naoko; Nishimura, Kiyohiko; Sagara, Akio

    2010-11-01

    The impurity effect on hydrogen isotopes retention in the boron film deposited in LHD was evaluated by means of XPS and TDS. It was found that the impurity concentrations in boron film were increased after H-H main plasma exposure in LHD. The ratio of hydrogen retention trapped by impurity to total hydrogen retention during H-H main plasma exposure was reached to 70%, although that of deuterium retention by impurity in D 2 + implanted LHD-boron film was about 35%. In addition, the dynamic chemical sputtering of hydrogen isotopes with impurity as the form of water and / or hydrocarbons was occurred by energetic hydrogen isotopes irradiation. It was expected that the enhancement of impurity concentration during plasma exposure in LHD would induce the dynamic formation of volatile molecules and their re-emission to plasma. These facts would prevent stable plasma operation in LHD, concluding that the dynamic impurity behavior in boron film during plasma exposure is one of key issues for the steady-state plasma operation in LHD. (author)

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  6. Chemically modified glasses for analysis of hydrogen isotopes by gas-chromatography

    International Nuclear Information System (INIS)

    Stanciu, Vasile; Stefanescu, Doina

    1999-01-01

    Hydrogen isotope separation process by such methods as cryogenic distillation or thermal diffusion method is one of the key technologies of the tritium separation from heavy water of CANDU reactors and in the tritium fuel cycle for a thermonuclear fusion reactor. In each process, the analytical techniques for measuring contents of hydrogen isotope mixture are necessary. An extensive experimental research has been carried out in order to produce the most suitable absorbent and define the best operating conditions for selective separation and analysis of hydrogen isotope by gas-chromatography. This paper describes the preparation of adsorbent materials utilised as stationary phase in the gas-chromatographic column for hydrogen isotope separation and treatment (activation) of stationary phase. Modified thermo-resisting glass with Fe(NH 4 ) 2 (SO 4 ) 2 6H 2 O and Cr 2 O 3 , respectively, have been experimentally investigated at 77 K for H 2 , HD and D 2 separation and the results of chromatographic runs are also reported and discussed. The gas-chromatographic apparatus used is composed of a Hewlett-Packard 7620A gas-chromatograph equipped with a gas carrier flow rate controller and a thermal conductivity detector (TCD). The apparatus comprises also a Dewar vessel containing the separation column. The hydrogen isotopes H 2 , HD, D 2 and their mixture have been obtained in our laboratories. The best operating conditions of the adsorbent column Fe (III)/glass and Cr 2 O 3 /glass, i.e. granulometry, column length, pressure-drop along the column, carrier gas flow rate, sample volume have been studied by means of the analysis of the retention times, separation factors and HETP. (authors)

  7. Metal/glass composites for analysis of hydrogen isotopes by gas-chromatography

    International Nuclear Information System (INIS)

    Nicolae, Constantin Adrian; Sisu, Claudia; Stefanescu, Doina; Stanciu, Vasile

    1999-01-01

    The separation process of hydrogen isotopes by cryogenic distillation or thermal diffusion is a key technology for tritium separation from heavy water in CANDU reactor and for tritium fuel cycle in thermonuclear fusion reactor. In each process, analytical techniques for analyzing the hydrogen isotope mixture are required. An extensive experimental research has been carried out in order to produce the most suitable adsorbents and to establish the best operating conditions for selective separation and analysis of hydrogen isotopes by gas-chromatography. This paper describes the preparation of adsorbent materials used as stationary phases in the gas-chromatographic column for hydrogen isotope separation and the treatment (activation) of stationary phases. Modified thermoresisting glass with Fe(NH 4 ) 2 (SO 4 ) 2 ·6H 2 O and Cr 2 O 3 respectively have been experimentally investigated at 77 K for H 2 , HD and D 2 separation and the results of chromatographic runs are reported and discussed. The gas-chromatographic apparatus used in this study is composed of a Hewlett-Packard 7620A gas-chromatograph equipped with a gas carrier flow rate controller and a thermal conductivity detector. The apparatus comprises also a Dewar vessel containing the separation column. The hydrogen isotopes, H 2 , HD, D 2 , and their mixture have been obtained in our laboratories. The best operating conditions and parameters of the Fe 3+ /glass adsorbent column , i.e. granulometry, column length, pressure-drop along the column, carrier gas flow rate and sample volume have been studied by means of the analysis of the retention times, separation factors and HETP. (authors)

  8. Hydrogen isotope storage behavior of Zr1-xTixCo alloys

    International Nuclear Information System (INIS)

    Jat, Ram Avtar; Pati, Subhasis; Parida, S.C.; Agarwal, Renu; Mukerjee, S.K.

    2016-01-01

    Tritium storage properties similar to uranium make ZrCo as a suitable candidate material for storage, supply and recovery of hydrogen isotopes in various tritium facilities. Beside non-radioactive, nonpyrophoric at room temperature and higher storage capacity (H/f.u. up to 3, f.u. = ZrCo), it has been reported that upon repeated hydriding-dehydriding cycles, ZrCo undergoes dis-proportionation as per the reaction; ZrCo + H 2 ↔ ZrH 2 + ZrCo 2 . The present study is aimed to investigate the effect of Ti content on the hydrogen storage behavior of Zr 1-x Ti x Co alloys and the hydrogen isotope effect

  9. Equation-of-state for fluids at high densities-hydrogen isotope measurements and thermodynamic derivations

    International Nuclear Information System (INIS)

    Liebenberg, D.H.; Mills, R.L.; Bronson, J.C.

    1977-01-01

    Hydrogen isotopes play an important role in energy technologies, in particular, the compression to high densities for initiation of controlled thermonuclear fusion energy. At high densities the properties of the compressed hydrogen isotopes depart drastically from ideal thermodynamic predictions. The measurement of accurate data including the author's own recent measurements of n-H 2 and n-D 2 in the range 75 to 300 K and 0.2 to 2.0 GPa (2 to 20 kbar) is reviewed. An equation-of-state of the Benedict type is fit to these data with a double-process least-squares computer program. The results are reviewed and compared with existing data and with a variety of theoretical work reported for fluid hydrogens. A new heuristic correlation is presented for simplicity in predicting volumes and sound velocity at high pressures. 9 figures, 1 table

  10. Mercury stable isotope fractionation in a tropical ecosystem including human hair: New insights for an isotope balance

    Science.gov (United States)

    Laffont, Laure; Sonke, Jeroen; Maurice, Laurence; Behra, Philippe

    2010-05-01

    Mercury contamination is an environmental problem in the Amazon basin still relevant today as impacts on human health are poorly studied. In Bolivia, indigenous people have elevated methylmercury concentrations (between 2719 and 23701 ng.g-1) in their hair. This highly toxic molecule is formed after methylation of inorganic Hg released by chemical and physical weathering and from human activities. The aim of our study is to propose a first isotope balance in a Bolivian Amazon ecosystem, through variations in Hg isotopic compositions. The discovery of mass-independent fracionation (MIF) of odd-isotopes in our organic samples (fish and human hair) opened a new way of research in tracing the sources and the processes involved in the cycle of Hg. Four types of samples are studied: liquid Hg0 from gold mining, sediment samples, fish coming from the Beni River basin (from the main channel and an associated floodplain lake) and hair from gold miners and fish-eating native populations. Hg isotopic compositions were analyzed on a Thermo-Finnigan Neptune MC-ICP-MS at the LMTG after sample digestion by HCl/HNO3 or by H2O2/HNO3 for fish samples, at 120°C. The δ202Hg values (relative to NIST 3133) are signicantly different with respect to the external precision on UM-Almaden#2 of 0.18 ‰ (2σ, n = 42): -0.34 ± 0.02 ‰ for liquid mercury, between -1.33 and -0.81 ‰ for bottom and floodplain sediments (n=18), between -0.87 and 2.22 ‰ for miners hair (n=26), +1.29 ± 0.41 ‰ for native hair (n=13) and between -0.91 and -0.21 ‰ for fish samples (n=53). A large mass-independent isotope fractionation (MIF) was observed for odd isotope ratios in all hair samples and fish samples whereas weak anomalies were measured for sediment samples: - ∆199Hg anomaly: -0.12 to -0.04 ‰ for sediment, -0.22 to +0.63 ‰ for fish samples and +0.13 to +1.63 ‰ for hair - ∆201Hg anomaly: -0.12 to -0.02 ‰ for sediment, -0.21 to +0.43 ‰ for fish samples and +0.06 to +1.25 ‰ for hair

  11. Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

    Science.gov (United States)

    Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

    2006-12-01

    The isotopic